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Conference Handbook

5-8 DECEMBER 2016

www.imstec.com.au

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• Water Technologies Pty Ltd



1300 661 809

CO-CONVENORS Professor Amanda Ellis Flinders University Dr Milena Ginic-Markovic University of South Australia

CONFERENCE COMMITTEE Associate Professor Sophie Leterme Flinders University Professor Namita Choudhury University of South Australia Associate Professor Sheng Dai University of Adelaide Hiep Le Osmoflo Professor Mikel Duke Victoria University

Contents Welcome 4 General Information 6

PROGRAM

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Conference Program

PROGRAM PLUS 25 Workshop 26 Social Program 27 SPEAKERS

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Professor Huanting Wang Monash University

ABSTRACTS

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Associate Professor Ho Kyong Shon University of Technology Sydney

POSTERS

Dr Dharma Dharmabalan TasWater

Dr Manh Hoang CSIRO Associate Professor Pierre Le-Clech University of NSW Professor Matthew Hill CSIRO

491

SPONSORS & EXHIBITORS

581 Sponsors 582 Conference Floor Plan 587 Trade Exhibitors 588

Aaron Thornton CSIRO Dr Andrew Groth Siemens Water Technologies

INTERNATIONAL ORGANISING COMMITTEE Professor Tony Fane Nanyang Technological University Dr Emile Cornelissen KWR, The Netherlands Mike Dixon Alberta WaterSMART Professor Linda Zou Masdar Institute of Science & Technology Professor Suzana Periera Nunes KAUST Dr.-Ing. Matthias Wessling RWTH Aachen Neil Palmer NCEDA/Murdoch University

CONFERENCE MANAGERS Leishman Associates 113 Harrington Street, Hobart TAS 7000 170 Elgin Street, Carlton VIC 3053 P. 03 6234 7844 F. 03 6234 5958 E. [email protected] W. leishman-associates.com.au GOLD SPONSOR

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Welcome

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

On behalf of the Membrane Society of Australasia (MSA), it is our pleasure to welcome you The Organising Committee extends a warm welcome to all radiation safety professionals, to the 9th International Membrane Science and Technology Conference at the Adelaide enthusiasts, students, supporting suppliers, businesses and related industries to participate Convention Centre, South Australia. in the 41st Annual Conference of the Australasian Radiation Protection Society. We would like to acknowledge the presenters who have travelled from many parts of the The 2016 ARPS Conference is being held in South Australia at a time of significant globe to attend this conference. It truly is an international event. community debate centred on risks and opportunities presented by a proposed During the conference we willfuel discuss all areas of inorganic membranes, expanded role in the nuclear cycle, particularly in relation to the longpolymeric term membranes, membrane science, membrane fabrication and modification, and management of radioactive wastes. The South Australian Government will be considering membrane applications in a broad variety of areas such as filtration, distillation, the findings handed down by the Nuclear Fuel Cycle Royal Commission, and work will desalination anddevelopment biological separations. Included willRadioactive be engineering and technologies increase on the of Australia’s National Waste Management from the latest innovations in synthesis, characterisation, processing and modeling toand the Facility. Both processes have generated much public discussion and public scrutiny advanced applications of membranes in health, energy and sustainability as well as future will continue to do so. The Management, Storage and Disposal of Radioactive Waste materials devices.will explore these issues with the expertise of our international and Technical and Symposium national speakers. As in past years IMSTEC will provide an opportunity for national and international networking through an theme exciting of both Risks formal presentations as well This year’s conference is forum “Perceptions, and Opportunities”. Theas theme is broad enhancement of and research in at order to contribute towards development of frontier and challenging aimed generating discussion andthe debate about good science membrane science.in radiation protection, including how we can influence perceptions and good practice and contribute effectively to government and community understanding and decisionWe hope you enjoy the conference, are inspired by new ideas and make new friends. making. I welcome you to Adelaide and hope that you enjoy the program that has been We look forward to meeting you over the next few days. assembled and take the opportunity to have strong and healthy discussions with Professor Amanda Ellis professional colleagues. Dr Milena Ginic-Markovic Ian Furness MARPS Co-Convenors ARPS 2016 Conference Convenor

GOLD SPONSOR

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GENERAL INFORMATION

REGISTRATION DESK

CONFERENCE NAME BADGES

The Registration Desk is located at the Adelaide Convention Centre in the Panorama Foyer. Please direct any questions you may have regarding the conference to the staff from Leishman Associates. The registration desk will be open at the following times:

All delegates and exhibitors will be provided with a name badge, please wear your name badge at all times as it will be your entry into all sessions and all social functions.

Monday 5 December

0800-1800

Tuesday 6 December

0800-1800

DRESS CODE The dress code for the conference sessions and social functions is smart casual.

Wednesday 7 December 0815-1800 Thursday 8 December

0815-1600

ACCOMMODATION If you have any queries relating to your accommodation booking, please first see the staff at your hotel. Your credit card details have been passed onto the hotel to secure your booking. If you have arrived 24 hours later than your indicated arrival day you may find that you have been charged one nights accommodation.

SPECIAL DIETS All catering venues have been advised of any special diet preferences you have indicated on your registration form. Please identify yourself to venue staff as they come to serve you and they will be pleased to provide you with all pre-ordered food. For day catering, there may be a specific area where special food is brought out, please check with catering or the Leishman team.

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ENTRY TO CONFERENCE SESSIONS It is suggested that delegates arrive at preferred sessions promptly to ensure a seat. If sessions become full then delegates will not be allowed entry.

ENTRY TO SOCIAL EVENTS Entry to social events will not require a ticket. Attendees and additional guests will appear on a guest list and must wear a name badge. If you are unsure about whether you are registered, please see the staff at registration.

WIFI Delegates have access to complimentary WIFI for the duration of the conference.

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

GENERAL INFORMATION

PHOTOGRAPHS, VIDEOS & RECORDING

DISCLAIMER

Delegates are not permitted to use any type of camera or recording device at any of the sessions unless written permission has been obtained from the relevant speaker.

MOBILE PHONES

The 2016 IMSTEC reserves the right to amend or alter any advertised details relating to dates, program and speakers if necessary, without notice, as a result of circumstances beyond their control. All attempts have been made to keep any changes to an absolute minimum.

As a courtesy to other delegates, please ensure that all mobile phones are turned off or in a silent mode during all sessions and social functions.

OCTOBER 15-20, 2017 WORLD TRADE CENTER SÃO PAULO SÃO PAULO, BRAZIL „ „ „ „ „ „

Robust Technical Programs Industry Leading Exhibition Panel Discussions Achievement Awards Networking Opportunities Educational Training Programs

Who Should Attend: IDA’s World Congress brings together stakeholders from all parts of the global desalination and water reuse industry, including end users (utilities), researchers, consultants, members of academia, manufacturers and suppliers of complete systems and components including chemicals and materials.

IDA’s World Congress is the premier water reuse and desalination event where global water industry leaders converge to network and exchange ideas that will shape the future of water solutions. Join us in São Paulo, a vibrant cosmopolitan city and one of the largest and most influential financial centers of Latin America. Discover this city of contrasts – from the arts, to restaurants and national parks, to shopping, nightlife, and diverse cultural experiences – São Paulo is in a league of its own. Organizer

wc.idadesal.org

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Representatives from Governmental, Financial, Development and Multilateral Agencies and Corporations are also welcome and will find participation worthwhile.

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Supporting Affiliate

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1300 661 809

PROGRAM

GOLD SPONSOR

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PROGRAM

MONDAY 5 DECEMBER 2016 0800

Registration Desk Open

0900-1600 WORKSHOP 1

Sponsored by

MEMBRANES IN MINING 0900-1600 WORKSHOP 2

Sponsored by

EARLY CAREER RESEARCHERS FORUM 1700-1710 WELCOME TO THE 9TH IMSTEC PLENARY SESSION Chair: Amanda Ellis 1710-1810 PLENARY PRESENTATION

Sponsored by

Professor Sandra Kentish MULTICOMPONENT GAS SEPARATION – THE IMPORTANCE OF IMPURITIES IN FLUE GAS CAPTURE 1810-2000 WELCOME RECEPTION

Sponsored by

RIVERBANK PROMENADE, ADELAIDE CONVENTION CENTRE

Join us on the outside deck overlooking the River Torrens

Crossing Barriers

The Future Industries Institute and Membrane Research With its eye on building knowledge and capability to grow the industries of the future, the University of South Australia (UniSA) launched a new multi-million dollar research institute at its Mawson Lakes campus. The Future Industries Institute (FII) develops UniSA’s internationally competitive research capacity in: • minerals and resources engineering • energy and advanced manufacturing • environmental science and engineering • biomaterials engineering and nanomedicine. FII represents UniSA’s largest single investment in research and forges national and global research partnerships in new technologies. It is home to the Future Industries Accelerator program, which puts the Institute at the vanguard of university/industry collaboration. Visit unisa.edu.au/fii

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

CRICOS number 00121B

Future Industries Institute

PROGRAM

TUESDAY 6 DECEMBER 2016 0800

Registration Desk Open PLENARY SESSION Chair: Aaron Thornton

0900-0910 Welcome and Housekeeping 0910-1000 PLENARY PRESENTATION

Sponsored by

Professor Benny Freeman ION SORPTION, DIFFUSION AND TRANSPORT IN CHARGED POLYMER MEMBRANES 1000-1030 Morning Refreshments & Trade Exhibition THEME: GAS SEPARATIONS PANORAMA 1

Chair: Matthew Hill

THEME: NOVEL MATERIALS AND SURFACE MODIFICATIONS PANORAMA 2

THEME: WINE, FOOD AND DAIRY APPLICATION PANORAMA 3

THEME: WATER AND WASTE WATER TREATMENT CITY 1

Chair: Mikel Duke

Chair: Stephen Gray

KEYNOTE PRESENTATION

INVITED PRESENTATION

KEYNOTE PRESENTATION

T2.1

T3.1

T4.1

Associate Professor Ken Morison

Professor Matthias Wessling

MEMBRANE PREPARATION FROM SOLUTIONS IN IONIC LIQUIDS

MEMBRANES IN DAIRY, JUICE AND BEVERAGE PROCESSING

FUNDAMENTALS OF SOFT MATTER MEMBRANE FILTRATION

T2.2

T3.2

T4.2

IMPROVING ANTIFOULING PROPERTIES OF CERAMIC MEMBRANES VIA SURFACE MODIFICATION

ION TRANSPORT MODELLING IN MEMBRANE CAPACITIVE DEIONISATION

Jongman Lee

PROTEIN RECOVERY FROM POTATO PROCESSING WATER: FOULING MINIMIZATION AND FUNCTIONAL PROPERTIES OF RECOVERED PROTEIN

T2.3

T3.3

T4.3

DESIGN AND FABRICATION OF SUPERHYDROPHILIC THIN FILM COMPOSITE NANOFIBROUS MEMBRANES FOR RECALCITRANT ORGANICS REMOVAL IN AN EXTRACTIVE MEMBRANE BIOREACTOR PROCESS

THE CHALLENGES OF EFFLUENT TREATMENT IN THE DAIRY INDUSTRY

FORWARD OSMOSIS FOR PHOSPHORUS RECOVERY FROM WASTEWATER

Chair: Mainak Majumder 1030-1100 KEYNOTE PRESENTATION T1.1

Professor Ingo Pinnau Professor Suzana Nunes FUNCTIONALIZED POLYMERS OF INTRINSIC MICROPOROSITY FOR HIGHLY ENERGYINTENSIVE GAS SEPARATIONS

1100-1115 T1.2 IDENTIFYING OPTIMAL MEMBRANE MATERIALS AND PROCESS CONFIGURATIONS FOR GAS SEPARATION Burkhard Ohs

1115-1130 T1.3 STOPPING PHYSICAL AGING IN GLASSY POLYMERS FOR EXCEPTIONAL SEPARATION PERFORMANCE Matthew Hill

Armineh Hassanvand

Shirin Dabestani

George Chen

Katie Charlotte Kedwell

Yuan Liao

GOLD SPONSOR

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PROGRAM

1130-1145 T1.4 UPGRADING SEWAGE SLUDGE DIGESTION GAS QUALITY USING THE MEMBRANE SEPARATION METHOD Asami Saito

T2.4

T3.4

T4.4

APPLICATION AND STABILITY OF LAYER-BY-LAYER MODIFIED MEMBRANES IN ACIDIC ENVIRONMENT FOR PHOSPHORUS RECOVERY

VIBRATING HOLLOW FIBRE MEMBRANE SYSTEM FOR MILK PROTEIN SEPARATION AND CONCENTRATION

HYDROPHILIC MICROFIBER-POLYMER HYDROGEL MONOLITH AS FORWARD OSMOSIS DRAW AGENT

Milton Chai

Ranwen Ou

T2.5

T3.5

T4.5

BIO-INSPIRED MEMBRANE SURFACE WITH PEI/PDA ASSISTED MINERALIZATION FOR SUPERHYDROPHOBIC MODIFICATION

VISUALIZATION OF PORE MEMCOR® CPII UF BLOCKING WITH THE MEMBRANE FOR ‘CLOGGOTRON’ SECONDARY EFFLUENT TREATMENT AT ULU Ties van de Laar PANDAN WATER RECLAMATION PLANT

Kirsten Remmen 1145-1200 T1.5 GAS SEPARATION OF STEELMAKING EMISSIONS WITH COMMERCIAL POLYMERIC DENSE MEMBRANES FOR GAS VALORIZATION AND CARBON FOOTPRINT REDUCTION: PROCESS DESIGN, LABORATORY TEST RESULTS, AND PERSPECTIVES FOR PILOT PLANT TRIALS

Wenwei Zhong

Steven Cao

Alvaro Ramirez Santos 1200-1215 T1.6 MEMBRANE CONTACTOR WITH HIGH CO2/AMINE SELECTIVITY: A VIABLE SOLUTION FOR THE USE OF ENERGY-EFFICIENT CO2 ABSORBENTS WITH HIGH VOLATILITY

T2.6

T3.6

T4.6

ULTRATHIN MUSSELINSPIRED SOLVENT RESISTANT NANOFILTRATION MEMBRANES

ARE POLYDOPAMINE MODIFIED FILTRATION MEMBRANES DURABLE ENOUGH FOR DAIRY PROCESSING?

PHYSICS BEHIND WATER TRANSPORT THROUGH NANOPOROUS GRAPHENE AND BORON NITRIDE

Liliana PerezManriquez

Thomas Barclay

Anthony Szymczyk

T2.7

T3.7

T4.7

DEVELOPMENT OF A NEW ULTRAFILTRATION MEMBRANE WITH LOW ADHESIVE SURFACE FOR DIRECT PRETREATMENT OF SEAWATER: BENCH SCALE AND PILOT STUDIES

MASS TRANSPORT ANALYSIS AND MEMBRANE CHARACTERIZATION FOR THE PRO AND FO PROCESSES

EFFECT OF INITIAL FEED AND DRAW FLOWRATES ON THE PERFORMANCE OF AN 8040 SPIRALWOUND FORWARD OSMOSIS MEMBRANE ELEMENT

Luca Ansaloni 1215-1230 T1.7 POLYMER-FLUORINATED SILICA COMPOSITE HOLLOW FIBER MEMBRANES FOR THE RECOVERY OF BIOGAS DISSOLVED IN ANAEROBIC EFFLUENT Sunee Wongchitphimon

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Endre Nagy

Seungho Kook

Emmanuelle Filloux

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PROGRAM

1230-1300 INVITED PRESENTATION

INVITED PRESENTATION

INVITED PRESENTATION

T1.8

T3.8

T4.8

Dr Kim Jelfs

Professor Karin Schroen

Dr Olgica Bakajin

STRUCTURE PREDICTION OF AMORPHOUS MOFS AND POROUS ORGANIC POLYMER MEMBRANES

PARTICLE MIGRATION USED AS A BASIS FOR EFFICIENT SEPARATION AND FRACTIONATION – MEASUREMENTS, MICROSTRUCTURES, MODELING

FORWARD OSMOSIS: A NEW TOOL TO MINIMIZE WASTE AND REUSE WATER FROM CHALLENGING WASTE STREAMS

1300-1400 Lunch & Trade Exhibition THEME: GAS SEPARATIONS PANORAMA 1

Chair: Matthias Wessling

THEME: NOVEL MATERIALS AND SURFACE MODIFICATIONS PANORAMA 2

THEME: MEMBRANE BIOREACTORS PANORAMA 3

Chair: Steven Cao and Pierre La-Clech

Chair: Suzana Nunes

THEME: WATER AND WASTE WATER TREATMENT CITY 1

Chair: Dharma Dharmabalan

INVITED PRESENTATION

INVITED PRESENTATION

INVITED PRESENTATION

T1.9

T2.9

T3.9

T4.9

Dr Ryan Lively

Associate Professor Mainak Majumder

Professor Xia Huang

Dr Eddy Ostarcevic

SYNERGISTIC GRAPHENE-BASED INTERATION BETWEEN MEMBRANES: SCALABLE SOLUBLE MICROBIAL MANUFACTURING AND PRODUCTS AND TARGETED PRODUCT MEMBRANE MATERIAL DEVELOPMENT DURING FOULING EVOLUTION OF MBRS

HARVESTED WATER CHARACTERISTICS IN THE CSG INDUSTRY AND THE ROLE OF REAL TIME MEMBRANE INTEGRITY MONITORING

1400-1430 INVITED PRESENTATION

LIGHT GAS SEPARATIONS USING PIM-1 HOLLOW FIBER SORBENTS AND MEMBRANES

T2.10

T3.10

T4.10

EFFECT OF IMPURITIES ON GAS SEPARATION PERFORMANCE IN MIXED MATRIX MEMBRANES

FREESTANDING ULTRATHIN GRAPHENEBASED MEMBRANES FOR WATER PURIFICATION

TREATING CLARIFIER AND BACKWASH WASTEWATER WITH ULTRAFILTRATION MEMBRANES

Shinji Kanehashi

Huiyuan Liu

CROSSING THE BORDER BETWEEN LABORATORY AND FIELD: BACTERIAL QUORUM QUENCHING FOR ANTI-BIOFOULING STRATEGY IN AN MBR

T2.11

T3.11

T4.11

GRAPHENE FUNCTIONALIZED MACRO-POROUS METAL FRAMEWORKS WATER DESALINATION BY MEMBRANE EVAPORATION

EFFECT OF TEMPERATURE ON A QUORUM QUENCHING MEMBRANE BIOREACTOR (QQ-MBR) FOR WASTEWATER TREATMENT.

DEVELOPMENT AND APPLICATION OF A HYDROPHILIC PVDF MEMBRANE FOR SEAWATER RO PRETREATMENT IN AUSTRALIA

Ludovic Dumee

Sojin Min

Geoffrey JohnstonHall

1430-1445 T1.10

1445-1500 T1.11 MASS TRANSFER IMPROVEMENT BY DEAN VORTEX: APPLICATION TO CO2 CAPTURE USING HOLLOW FIBER MEMBRANES CONTACTORS Deisy Mejia

Sang Hyun Lee

Pamela El Jbeily

GOLD SPONSOR

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PROGRAM

1500-1515 T1.12 THE IMPACT OF HYDROGEN SULFIDE AND ETHYLENE GLYCOLS ON THE PERFORMANCE OF CELLULOSE TRIACETATE MEMBRANE FOR CO2 SEPARATION

T2.12

T3.12

T4.12

NOVEL 2D HYBRID MOF/GRAPHENE OXIDE SEEDING FOR SYNTHESIS ULTRATHIN MOLECULAR SIEVING MEMBRANES

AN INTEGRATED MEMBRANE SYSTEM FOR ENZYMATIC COFACTOR REGENERATION AND DOWNSTREAM PURIFICATION OF PRODUCTS

DESIGN OF ELECTROSPUN METAL-BASED CATALYTIC FILTERS FOR WASTEWATER TREATMENT

Yaoxin Hu

Hiep (Bill) Lu 1515-1530 T1.13

Elise Des Ligneris

Sofie T. Morthensen T2.13

T3.13

T4.13

MIXED-MATRIX MEMBRANES CONTAINING ENGINEERED NANOPOROUS MATERIALS FOR BIOGAS PURIFICATION

EFFECTIVE GRAPHENEBASED SURFACE MODIFICATION OF FORWARD OSMOSIS MEMBRANES FOR IMPROVING THEIR PROPERTIES

CRITICAL SUCCESS PARAMETERS FOR MBR MODULE IMPROVEMENTS

RECYCLING CARWASH WASTE WATER USING CERAMIC MEMBRANE ULTRAFILTRATION

Lisa Leckie

Shammima Moazzem

Tae-Hyun Bae

Hanaa Hegab

1530-1600 Afternoon Refreshments & Trade Exhibition THEME: GAS SEPARATIONS PANORAMA 1

Chair: Aaron Thornton

THEME: APPLICATION THEME: MEMBRANE IN MINING INDUSTRY BIOREACTORS AND AGRICULTURE PANORAMA 3 PANORAMA 2

Chair: David Stuckey

Chair: Neil Palmer

THEME: MIXED SESSION ON MEMBRANES CITY 1

Chair: Hideto Matsuyama

INVITED PRESENTATION

INVITED PRESENTATION

INVITED PRESENTATION

T1.14

T2.14

T3.14

T4.14

Dr Ruilan Guo

Professor Greg Leslie

HIERARCHICALLY FUNCTIONAL IPTYCENE-CONTAINING POLYMERS FOR GAS SEPARATION MEMBRANES

Dr Lisendra Marbelia Professor Stephen RECENT DEVELOPMENTS Gray

INTERFACES IN URBAN METABOLISM: THE ROLE IN MEMBRANE FOR OF MEMBRANES IN THE BIOREACTORS RECOVERY OF ENERGY, WATER AND NUTRIENTS IN THE URBAN WATER CYCLE

1600-1630 INVITED PRESENTATION

1630-1645 T1.15 ACCELERATED AGING OF MEMBRANES MADE FROM POLYMERS OF INTRINSIC MICROPOROSITY WITH SUPERCRITICAL CARBON DIOXIDE Ze Xian Low

SMALL SCALE POTABLE WATER RECYCLING

T2.15

T3.15

T4.15

THE INFLUENCE OF CO2 LOADED SOLVENTS ON MICROALGAE GROWTH THROUGH A PDMS MEMBRANE SYSTEM

OPPORTUNITIES AND CHALLENGES TO RETROFIT EXISTING MEMBRANE BIOREACTOR (MBR) IN OSMOTIC MEMBRANE BIOREACTOR (OMBR) FOR (POTABLE) WATER REUSE

COMPUTATIONAL FLUID DYNAMIC ANALYSIS OF CONCENTRATION POLARIZATION AND WATER FLUX OPTIMIZATION IN SPIRAL WOUND MODULES

Qi Zheng

Fynn Aschmoneit

Gaetan Blandin

14

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PROGRAM

1645-1700 T1.16 NOVEL APPROACH TO PREPARE HIGHLYLOADED ASYMMETRIC MOF-MIXED MATRIX MEMBRANES USING PARTICLE FUSION TECHNIQUE

T2.16

T3.16

T4.16

PILOT-SCALE FORWARD OSMOSIS DESALINATION OF MINE IMPAIRED WATER FOR FERTIGATION

CONTROLLING SALINITY BUILD-UP IN OSMOTIC MEMBRANE BIOREACTORS

RO EFFICIENCY INCREASE WITHOUT ANTI-SCALANTS: A PILOT-STUDY

Wenhai Luo

Marjolein Vanoppen

T2.17

T3.17

T4.17

MEMBRANE SCREENING FOR IN-SITU SUBSURFACE DESALINATION IRRIGATION SYSTEMS

FORWARD OSMOSIS PROCESS FOR MICROALGAE SEPARATION FROM WATER

INTEGRATED SYSTEM FOR FLOWBACK TREATMENT

Valeria Almeida Lima

Li-hua Cheng

T2.18

T3.18

T4.18

INFLUENCE OF PH ON THE RETENTION OF STRATEGIC ELEMENTS FROM SYNTHETIC LEACHING SOLUTIONS BY NANOFILTRATION

EXTERNAL OSMOTIC MEMBRANE BIOREACTOR OPERATED WITH A NOVEL MEMBRANE

MEMBRANE SYSTEMS FOR RECOVERY AND REUSE OF PLANT TRANSPIRATION WATER IN GREENHOUSES

Murat Eyvaz

Ryan Lefers

T2.19

T3.19

T4.19

ACID RECOVERY FROM MINING PROCESSING WATER USING MEMBRANE DISTILLATION AND SOLVENT EXTRACTION (MD-SX)

VIBRATORY SHEAR ENHANCED SYSTEMS IN LAB-SCALE MBR

TOWARDS A NEW PARADIGM OF PROCESS INTENSIFICATION IN MEMBRANE GAS SEPARATION BY NOVEL PULSED RETENTATE FLOW APPROACH

Ho Kyong Shon

Salman Shahid 1700-1715 T1.17 INORGANIC NANOPARTICLES/ MOFS COMPOSITE MEMBRANE REACTORS FOR CO2 SEPARATION AND CONVERSION James Maina 1715-1730 T1.18 POLYMERIC MEMBRANES FOR HELIUM SEPARATION Colin Scholes

Katja Meschke 1730-1745 T1.19 MIXED MATRIX MEMBRANES COMPRISING OF FLUORINATED AND SULFONATED PEEK AND FUNCTIONALIZED MESOPOROUS COK-12 FOR CO2 SEPARATION Asim Khan

Recep Kaya

Xing Yang

Marian Turek

Ilya Vorotyntsev

1745-1915 POSTER SESSION AND YOUNG PROFESSIONALS MIXER

Sponsored by

GOLD SPONSOR

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PROGRAM

WEDNESDAY 7 DECEMBER 2016 PLENARY SESSION Chair: Linda Zou 0815

Registration Open

0900-0910 Welcome and Housekeeping 0910-1000 PLENARY PRESENTATION

Sponsored by

Professor Xiao-Lin Wang UNDERSTANDING NANOFILTRATION: A MOLECULAR SEPARATION WITH NANOMETER EFFECTS 1000-1030 Morning Refreshments & Trade Exhibition THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION PANORAMA 1

Chair: Klaus-Viktor Peinemann

THEME: ADVANCES IN THEME: MEMBRANE MF AND UF FOULING MEMBRANES PANORAMA 3 PANORAMA 2

Chair: Hiep (Bill) Le

Chair: Emile Cornelissen

THEME: PERVAPORATION VAPOUR SEPARATION AND MEMBRANE DISTILLATION CITY 1

Chair: Simon Smart INVITED PRESENTATION

KEYNOTE PRESENTATION

KEYNOTE PRESENTATION

W1.1

W2.1

W3.1

W4.1

Professor Greg Qiao

Professor Mikel Duke

Professor Rong Wang

HIGH FLUX ULTRA-THIN COMPOSITE MEMBRANES FOR CO2 SEPARATIONS

NEW APPLICATIONS AND FUNCTIONS FOR UF AND MF USING INORGANIC AND INORGANIC/ORGANIC COMPOSITE MATERIALS

Professor Anthony Fane

1030-1100 INVITED PRESENTATION

1100-1115 W1.2 EFFECT OF HYGROSCOPIC MATERIALS ON WATER VAPOR PERMEATION AND DEHUMIDIFICATION PERFORMANCE OF PVA MEMBRANES D Thuan Bui 1115-1130 W1.3 AN ORGANICSOLVENT-FREE METHOD TO FABRICATE INORGANIC POROUS HOLLOW FIBERS Patrick De Wit

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MEMBRANE FOULING: CAUSES, CONSEQUENCES AND CONTROL

BRINE TREATMENT BY MEMBRANE DISTILLATION CRYSTALLIZATION: NOVEL MEMBRANE DEVELOPMENT, MODULE DESIGN AND OPERATING CONDITION OPTIMIZATION

W2.2

W3.2

W4.2

ENHANCED ANTIFOULING OF NOVEL NANOFIBROUS BI-LAYER COMPOSITE ULTRAFILTRATION (UF) MEMBRANES

FOULING REDUCTION BY MEMBRANE BIOREACTOR USED AS A PRETREATMENT IN DESALINATION

NOVEL MODULE DESIGN FOR MEMBRANE DISTILLATION

Anbharasi Vanangamudi

Sanghyun Jeong

Bart Nelemans

W2.3

W3.3

W4.3

DESIGN OF BLOCK COPOLYMER MEMBRANES USING A MASTER CURVE FOR VARIOUS COPOLYMER ARCHITECTURES

ENHANCING MEMBRANE FOULING MITIGATION BY FLUIDIZED GRANULAR ACTIVATED CARBON

REVERSE OSMOSIS BRINE WASTE MINIMIZATION BY MEMBRANE DISTILLATION PROCESS

Bing Wu

Po Zhang

Burhannudin Sutisna

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PROGRAM

1130-1145 W1.4 DEGRADATION OF POLYETHERSULFONE/ POLYVINYLPYRROLIDONE MEMBRANES BY SODIUM HYPOCHLORITE Anthony Szymczyk

W2.4

W3.4

W4.4

APPLYING ADVANCED AERATION DESIGN TO DOUBLE-ENDED SUBMERGED FILTRATION

FACILE CONTROL OF ANTIFOULING AND HYDROPHILICITY IN BPPO ULTRAFILTRATION MEMBRANES VIA DIETHYLENETRIAMINE SURFACE MODIFICATION

ZN(TBIP)-PDMS: A NOVEL MOF MIXED MATRIX MEMBRANE FOR ENHANCED SEPARATION OF BIOBUTANOL

Lisa Leckie

Darrell Patterson

Muayad Al-shaeli W2.5

W3.5

W4.5

SMALL ANGLE X-RAY SCATTERING AS CHARACTERIZATION FOR BLOCK COPOLYMER MEMBRANES

EFFECT OF SPACER AND CROSSFLOW VELOCITY ON THE CRITICAL FLUX OF BIDISPERSE SUSPENSIONS IN MICROFILTRATION

Valentina Musteata

Jia Wei Chew

MEMBRANE FOULING IDENTIFICATION, MECHANISMS AND CONTROL FOR PRESSURE-RETARDED OSMOSIS (PRO) WITH REAL WASTEWATER RECLAMATION RETENTATE AS FEED

EFFECT OF COFERMENTATION PRODUCTS ON THE PERVAPORATION OF ETHANOL BY ZIF-8-PDMS MIXED MATRIX MEMBRANES

1145-1200 W1.5

Darrell Patterson

Qianhong She 1200-1215 W1.6 TAILORING THE IN-FILTRATION FLUX AND MWCO TUNEABILITY OF CONDUCTIVE POLYANILINE MEMBRANES: EFFECT OF DIFFERENT MOLECULAR WEIGHT ACID DOPANTS AND DOPING TEMPERATURES Salman Shahid 1215-1230 W1.7 PREDICATION OF GAS AND VAPOUR SORPTION IN GLASSY POLYMERS THROUGH A PC-SAFT BASED MODEL Liang Liu

W2.6

W3.6

W4.6

PARTICLE DEPOSITION ON FLAT SHEET MICROFILTRATION MEMBRANES UNDER BUBBLY AND SLUG FLOW AERATION: EFFECTS OF PARTICLE SIZE AND PORE BLOCKING

FOULING IN ANAEROBIC MEMBRANE BIOREACTORS: TOWARDS A MORE NUANCED APPROACH

OPEN-SOURCE PREDICTIVE SIMULATORS FOR SCALE-UP OF DIRECT CONTACT MEMBRANE DISTILLATION MODULES FOR SEAWATER DESALINATION

David Stuckley

Guangxi Dong

Xing Du W2.7

W3.7

W4.7

DETERMINISTIC RATCHET USING SIEVE STRUCTURED OBSTACLES FOR LARGESCALE SEPARATION OF PARTICLE SUSPENSIONS

IN-SITU CHARACTERIZATION OF BIO-FOULING ON RO MEMBRANES USING ELECTRICAL IMPEDANCE SPECTROSCOPY: THRESHOLD FLUXES AND BIOFILM FORMATION

TREATMENT OF BRACKISH GROUNDWATER CONTAINING FLUORIDE AND PESTICIDES WITH DIRECT CONTACT MEMBRANE DISTILLATION (DCMD)

Jaap Dijkshoorn

Julia Plattner

Hans Coster W2.8

W3.8

W4.8

A NEW COMPOSITE FORWARD OSMOSIS MEMBRANE WITH LOW FOULING TENDENCY AND HIGH SEPARATION EFFICIENCY

PREPARATION AND CHARACTERIZATION OF PVDF HOLLOW FIBER MEMBRANE WITH GRADIENT PORE STRUCTURES

SCALE UP OF CHEMICAL CLEANING: SUCCESS FROM FIBRE CLEANING IN THE LAB TO A FULL MODULE CLEAN

SCALE FORMATION OF CALCIUM PHOSPHATE IN DIRECT CONTACT MEMBRANE DISTILLATION

Zhaoyang Liu

Hui Liu

Steven Cao

1230-1245 W1.8

Zongli Xie

GOLD SPONSOR

17

PROGRAM

1245-1300 W1.9 3D PRINTING FOR MEMBRANE SEPARATION SYSTEMS Ze Xian Low

W2.9

W3.9

W4.9

CHARGE AND SIZE-SELECTIVE MOLECULAR SEPARATION USING ULTRATHIN CELLULOSE MEMBRANES

NON-INVASIVE AND DIRECT MONITORING OF HOLLOW FIBRE MEMBRANE FOULING DISTRIBUTION

THIN FILM FORMATION FROM AEROSOL ASSISTED PLASMA DEPOSITION FOR SOLVENT SEPARATION APPLICATION

Tiara Puspasari

Filicia Wicaksana

Xiao Chen

1300-1400 Lunch & Trade Exhibition THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION PANORAMA 1

Chair: Ingo Pinnau

THEME: ADVANCES IN NF AND RO MEMBRANES PANORAMA 2

Chair: Eric Hoek

THEME: MEMBRANE FOULING PANORAMA 3

Chair: Sophie Leterme

THEME: ELECTRICALLY ENHANCED MEMBRANE OPERATIONS CITY 1

Chair: Namita Choudhury KEYNOTE PRESENTATION

INVITED PRESENTATION

INVITED PRESENTATION

W1.10

W2.10

W3.10

W4.10

Professor Klaus-Viktor Peinemann

Professor Eric Hoek

Professor TorOve Leiknes

Professor Linda Zou

W2.11

W3.11

W4.11

SEPARATION OF ORGANIC SOLUTES BY REVERSE OSMOSIS MEMBRANES: AN EXPERIMENTAL AND COMPUTATIONAL STUDY

FOULING OF DRINKING WATER PRODUCTION MEMBRANE BY NANOPARTICLES

A NEW MODE OF REVERSE ELECTRODIALYSIS OPERATION TO REDUCE SEAWATER RO ENERGY DEMAND

1400-1430 INVITED PRESENTATION

ADVANCED MEMBRANE STRUCTURES MADE BY “PHASE INVERSION”

1430-1445 W1.11 PREPARATION OF NOVEL PVDF HOLLOW FIBER MEMBRANES FROM A TERNARY SYSTEM VIA COMBINED THERMALLY AND NONSOLVENT INDUCED PHASE SEPARATION (TIPS-NIPS) METHOD

ADVANCES IN MEMBRANE FILTRATION: BIOFOULING CERAMIC MEMBRANES, ASSESSMENT IN MEMBRANE FILTRATION POLYMERIC SYSTEMS APPLYING MEMBRANES AND INTELLIGENT CONTROLS IN-SITU NONDESTRUCTIVE METHODS

Morgane Le Hir

USING RGO LAMINATE FILM AS AN ION SELECTIVE BARRIER OF COMPOSITE MEMBRANE FOR WATER PURIFICATION

Marjolein Vanoppen

Anthony Szymczyk

Jie Zhao 1445-1500 W1.12 MICRO-WAVES TO STUDY THE LONG TERM STABILITY OF A MEMBRANE: WHY NOT? Murielle RabillerBaudry

W2.12

W3.12

W4.12

SURFACE MODIFICATION OF THIN FILM COMPOSITE MEMBRANES FOR FOULING REDUCTION AND ENHANCED CHLORINE STABILITY

COMMUNITY STRUCTURE AND IDENTIFICATION OF BIOFOULERS IN A SEAWATER REVERSE OSMOSIS DESALINATION PLANT

REVERSE ELECTRODIALYSIS DRIVEN WATER ELECTROLYSIS FOR HYDROGEN PRODUCTION

Jochen Meier-Haack Tamar Jamieson

18

Ramato Ashu Tufa

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PROGRAM

1500-1515 W1.13 HYBRID POLYMERLIQUID MEMBRANES: EFFECTS OF LOW MOLECULAR WEIGHT MOLECULES AND WATER VAPOR Luca Ansaloni

W2.13

W3.13

W4.13

FABRICATION AND CHARACTERIZATION OF NEW CERAMIC NANOFILTRATION MEMBRANES

MEMBRANE PERFORMANCES IN MEMBRANE PHOTOBIOREACTORS (MPBRS): THE EFFECT OF HYDRAULIC RENTENTION TIME (HRT)

IN-SITU FOULING CONTROL USING INTEGRALLY SKINNED FLAT SHEET HIGHLY CONDUCTIVE POLYANILINE ULTRAFILTRATION MEMBRANES WITH POLYMER DOPANTS

Shuaifei Zhao

Yunlong Luo

Salman Shahid W2.14

W3.14

W4.14

THE NOVEL GAS SEPARATION MEMBRANES FROM CHITOSAN MODIFIED BY ORGANIC AND INORGANIC MEDIA

ULTRAFILTRATION MEMBRANES FROM PES-PEG BLOCKCOPOLYMERS WITH IMPROVED FOULING PROPERTIES

RO FOULING CONTROL BY OPTIMIZING PRE-TREATMENT, MEMBRANE FLUX AND AIR/WATER CLEANING

Ilya Vorotyntsev

Jochen Meier-Haack

HYBRID HOLLOW-FIBER MEMBRANE ELECTRODES FOR THE REMOVAL OF TRACE ORGANIC POLLUTANTS IN MUNICIPAL WASTEWATER

1515-1530 W1.14

Emile Cornelissen

Francois Marie Allioux

1530-1600 Afternoon Refreshments & Trade Exhibition THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION PANORAMA 1

Chair: Greg Qiao

THEME: ADVANCES IN THEME: MEMBRANE NF AND RO FOULING MEMBRANES PANORAMA 3 PANORAMA 2

Chair: Anthony Fane

Chair: Sheng Dai

THEME: PERVAPORATION VAPOUR SEPARATION AND MEMBRANE DISTILLATION OPERATIONS CITY 1

Chair: Mikel Duke INVITED PRESENTATION

INVITED PRESENTATION

W1.15

W2.15

W4.15

Professor Hideto Matsuyama

Dr Hosik Park

Dr Simon Smart

ENGINEERED OSMOSIS

INORGANIC MEMBRANES: NOVEL MATERIALS FOR PERVAPORATION AND MEMBRANE DISTILLATION

1600-1630 KEYNOTE PRESENTATION

IONIC LIQUID-BASED FACILITATED CO2 TRANSPORT MEMBRANE WITH HIGH PRESSURE RESISTANCE

W2.16

W3.16

W4.16

FUNCTIONALIZED CARBON NANOTUBE ELECTROSPUN MEMBRANE USED IN MEMBRANE DISTILLATION FOR SEAWATER DESALINATION

IMPROVING ORGANIC SOLVENT NANOFILTRATION THROUGH PROCESS ENGINEERING: AN EXPERIMENTAL AND SIMULATION STUDY FOR OLEFIN METATHESIS

EVALUATION OF POTENTIAL PARTICULATE/ COLLOIDAL TEP FOULANTS ON A PILOT SCALE SWRO DESALINATION STUDY

MODELLING OF PERMEATION BLOCKING EFFECT BY ADSORBED GASES IN ZEOLITE MEMBRANES

Sanghyun Jeong

Murielle RabillerBaudry

1630-1645 W1.16

Alessio Caravella

Sheng Li

GOLD SPONSOR

19

PROGRAM

1645-1700 W1.17 CERAMIC HOLLOW FIBRE CATALYTIC CONVERTERS FOR AUTOMOTIVE EMISSIONS CONTROL

W2.17

W3.17

W4.17

SEPARATION IN HARSH CONDITIONS: ULTRA-THIN LAYERS ON CERAMIC HOLLOW FIBERS

THE BIOFOULING ROLE OF MICROBES IN THE DESALINATION SYSTEM

NUMERICAL STUDY ON THE TEMPERATURE POLARIZATION, CONCENTRATION POLARIZATION AND CACO3 FOULING RATE IN SUBMERGED VACUUM MEMBRANE DISTILLATION AND CRYSTALLIZATION (VMDC)

Sophie Leterme

Nur Izwanne Mahyon Evelien Maaskant

Helen Julian 1700-1715 W1.18 THE EFFECTS OF DISSOLUTION CONDITIONS ON THE PROPERTIES OF PVDF MEMBRANES FOR WATER FILTRATION Ikechukwu Ike

W2.18

W3.18

W4.18

EVALUATING THE AGING OF ORGANIC SOLVENT NANOFILTRATION MEMBRANES

RECOVERY PROPERTIES OF PERMEABILITY BY PHYSICAL CLEANING TO FO MEMBRANES FOULED BY HYDROPHILIC AND HYDROPHOBIC ORGANIC MATTER

OPTIMISING MEMBRANE DISTILLATION FOR SMALL-SCALE SEAWATER DESALINATION

Ze Xian Low

Hung Duong

Jaehyun Jung 1715-1730 W1.19 DEMONSTRATION OF AMMONIA CAPTURE FROM INDUSTRIAL EFFLUENTS Xing Yang

W2.19 COMPARISON OF AQUAPORIN Z EMBEDDED MEMBRANES FOR NANOFILTRATION APPLICATIONS Reyhan SengurTasdemir

1900-2300 CONFERENCE DINNER

Sponsored by

THE NATIONAL WINE CENTRE

A bus will leave the Adelaide Convention Centre at 6.40pm for the transfer to the National Wine Centre. Return transfers will commence from 10.00pm

20

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PROGRAM

THURSDAY 8 DECEMBER 2016 PLENARY SESSION Chair: Milena Ginic-Markovic 0815

Registration Open

0900-0910 Welcome and Housekeeping 0910-1000 PLENARY PRESENTATION

Sponsored by

Professor Menachem Elimelech MEMBRANE-BASED PROCESSES AT THE WATER-ENERGY NEXUS

1000-1030 Morning Refreshments & Trade Exhibition THEME: MIXED SESSION ON MEMBRANES PANORAMA 1

Chair: Greg Leslie

THEME: ENGINEERED OSMOSIS PANORAMA 2

Chair: Ho Kyong Shon

THEME: MEMBRANE BIOREACTORS ROOM PANORAMA 3

Chair: Sophie Leterme INVITED PRESENTATION

1030-1100 INVITED PRESENTATION TH1.1

TH3.1

Dr Anil Kumar Pabby

Associate Professor Pierre Le-Clech

CONCENTRATION AND PRESSURE DRIVEN MEMBRANE PROCESSES IN CHEMICAL AND RADIOACTIVE WASTE PROCESSING: CURRENT SCENRIO AND FUTURE CHALLENGES 1100-1115 TH1.2 ROLE OF PROTEIN ADSORPTION ON THEIR DETECTION BY SINGLE NANOPORE MEMBRANE Sébastien Balme

FACTORS INFLUENCING LOG REMOVAL OF PATHOGENS IN MEMBRANE BIOREACTORS, THE KEY FOR PROCESS VALIDATION

TH2.2

TH3.2

THERMORESPONSIVE ANIONIC COPOLYMER MICROGELS AS FORWARD OSMOSIS DRAW AGENTS: EFFECT OF ANIONIC COMONOMER CHEMICAL STRUCTURES

EFFECT OF SALINITY ON THE CHARACTERISTICS OF SOLUBLE MICROBIAL PRODUCTS (SMP) AND MEMBRANE FOULING David Stuckey

Hesamoddin Rabiee 1115-1130 TH1.3 TOWARD A BETTER UNDERSTANDING OF THE FOULING MECHANISMS DURING MICROALGAE DEWATERING BY FORWARD OSMOSIS Mathieu Larronde-larretche 1130-1145 TH1.4 ORGANIC MATTER CHARACTERISTICS AND TREATABILITY OF CONCENTRATES PRODUCED FROM RAW WASTEWATER, PRIMARY, AND SECONDARY EFFLUENTS

TH2.3

TH3.3

UP SCALING FORWARD OSMOSIS AND PRESSURE ASSISTED OSMOSIS TO COMBINE DESALINATION AND WATER REUSE: A PILOT SCALE STUDY ON 8´´ MODULES

BIO-METHANE PRODUCTION VARIATION UNDER DIFFERENT DRAW SOLUTE REVERSE DIFFUSIONS IN AN ANAEROBIC DIGESTER SIMULATED FOR FO-ANMBR

Gaetan Blandin

Sheng Li

TH2.4

TH3.4

ORGANIC MICRO-POLLUTANTS (OMP) REJECTION IN CLOSED-LOOP FO/RO: A PILOT PLANT STUDY

THIN FILM COMPOSITE HOLLOW FIBER MEMBRANES FOR EXTRACTIVE MEMBRANE BIOREACTOR

Emile Cornelissen

Chun Heng Loh

Junhee Ryu

GOLD SPONSOR

21

PROGRAM

1145-1200 TH1.5 CHEMICAL CLEANING STUDY IN COAL SEAM GAS (CSG) RO BRINE TREATMENT BY FERTILIZERDRAWN FORWARD OSMOSIS Youngjin Kim

TH2.5

TH3.5

INTEGRATING FORWARD OSMOSIS WITH ANAEROBIC TREATMENT FOR SIMULTANEOUS WASTEWATER TREATMENT AND RESOURCE RECOVERY – PROCESS PERFORMANCE AND CHALLENGES

EFFECT OF OPERATING PARAMETERS ON SOLUBLE MICROBIAL PRODUCTS (SMPS) IN A SUBMERGED ANAEROBIC MEMBRANE BIOREACTOR Chinagarn Kunacheva

Ashley Ansari 1200-1215 TH1.6 NUMERICAL MODELLING OF HYDRODYNAMIC CHARACTERISTICS OF SPHERICAL CAP BUBBLE FLOW IN AN IMMERSED HOLLOW FIBRE MEMBRANE SYSTEM

TH2.6

TH3.6

TRANSPORT OF OMPS THROUGH FO MEMBRANES: INFLUENCE OF OMP AND DRAW SOLUTE PROPERTIES

SYNERGY OF MICROBIAL QUORUM QUENCHING AND CHEMICALLY ENHANCED BACKWASHING FOR BIOFOULING CONTROL IN MEMBRANE BIOREACTORS

Arnout D’Haese

Elham Radaei 1215-1230 TH1.7 EXPLORING THE DUALITY OF JANUS MEMBRANES: A PATHWAY TO REALIZE HIGHLY EFFICIENT SEPARATIONS Jingwei Hou

1230-1245 TH1.8 REMOVAL OF REACTIVE BLACK DYE USING MIL-101-CR METAL ORGANIC FRAMEWORK IMPREGNATED CELLULOSE ACETATE PHTHALATE MIXED MATRIX ULTRAFILTRATION MEMBRANE

Kwang-ho Choo TH2.7

TH3.7

INFLUENCE OF MECHANICAL WASTEWATER PRETREATMENT ON MEMBRANE FOULING DURING MUNICIPAL WASTEWATER TREATMENT BY FORWARD OSMOSIS

PERFORMANCE OF VARIOUS FERTILIZER DRAW SOLUTIONS IN A NOVEL HYBRID MICROFILTRATION FERTILIZER-DRAWN FORWARD OSMOSIS AEROBIC BIOREACTOR (MF-FDFO-MBR)

Agata Zarebska

Laura Chekli

TH2.8

TH3.8

UP-CONCENTRATION OF SUGAR SOLUTION BY USING FORWARD OSMOSIS FOR BIOETHANOL PRODUCTION PROCESS Masafumi Shibuya

FOULING CONTROL OF SUBMERGED ANAEROBIC MEMBRANE BIOREACTORS WITH SANDWICH VIBRATORY-STIRRING (SVS) MEMBRANE MODULES

TH2.9

TH3.9

SILICA SCALING IN FORWARD OSMOSIS: FROM SOLUTION TO MEMBRANE INTERFACE

EVALUATION OF N-ACYLHOMOSERINE LACTONE DEGRADATION BY BACTERIA ISOLATED FROM MARINE, POND, SALTERN, LEACHATE AND BIOFOULING CONTROL WITH BACILLUS SP. T5 IN MBR

Tian Li

Sankha Karmakar 1245-1300 TH1.9 REMOVAL OF CONGO RED DYE USING MAGNETIC NICKEL–IRON OXIDE (NFO) NANOPARTICLE INCORPORATED POLYSULFONE (PSF) MIXED MATRIX ULTRAFILTRATION HOLLOW FIBER MEMBRANE Mrinmoy Mondal

Ming Xie

Bahar Yavuztürk Gül

1300-1400 Lunch & Trade Exhibition

22

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PROGRAM

THEME: MEMBRANE DISTILLATION PANORAMA 1 & 2

Chair: Rong Wang 1400-1430 INVITED PRESENTATION

THEME: MIXED SESSION ON MEMBRANES PANORAMA 3

Chair: Pierre Le-Clech INVITED PRESENTATION

TH1.10

TH2.10

Dr Guillermo Zaragoza

Dr Tao He

MEMBRANE DISTILLATION: A REVIEW OF COMMERCIAL MODULES AND THEIR PERFORMANCE

INTEGRAL FORWARD OSMOSIS-MEMBRANE DISTILLATION PROCESS: RESEARCH HYPE OR SUSTAIN­ABLE SOLUTION FOR WATER REUSE?

1430-1445 TH1.11 OMNIPHOBIC MEMBRANE TO TREAT REVERSE OSMOSIS BRINE FROM COAL SEAM GAS PRODUCED WATER BY MEMBRANE DISTILLATION Yunchul Woo 1445-1500 TH1.12 FOULANT – MEMBRANE INTERACTION DURING MEMBRANE DISTILLATION: INSIGHTS FROM SYNCHROTRON FOURIER TRANSFORM INFRARED SPECTROSCOPY

TH2.11 GAS FIELD PRODUCED/PROCESS WATER TREATMENT USING FORWARD OSMOSIS HOLLOW FIBER MEMBRANE: MEMBRANE FOULING AND CHEMICAL CLEANING Shanshan Zhao TH2.12 MEMBRANE TECHNOLOGY FOR WATER AND HEAT RECOVERY FROM POWER STATION FLUE GAS Shuaifei Zhao

Dr Ming Xie 1500-1515 TH1.13

TH2.13

MEMBRANE DISTILLATION FOR SEAWATER REVERSE INTERNAL APPLICATION OF NANOFIBER OSMOTIC OSMOSIS (SWRO) BRINE TREATMENT AND METAL MEMBRANE IN MEMBRANE BIOREACTOR RECOVERY Serkan Arslan Gayathri Naidu 1515-1530 TH1.14 TREATMENT AND REUSE OF BIO-TREATED COKING WASTEWATER (BTCW) WITH MEMBRANE DISTILLATION: POSSIBILITIES AND CHALLENGES Jianfeng Li 1530-1545 TH1.15

TH2.14 INTEGRATION OF FOULING INTO MODELS OF OSMOTICALLY DRIVEN MEMBRANE PROCESSES Endre Nagy TH2.15

2D-ZEOLITE/MOF MEMBRANES FOR GAS AND VAPOUR SEPARATION

PERFORMANCE OF FO-RO AND RO FOR SEAWATER DESALINATION

Berna Topuz

Ali Altaee

1545-1600 CLOSING CEREMONY Professor Amanda Ellis & Dr Milena Ginic-Markovic

GOLD SPONSOR

23

IXOM WATER TREATMENT SYSTEMS (WTS) WTS provides practical, customised and innovative industrial water and wastewater treatment solutions.

What’s your challenge? Ixom Water Treatment Systems 1 Nicholson St East Melbourne VIC 3002 Australia

T Australia 1300 550 136 New Zealand 0800 734 607 All other locations +61 3 9906 3000

F 1300 550 081 E [email protected] ixom.com

Issued by Ixom Water Treatment Systems (WTS), a division of Ixom Operations Pty Ltd (ABN 51 600 546 512), 1 Nicholson Street, Melbourne. Ixom and the Ixom logo are trademarks of Ixom Group

PROGRAM PLUS

GOLD SPONSOR

25

WORKSHOPS

PRE-CONFERENCE WORKSHOP

Early Career Researchers Forum Date:

Monday 5 December 2016

Time:

0900-1600

Inclusions: Morning Refreshments & Lunch Cost: $100 The Early Career Research workshop will feature presentations from leaders in the field of membranes including Matthias Wessling, Benny Freeman and Sandra Kentish, giving advice and help to junior researchers looking to forge a pathway in the field. There will be opportunities for questions to these leaders, and a chance to work on your presentation skills with an ‘elevator pitch’ session to follow. This workshop should be attended by students, postdocs, and any person involved in the membrane field looking to contribute to the development of up and coming researchers.

PRE-CONFERENCE WORKSHOP

Membranes in Mining Date:

Monday 5 December 2016

Time:

0900-1600

Inclusions: Morning Refreshments & Lunch Cost: $220 Process streams within the mining and resources sector are often characterised by their extreme pH conditions and particles loads, which can limit the use of membranes. The pre-conference workshop will have discuss the issues and opportunities that can arise from treating these process streams, providing examples of operational performance delivered by industry experts. New commercial membrane and pre-treatment technologies will also be presented and the workshop is structured to encourage discussion and attendee participation within the workshop. It provides an opportunity for industry practitioners to hear about the latest technology developments and provides researchers with an opportunity to better understand the issues in the mining and resources industry.

26

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

SOCIAL PROGRAM

WELCOME RECEPTION Date:

Monday 5 December 2016

Time:

1810-2000

Venue:

Panorama Foyer, Adelaide Convention Centre

Cost:

Included in full registrations. Additional tickets $70 per person

Dress:

Smart casual

The IMSTEC 2016 Conference will begin with the Welcome Reception held at the Adelaide Convention Centre, Riverbank Promenade This is a great opportunity to catch up with colleagues and meet other attendees. This will be a relaxed event.

GOLD SPONSOR

27

SOCIAL PROGRAM

Conference Dinner

Date:

Wednesday 7 December 2016

Time:

1900-2300

Venue:

The National Wine Centre Pre dinner drinks begin at 7.00pm Dinner will commence at 7.30pm

Cost:

Included in full registrations. Additional tickets $125 per person. Bookings required.



Transport: A bus will leave the Adelaide Convention Centre at 6.40pm for the transfer to the National Wine Centre. Return transfers will commence from 10.00pm The dinner is always an enjoyable evening. The National Wine Centre is one of Adelaide’s premier venues, and is owned and operated by The University of Adelaide.

28

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

SOCIAL PROGRAM

Post Conference Tour Date:

Friday 9 December 2016

Time:

0930-1645

Venue:

Adelaide Desalination Plant at Port Stanvac d’Arenberg Winery and the town of Hahndorf

Cost:

$100 per person

0930 Depart Adelaide Convention Centre

The Adelaide Desalination Plant (ADP) at Port Stanvac was built to provide long-term water security for South Australia. The ADP has been delivering drinking water since 2011, and thus far has supplied approximately 134 GL to the SA Water distribution network. The plant is fully owned by SA Water.

1015 Arrive at Plant

In December 2012, after construction and a comprehensive commissioning period, the plant was handed over to the Operator, Adelaide Aqua Pty Ltd (AAPL). AAPL are contracted to operate and maintain the ADP on SA Water’s behalf for 20 years.

1430 Depart d’Arenberg Winery

1030 Tour commences 1230 Tour concludes 1330 Lunch & Tasting – d’Arenberg Winery

1500 Arrive at Hahndorf 1600 Depart Hahndorf

1645 Arrive back in In full operation, the plant can deliver 100 gigalitres (GL) per Adelaide year, through two identical process plants each capable of producing 150 megalitres per day. The water production capacity is extremely flexible, with the Plant being capable of output between 10% and 100% of its capacity in 10% increments. This allows SA Water to set a production schedule to suit customer demand and prevailing environmental conditions such as weather and catchment inflows. The plant utilises a 3 stage pre-treatment process including ultrafiltration membranes to remove particulates from the raw seawater, followed by a two pass reverse osmosis system to remove the majority of the dissolved salts. A post-treatment process ensures water leaving the plant is ready to drink and this water is transported approximately 14km to the Treated Water Storage Tanks at Happy Valley from where it is distributed to the network. The tour of the plant will include a walk-through of the treatment process from beginning to end, including one of the main process buildings which house the ultrafiltration and reverse osmosis treatment systems. After the technical tour delegates will enjoy lunch at the beautiful d’Arenberg Winery and then a free hour to wander the township of historic Hahndorf. Settled in 1939 by Prussian Lutherans bravely seeking religious freedom on the other side of the world, Hahndorf’s picturesque colonial charm remains remarkably intact. Hahndorf is Australia’s oldest surviving German settlement and celebrated 175 years in 2014. GOLD SPONSOR

29

SOCIAL PROGRAM

Flinders University is proud to launch its new Bachelor of Science (BSc). The degree is one of the most innovative and flexible science programs on offer with an extensive range of majors and specialisations, and the opportunity to build your own study program.

30

You can choose to study a particular field of science in depth, or select a range of subjects from across the sciences. For a broad education, the new science degree also provides the opportunity to include non-science electives. Whichever program you choose, you will acquire the science skills and knowledge to prepare you for your future career and get a head start in the field of science.

FLINDERS.EDU.AU/BSC

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PLENARY SPEAKERS

GOLD SPONSOR

31

PLENARY SPEAKERS

PROFESSOR SANDRA E. KENTISH MULTICOMPONENT GAS SEPARATION - THE IMPORTANCE OF IMPURITIES IN FLUE GAS CAPTURE Peter Cook Centre for CCS Research, Department of Chemical and Biomolecular Engineering, University of Melbourne There are an increasing number of researchers developing novel materials for carbon dioxide capture and other gas separation applications. However, most researchers only complete experiments with streams of pure gases and compare their data to the famous Robeson’s bound. In this presentation, an overview will be given of how this approach can often fail. It is essential to instead consider multicomponent gas streams in analysing performance. In addition to carbon dioxide and nitrogen, post-combustion flue gases can contain sulfur oxides, nitrogen oxides, water vapor and fly ash. Pre-combustion flue gases can contain carbon monoxide, a range of hydrocarbon molecules, hydrogen sulfide, particulates and water vapor; while raw natural gas can contain compressor oil, hydrogen sulfide and hydrocarbons such as benzene and toluene, in addition to the carbon dioxide and methane. These other components in the gas stream can be of significant influence through phenomena such as competitive sorption, plasticization, anti-plasticization and concentration polarisation. In our work, we have used a combination of pilot plant trials, experimental data and mathematical models to better understand these challenging multicomponent systems. This work shows that competitive sorption can influence both glassy and rubbery membranes and indeed mixed matrix membranes, usually (but not always) causing a loss in permeability and selectivity. The presence of water vapor can readily cause plasticization of the polymer, which in turn can increase fractional free volume and reduce selectivity. This molecule can also become involved in ‘antiplasticisation’ where water clusters limit diffusional pathways. As water vapor has very high permeability, it readily causes concentration polarization, reducing performance. However, in post-combustion capture, water vapor can also have a positive influence, by reducing the partial pressure of carbon dioxide on the permeate side of the membrane.

32

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

PLENARY SPEAKERS

DR BENNY FREEMAN ION SORPTION, DIFFUSION AND TRANSPORT IN CHARGED POLYMER MEMBRANES Richard B. Curran Centennial Chair in Engineering, McKetta Department of Chemical Engineering, Texas Materials Institute, Center for Energy and Environmental Resources, and Center for Research in Water Resources, University of Texas at Austin Charged polymer membranes are widely used for water purification applications involving control of water and ion transport, such as reverse osmosis and electrodialysis. Efforts are also underway worldwide to harness separation properties of such materials for energy generation in related applications such as reverse electrodialysis and pressure retarded osmosis. Additional applications, such as energy recovery ventilation and capacitive deionization, rely on polymer membranes to control transport rates of water, ions, or both. Improving membranes for such processes would benefit from more complete fundamental understanding of the relation between membrane structure and ion sorption, diffusion and transport properties in both cation and anion exchange membrane materials. Ion-exchange membranes often contain strongly acidic or basic functional groups that render the materials hydrophilic, but the presence of such charged groups also has a substantial impact on ion (and water) transport properties through the polymer. We are exploring the influence of polymer backbone structure, charge density, and water content on ion transport properties. Results from some of these studies will be presented, focusing on ion transport through various positively charged and negatively charged membranes via concentration gradient driven transport (i.e., ion permeability) and electric field driven transport (i.e., ionic conductivity). One long-term goal is to develop and validate a common framework to interpret data from both electrically driven and concentration gradient driven mass transport in such polymers and to use it to establish structure/property relations leading to rational design of membranes with improved performance. Ion sorption and permeability data were used to extract salt diffusion coefficients in charged membranes. Concentrations of both counter-ions and co-ions in the polymers were measured via desorption followed by ion chromatography or flame atomic absorption spectroscopy. Salt permeability, sorption and electrical conductivity data were combined to determine individual ion diffusion coefficients in neutral, cation exchange and anion exchange materials. Manning’s counter-ion condensation model is used to predict ion sorption in charged polymers. Manning’s diffusion model is coupled with the Mackie/Meares model to predict co-ion diffusion coefficient data and to model, with one adjustable parameter, counter-ion diffusion coefficient data.  

GOLD SPONSOR

33

PLENARY SPEAKERS

PROFESSOR XIAO-LIN WANG UNDERSTANDING NANOFILTRATION: A MOLECULAR SEPARATION WITH NANOMETER EFFECTS Department of Chemical Engineering, Tsinghua University, Beijing 100084, P.R. China Nanofiltration (NF) membrane, firstly named as “loose” Reverse osmosis (RO) or “dense” Ultrafiltration (UF) membrane, has two remarkable features: one is the molecular weight cut-offs (MWCO) ranges from 200 to 2000Da, and the other is the salt rejection depends on the ion valence and concentration. Several models for NF processes have been proposed, such as the pore model based on the sieving effect, the charge model1 based on the electrostatic effect, the electrostatic steric-hindrance (ES) model2, and the Donnan steric pore model (DSPM) have been proposed, which play an important role in understanding the separation mechanism and promoting the application of NF3,4. Afterward, almost all of the RO membrane manufacturers have produced a series of NF membranes for the purification and advanced treatment of water. However, the performances of these NF membranes with features of “loose” RO membranes cannot be predicted by commercial RO simulation software. It leads to a long period of previous experiments and scale-up process, which severely restricts the large scale standardization applications of NF. In regard to these problems, we proposed a simple simulation model for the separation performance of mixed salts solution across NF membranes to promote the application of NF during the water treatment in the light of the competitive effect among co-ions and regulation effect among counter-ions. Both two effects can be determined by some specific experiments [5, 6]. And then based on the in-depth experimental studies on rejection performance and the attendant electrokinetic properties, some researchers have found that the performance of NF membranes cannot be predicted completely by merely considering the sieving and electrostatic effect, but some drawbacks still exist in the analysis of electrokinetic properties. The further studies have contributed to a deeper understanding on the particular effect caused by the nano-scale pore size and charge features caused by the complicated interaction in solution7, 8. Moreover, the dielectric effect in the transport process of ions through NF membranes9 has been addressed and quantitatively analyzed. Recent studies have been paid much attention on the new generation of NF membranes improved by various nanostructured materials10, 12. We also made some try to develop some novel thin-film nano-composite NF membranes derived from the dual layer (PES/PVDF) hollow fiber UF membranes 13-20. Keywords: Nanofiltration; Separation mechanism; Separation performance; Nanostructured materials

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REFERENCES: 1

X-L WANG, T TSURU, S NAKAO, S KIMURA, Electrolyte transport through nanofiltration membranes by the space charge model and the comparison with Teorell - Meyer - Sievers model. J. Membrane Sci., 1995, 103(1-2):117-132

2

X-L WANG, T TSURU, S NAKAO, S KIMURA, The electrostatic and steric - hindrance model for the transport of charged solutes through nanofiltration membranes. J. Membrane Sci., 1997, 135(1):19-32

3

X-L WANG, A-L YING, W-N WANG,Nanofiltration of L-phenylalanine and L-aspartic acidaqueous solution. J. Membrane Sci, 2002, 196:59-67

4

X-L WANG, C-H ZHANG, P-K OUYANG, The possibility of separating saccharides from a NaCl solution by using NF in diafiltration mode. J. Membrane Sci, 2002, 204:271-281

5

D-X WANG, X-L WANG, Y TOMI, M ANDO, T SHINTANI, Modeling the separation performance of nanofiltration membranefor mixed salts solution. J. Membrane Sci., 2006, 280(1-2):734-743

6

D-X WANG, L WU, Z-D LIAO, X-L WANG, Y TOMI, M ANDO, T SHINTANI, Modeling the separation performance of nanofiltration membranefor the mixed salts solution with Mg2+ and Ca2+. J. Membrane Sci., 2006, 284(1-2):384-392

7

W-J SHANG, X-L WANG, Y-X YU, Theoretical calculation on the membrane potential of charged porous membranes in 1-1, 1-2, 2-1 and 2-2 electrolyte solutions. J. Membrane Sci., 2006, 285(1-2):362-375

8

C-H TU, H-L WANG, X-L WANG. Study on Transmembraneelectrical potential of nanofiltrationmembranes in KCl and MgCl2 solutions. Langmuir, 2010, 26(22):17656–17664

9

C-H TU, Y-Y FANG, J ZHU, B VANDER BRUGGEN, X-L WANG. Free energies of the ion equilibrium partition of KCl intonanofiltrationmembranes based on transmembrane electrical potential and rejection. Langmuir, 2011, 27(16):10274-10281

10 X-L WANG, Y-Y FANG, C-H TU, B VAN DER BRUGGEN. Modelling of the separation performance and electrokinetic properties of nanofiltration membranes. Int . Rev. Phys. Chem. 2012, 31(1):111-130. 11 R-X ZHANG, L BRAEKEN, P LUIS, X-L WANG, B VAN DER BRUGGEN. Novel binding procedure of TiO2 nanoparticles to thin film composite membranes via self-polymerized polydopamine. J. Membrane Sci. 2013, 437:179-188. 12 Q LI, Q-Y BI, H-H LIN, L-X BIAN, X-L WANG. A novel ultrafiltration (UF) membrane with controllable selectivity for protein separation. J. Membrane Sci. 2013, 427:155-167. 13 Y-H TANG, Y-D HE, X-L WANG. Three-dimensional analysis of membrane formation via thermally induced phase separation by dissipative particle dynamics. J. Membrane Sci. 2013, 437:40-48. 14 T-Y LIU, R-X ZHANG, Q LI, B VAN DER BRUGGEN, X-L WANG. Fabrication of a novel dual-layer (PES/PVDF) hollow fiber ultrafiltration membrane for wastewater treatment. J. Membrane Sci. 2014, 472:119-132. 15 T-Y LIU, L-X BIAN, H-G YUAN, B PANG, Y-K LIN, Y TONG, B VAN DER BRUGGEN, X-L WANG. Fabrication of a High-flux Thin Film Composite Hollow Fiber Nanofiltration Membrane for Wastewater Treatment. J. Membrane Sci. 2015, 478:25-36. 16 Y-H TANG, Y-D HE, X-L WANG. Investigation on the membrane formation process of polymer–diluent system via thermally induced phase separation accompanied with mass transfer across the interface: Dissipative particle dynamics simulation and its experimental verification. J. Membrane Sci. 2015, 474:196–206. 17 T-Y LIU, C-K LI, B PANG, B VAN DER BRUGGEN, X-L WANG. Fabrication of a dual-layer (CA/PVDF) hollow fiber membrane for RO concentrate treatment. Desalination 2015, 365:57-69. 18 T-Y LIU, Y TONG, Z-H LIU, H-H LIN , Y-K LIN, B VAN DER BRUGGEN, X-L WANG. Extracellular polymeric substances removal of dual-layer (PES/PVDF) hollow fiber UF membrane comprising multi-walled carbon nanotubes for preventing RO biofouling. Sep. Purif. Technol. 2015, 148:57–67. 19 T-Y LIU, Z-H LIU, H-G YUAN, X-L WANG, et.al. Fabrication of a thin film nanocomposite hollow fiber nanofiltration membrane for wastewater treatment. J. Membrane Sci. 2015, 488:92-102. 20 T-Y LIU, H-G YUAN, X-L WANG, et.al. Ion-Responsive Zwitterion Gatekeepers on Carbon Nanotube Membrane with Rapid Water Channels and Ultra-high Multivalent Ion Rejection. ACS Nano, 2015, 9(7): 7488–7496 GOLD SPONSOR

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PROFESSOR MENACHEM ELIMELECH MEMBRANE-BASED PROCESSES AT THE WATERENERGY NEXUS Department of Chemical and Environmental Engineering, Yale University Membrane-based processes play a critical role in technologies for desalination and water purification, as well as emerging technologies for sustainable power generation from natural salinity gradients and waste heat. In this presentation we will discuss several membrane processes which play an important role at the water-energy nexus. One of these technologies is reverse osmosis, which is being used extensively worldwide for seawater desalination. The energy efficiency and the state of the technology of seawater desalination will be critically reviewed. Another emerging process for water purification is forward osmosis. Several applications of forward osmosis that enhance sustainability at the water-energy nexus will be presented and research needs to advance the technology will be discussed. Another closely related process is pressure retarded osmosis, an emerging technology for capturing salinity gradient energy from saline waters. We will focus on the viability of the process and highlight most beneficial applications of this process. Lastly, we will describe a newly developed membrane-based process that can generate energy from low-grade or waste heat. In this thermo-osmotic energy conversion process, hydrophobic membranes utilize a temperature gradient to drive a vapor flux against a hydraulic pressure difference, effectively converting low-grade heat to useful work. The fundamental principles of this thermo-osmotic energy conversion process will be delineated and research needs to enhance the viability of the process will be discussed.

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KEYNOTE SPEAKERS

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KEYNOTE SPEAKERS

T1.1 PROFESSOR INGO PINNAU FUNCTIONALIZED POLYMERS OF INTRINSIC MICROPOROSITY FOR HIGHLY ENERGY-INTENSIVE GAS SEPARATIONS

PROFESSOR INGO PINNAU, BADER GHANEM, XIAOHUA MA, NASSER ALASLAI, FAHD ALGHUNAIMI, RAMY SWAIDAN King Abdullah University Of Science And Technology Key Words: Polymers of intrinsic microporosity, gas separation, natural gas, olefin/paraffin, air separation. Membrane-based gas separation is a rapidly emerging technology that has been established in the purification of air and hydrogen streams and is showing an increasingly larger role in natural gas sweetening and vapor/gas separations. One strategy actively pursued to generate polymers with combinations of high permeability and high selectivity is the introduction of microporosity (pores < 20 Å) in the polymer matrix. It has been shown that rigid ladder-type chains comprising fused rings joined by sites of contortion pack inefficiently in the solid state to produce polymers of intrinsic microporosity (PIMs). Recently, a successful integration of monomers contorted by spirobisindane, ethanoanthracene, Tröger’s base and triptycene moieties into polyimide structures has also generated highly permeable intrinsically microporous polyimides (PIM-PIs). Some of these PIM-PIs have shown significantly enhanced performance for O2/N2, H2/N2 and H2/CH4 separations with properties defining the most recent 2015 permeability/selectivity upper bounds. Here, we will discuss several series of novel PIM-PIs and ladder PIMs based on rigid and bicyclic moieties, which are solution processable to form mechanically robust films with high internal surface areas (up to 1100 m2/g). Gas permeation and physisorption data indicate the development of an ultramicroporous structure that is tunable for different gas separation applications. Specific emphasis will be placed on the potential use of hydroxyland carboxyl-functionalized PIMs for highly-energy demanding applications for natural gas treatment and olefin/paraffin separation.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

KEYNOTE SPEAKERS

T2.1 PROFESSOR SUZANA P. NUNES MEMBRANE PREPARATION FROM SOLUTIONS IN IONIC LIQUIDS

DOOLI KIM, SUZANA P. NUNES King Abdullah University of Science and Technology, Biological and Environmental Science and Engineering Polymeric membranes are mainly manufactured by solution casting and phase inversion induced by immersion in water. The process has been implemented for polymers, such as cellulose acetate, polyacrylonitrile, poly(vinylidene fluoride) and polysulfone, and optimized for decades. Polar solvents such as dimethylformamide (DMF) and N-methylpyrrolidone (NMP) are normally used for solubilization. These solvents are however considered toxic by inhalation in large-scale production and are expected to be banned in the near future. Alternative solvents are urgently needed. Our group has been investigating the preparation of polymeric membranes by partial or total solubilization in ionic liquids. As a first example cellulose membranes were prepared from solution in 1-ethyl-3-methylimidazolium acetate, instead of using the much more aggressive cuprammonium or viscose solubilization processes.1 Polyacrylonitrile hollow fiber membranes were prepared from solution in the same ionic liquid and dimethylsulfoxide.2 Polysulfone membranes were prepared from solution in 1-ethyl-3-methylimidazolium dimethylphosphate.3 The rheological investigation and determination of the phase diagram allowed an efficient optimization of the preparation process. In this way polysulfone membranes with low molecular weight cut-off, able to separate peptide mixtures, could be obtained with permeance varying from 20 to 140 L m-2 h-1 bar-1. Analogous processes are being explored also for other polymeric membrane materials, demonstrating that ionic liquids can be used in the membrane production as alternative to the traditional manufacture. Industries have been quietly adopting membrane processes for clarification, concentration and flavour modification with very little academic input. There are several smaller operations using separations such as mineral reduction, protein recovery or clarification in the pharmaceutical/nutraceutical industries. None of these are likely to be large enough to drive membrane research. This paper will review the current state of the art in the food and beverage industry and will seek to identify areas of research that could lead to changes in industrial practice. REFERENCES 1. S. Livazovic et al., J. Membr. Sci. 2015, 490, 282-293. 2. D. Kim et al., Polym. Chem. 2016, 7, 113-124. 3. D. Kim et al., Green Chem. 2016, DOI: 10.1039/C6GC01259K.

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T4.1 PROFESSOR DR.-ING. MATTHIAS WESSLING FUNDAMENTALS OF SOFT MATTER MEMBRANE FILTRATION

M. WESSLING, J. LINKHORST, J. LOELSBERG, O. NIR, J. LOHAUS As fouling remains one of the major hurdles in membrane filtration processes, its fundamental phenomena still need to be elucidated and the underlying principle need to be fully comprehended. While deposition and removal of hard colloidal matter such is silica is well studied, soft matter other than proteins have received too little attention. In this lecture, we present our current work on the use of microgels as a generic platform soft colloidal matter. Microgels are highly swollen polymeric colloids having elasticity, deformability, homogenous or inhomogeneous charge distribution, and sometimes even core-shell or janus architectures. They are hence a versatile platform for comprehensive studies on colloidal filtration physics. Four new topics are addressed: 1. the simultaneous measurement of hydraulic and electrical resistance during dead-end filtration of microgels through micro filtration membranes1. This new technique allows to clearly distinguish between surface deposition and depth filtration. 2. the visualization of translocation events of hard nanoparticles through a soft filter cake made of micro filtration2 using a microfluidic confocal microscopy technique2 3. the 3D printing of designer filtration membranes having sub-micron pores allowing the templating of soft colloidal crystals and studying their compressibility under convective flow. 4. the simulation of colloidal aggregation and deposition in porous membranes using colloids represented by an DLVO potential The lecture suggests a rigorous methodology to deconvolute and quantify microscopic events occurring during soft matter membrane filtration. REFERENCES 1

Nir, O., Trieu, T., Bannwarth, S., & Wessling, M. (2016). Microfiltration of deformable microgels. Soft Matter, 1–6. http://doi.org/10.1039/C6SM01345G

2 Linkhorst, J., Beckmann, T., Go, D., Kuehne, A. J. C., & Wessling, M. (2016). Microfluidic colloid filtration. Scientific Reports, 6, 22376–8. http://doi.org/10.1038/srep22376

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KEYNOTE SPEAKERS

W3.1 PROFESSOR TONY FANE MEMBRANE FOULING: CAUSES, CONSEQUENCES AND CONTROL Nanyang Technological University, Singapore Membrane fouling is inevitable given the accumulation of retained species at the membrane surface. Fouling is usually detrimental leading to increased costs and energy usage. It is the ‘Achilles heal’ of membrane technology. Fouling can take the form of an additional flow resistance (RF) and in some cases it causes a decrease in driving force (-DF); the latter effect may be overlooked but can dominate the loss of performance. This presentation reviews fouling phenomena in the liquid-phase membrane processes and highlights mechanisms and control strategies. Low pressure (LP) membranes are used in MBRs where fouling is complex1 with a series of fouling stages. The final ‘TMP jump’2 signifies serious fouling, and could be due to a number of ‘self accelerating’ phenomena. The jump can be delayed by judicious choice of operating conditions, use of certain additives, and interfering with or quenching the biofilm development. LP hollow fibre membranes are often used under suction and this can lead to ‘fouling-like’ problems due to two phase flow in the lumen of the hollow fibres. The presence of trapped air on the permeate side can diminish the effectiveness of back wash3 and this can be controlled by avoiding low suction pressures and by design considerations. For MBRs fouling can be alleviated by unsteady-state hydrodynamics, such as by using vibrations and fluidized bed interactions15, 16. Reverse Osmosis, the key to desalination and reclamation, experiences many types of fouling that can contribute both resistance (RF) and loss of driving force (-DF) known as cake enhanced osmotic pressure (CEOP)4,5. Using methods that allow separate measurement of RF and CEOP we find that CEOP dominates in many cases; examples include organic, colloidal and biofouling. The fouling by biofilms is a serious problem for RO and is driven by nutrient supply and influenced by flux and module hydrodynamics6; TMP rise correlates with the concentration polarization of nutrient. This leads to control strategies including pre-treatment to reduce assimilable organic carbon and limiting the extent of elevated flux. An exciting prospect is to use biomimicry to limit or disperse the biofilm1. Forward Osmosis (FO) is sometimes considered to be a low fouling option, but this depends on membrane orientation, as observed in FOMBR studies [8]. Fouling in FO is exacerbated when the support layer faces the feed, although ‘double-skinned’ FO membranes can alleviate this effect9. The phenomena of critical flux also applies to FO as observed for an algae suspension10, and this study also showed that back diffusion of divalent cations from the draw could enhance fouling.

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Membrane Distillation (MD) also exhibits fouling. When applied to wastewater in the MDBR the fouling can be severe11. The fouling in this system is complex with resistances (RF) due to biofilm and inorganic deposits and loss of vapour pressure driving force (-DF) due to the Kelvin effect11; both RF and -DF can be significant. However effective hydrodynamics and regular cleaning can maintain the flux. Sensors and monitors are being developed to provide early warning of membrane fouling. Examples will be provided and include sensors using electrical impedance spectrophotometry12, ultrasound13 and the feed fouling monitor14 so that fouling trends can be predicted. Other methods, such as optical coherence tomography (OCT) provide new insights into fouling phenomena. Overall, improved understanding of fouling phenomena, coupled with rapid detection systems should allow much improved control of membrane fouling. REFERENCES 1. J.S.Zhang et al., J. Membr. Sci., 284, 54-66 (2006). 2. B.D.Cho & A.G.Fane, J. Membr.Sci., 209, 391-403 (2002). 3. E.Akhondi et al., J. Membr. Sci., 456, 77-84 (2014). 4. E.Hoek and M.Elimelech, ES & T.,37,5581-5588 (2003). 5. T.H.Chong et al., J. Membr. Sci., 314, 101-111 (2008). 6. S. Suwarno et al., J. Membr. Sci., 467, 116-125 (2014). 7. R.J.Barnes et al., Biofouling, 29(2), 203-212 (2013); Appl.Env. Microbiol, 81, 2515-2524 (2015) 8. J.S.Zhang et al., J.Membr. Sci., 403, 8-14 (2012). 9. W.Fang et al., J.Membr. Sci., 394-395, 140-150 (2012). 10. S.Zou et al., J.Membr. Sci., 436, 174-185 (2013). 12. L.Sim et al., J.Membr. Sci., 443, 45-53 (2013). 13. V.Sim et al., J.Membr. Sci., 428, 24-37 (2013). 14. A.H.Taheri et al., J.Membr. Sci., 448, 12-22 (2013); 475, 433-444 (2015) 15. T.Li et al., J.Membr. Sci., 455, 83-91 (2014), 505, 216-224 (2016) 16. J.Wang et al., J.Membr. Sci., 498, 105-115 (2016), 510, 38-49 (2016)

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KEYNOTE SPEAKERS

W4.1 PROFESSOR RONG WANG BRINE TREATMENT BY MEMBRANE DISTILLATION CRYSTALLIZATION: NOVEL MEMBRANE DEVELOPMENT, MODULE DESIGN AND OPERATING CONDITION OPTIMIZATION School of Civil and Environmental Engineering, Nanyang Technological University, Singapore 639798, Singapore Membrane Technology Center, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore The concentrated brine generated by reverse osmosis (RO) or other desalination plants may cause critical environmental problem if it cannot be handled properly. The integration of membrane distillation (MD) with crystallization can serve as a potential way to mitigate the problem by having an almost complete water recovery and eliminating the secondary disposal problem.1 Pure water can be recovered in the MD unit and the resultant supersaturation of the soluble salt can serve as a feed solution in the coupled crystallization process from which precipitated solids can be produced for potential use. In this way, the membrane distillation crystallization (MDC) can realize zero discharge of concentrated brine to the environment. Moreover, the supersaturation level can be optimized in MDC, which enables the formation of higher quality crystals than other solid separation technologies such as cooling or evaporation crystallization. However, there are still several challenges to be addressed in order to develop a viable MDC process for concentrated brine treatment, which include: (1) development of novel membranes with high hydrophobicity for MD process; (2) design of membrane modules with high mass transfer efficiency; (3) optimization of operating conditions to prevent crystal deposition on membranes surface. The current MD membranes are subjected to a lower than expected flux due to the lower porosity and mass transfer efficiency, and unsatisfied wetting resistance because of insufficient hydrophobicity. Therefore, we have fabricated nanofiber polyvinylidene fluoride (PVDF) membranes with adjustable thickness, high hydrophobicity, and high porosity by electrospinning.2 Additionally, superhydrophobic nanofiber membranes have been successfully achieved by modifications to optimize the surface morphology and roughness.3 The characterizations revealed that the modifications have altered the membrane surface morphology and topology, and made the membrane superhydrophobic due to their hierarchical structures. Moreover, a novel superhydrophobic membrane consisting of a silica-PVDF composite skin formed on PVDF porous nanofiber scaffold has been developed via electrospinning.4 This fabrication method could be easily scaled up due to its simple preparing procedures. To further improve the mechanical properties of electrospun superhydrophobic membranes, superhydrophobic dual-layer membranes were designed, constructed and compared.5 Figure 1 shows the sample of superhydrophobic silica-PVDF composite membrane. GOLD SPONSOR

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The performance of MD depends on both membrane and module characteristics. MD module configurations, such as fiber length, packing density and the effects of module diameter and flow rates need to be optimized to enhance MD performance.6 Single fiber tests in combination with heat transfer analysis verified that a critical fiber length exists, that is the required length to assure sufficient driving force along the fiber to maintain adequate MD performance. For multi-fiber modules, the overall MD coefficient decreased with increasing packing density, possibly due to flow maldistribution. We also explored the potential of microstructured hollow fiber designs to enhance process performance in a MD system.7 Hollow fibers with 10 different geometries Figure 1. Superhydrophobic silica-PVDF composite membrane. (wavy- and gear-shaped cross sections) were evaluated. It was found that the enhancement of the heat-transfer coefficients was up to 4.5-fold for a module with a wavy fiber design and an approximate 5.5-fold increase for a gear-shaped fiber design. The average temperature polarization coefficient and mass flux of the gear-shaped fiber module showed an improvement of 57% and 66%, respectively, over the original straight fiber design. The enhanced module performance was attributed to the improved hydrodynamics through the flow channels of various fiber geometries. Investigations of the fiber-length effects showed that the gear-shaped fiber modules exhibited the highest flux enhancement of 57-65% with the same length, compared to the modules with original straight and wavy fibers. Furthermore, as an extended exploration of process enhancing strategies, nine modified hollow fiber modules with various turbulence promoters were designed.8 Another major barrier in MDC application is the dramatic flux decline due to the blockage of water transport passage caused by salt crystals deposited on the membrane surface. Therefore, in order to prevent the decrease of water permeation and prolong membrane life in a high concentration MD process, the operating conditions need to be optimized. We have carried out process optimization in the bubbling assisted MD process.9 Due to intensified local mixing and physical flow disturbance in the liquid boundary layer on the feed side, a higher flux enhancement could be achieved in a bubbling system with either a higher feed operating temperature, lower feed and permeate flow velocities, inclined module orientation, shorter fiber length or lower packing density. It was also found that gas bubbling not only enhanced the permeation flux by average 26% when concentrating feed solution from 18% salt concentration to saturation, but also delayed the occurrence of major flux decline due to crystal deposition. Moreover, the bubbles with small mean bubble size and narrow size distribution were preferred for creating even flow distribution, intensifying mixing and enhancing surface shear rate.10 The total water removal for the

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

KEYNOTE SPEAKERS

brine concentration process was significantly improved by 131% and the discharged brine volume was reduced accordingly at appropriately selected gas flow rates. We have also developed a newly established mathematical method, namely, crystallization on membrane surface modeling, to investigate the scaling formation along the operation time and quantify the critical point of a major flux decline.11 In addition, an orthogonal fractional factorial (OFF) experiment design was used to optimize the flow rates and operating temperatures on both the feed and permeate sides to realize a near zero discharge in MDC process.1 It was found that the flow rates on the feed and permeate sides are the principal factors controlling MDC performance, whereas the temperatures either on feed or permeate sides are not main factors. The feed flow rate and inlet temperature had more influence on the mean crystal size and crystal size distribution, whereas the permeate flow rate and inlet temperature had relatively less effect. REFERENCES 1

G. Chen, Y. Lu, W. B. Krantz, R. Wang, A. G. Fane, J. Membr. Sci. 2014, 450, 1-11.

2

Y. Liao, R. Wang, M. Tian, C. Qiu, A. G. Fane, J. Membr. Sci. 2013, 425–426, 30-39.

3

Y. Liao, R. Wang, A. G. Fane, J. Membr. Sci. 2013, 440, 77-87.

4

Y. Liao, R. Wang, A. G. Fane, Environ. Sci. Technol. 2014, 48, 6335-6341.

5

Y. Liao, C.-H. Loh, R. Wang, A. G. Fane, ACS Appl. Mat. Interfaces 2014, 6, 16035-16048.

6

X. Yang, R. Wang, L. Shi, A. G. Fane, M. Debowski, J. Membr. Sci. 2011, 369, 437-447.

7

X. Yang, H. Yu, R. Wang, A. G. Fane, J. Membr. Sci. 2012, 421–422, 258-270.

8

X. Yang, H. Yu, R. Wang, A. G. Fane, J. Membr. Sci. 2012, 415–416, 758-769.

9

G. Chen, X. Yang, R. Wang, A. G. Fane, Desalination 2013, 308, 47-55.

10 G. Chen, X. Yang, Y. Lu, R. Wang, A. G. Fane, J. Membr. Sci. 2014, 470, 60-69. 11 G. Chen, Y. Lu, X. Yang, R. Wang, A. G. Fane, Ind. Eng. Chem. Res. 2014, 53, 15656-15666.

RONG WANG Professor, PhD Chair, School of Civil and Environmental Engineering, Nanyang Technological University, Singapore 639798 Director, Singapore Membrane Technology Center (SMTC), Nanyang Environment and Water Research Institute (NEWRI) Nanyang Technological University, Singapore 637141 Phone: +65 6790-5264/5327 Fax: +65 6791 0756 E-mail: [email protected] Personal History: Associate Professor/Professor, Nanyang Technological University Deputy Director/Co-director/Director, Singapore Membrane Technology Center, Nanyang Environment & Water Research Institute, Nanyang Technological University Senior Research Scientist/Group Leader/Deputy Centre Director/Centre Director, Institute of Environmental Science & Engineering (IESE), Singapore Assistant Professor/Associate Professor, Institute of Process Engineering (IPE), CAS, China Editor - Journal of Membrane Science Editorial Board Member – Desalination Founding President, Membrane Society in Singapore Research interests: membrane science & technology, chemical & environmental engineering processes

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W2.10 PROFESSOR ERIC M.V. HOEK ADVANCES IN MEMBRANE FILTRATION: CERAMIC MEMBRANES, POLYMERIC MEMBRANES AND INTELLIGENT CONTROLS Water Planet, Inc. Over the past two decades, membrane filtration has proliferated globally to become the gold standard for removing pathogens, suspended solids, emulsified oils and colloids from virtually every type of water source – traditional and non-traditional, fresh and saline. Hence, everywhere nanofiltration (NF) and reverse osmosis (RO) membranes are used – and – anywhere filtration or clarification is required microfiltration (MF) and ultrafiltration (UF) membranes are now considered. Globally, about 90% of membrane installations for municipal water and wastewater utilize polymeric hollow fiber membranes (with some exceptions, but) predominantly made from either poly(ethersulfone), PES, or poly(vinylidene fluoride), PVDF. Industrial wastewaters are treated with PES/PVDF hollow fiber MF/UF membranes, but also with fabric supported flat-sheet PES/PVDF or poly(acrylonitrile), PAN, membranes in various module form factors (spiral-wound, plate-and-frame, rotating, vibrating, etc.) and ceramic membranes predominantly made from stainless steel, metal-oxides (alumina, titania, zirconia, silica) or silicon-nitride in the form of multi-channel flat plates or cylindrical monolithic elements. Generally, ceramic modules cost 10-20X more per unit area of membrane than polymeric modules, and because ceramic system wetted parts are constructed from stainless or higher grade steel (pumps, vessels, header/footer pipes, valves, etc.) system costs are about 4-5X more than polymer membrane systems. However, ceramic membranes are more fouling tolerant, thermally and chemically stable, clean up easier and last longer than polymerics, so there are new scenarios emerging where overall life cycle costs may be comparable for polymerics and ceramics. Generally, MF/UF membranes suffer from two key limitations – fouling and integrity. Membrane integrity issues are somewhat specific to hollow fiber filters in municipal applications, where fiber breakage can be a frequent occurrence and significant operating costs are incurred due to the labor and downtime associated with integrity testing and fiber pinning. This is exacerbated for high fouling feed waters where frequent backwashing and cleaning are required to combat flux decline, where the mechanical limits of hollow fibers are overextended during flux maintenance actions (backwashing and cleaning). Over time, MF/UF plant capacities can drop off significantly due to fouling and fiber pinning. All MF/UF membranes foul, increasing downtime, cleaning and OpEx. This talk will review state-of-the-art and emerging MF/UF technologies including ceramic membranes, novel polymeric membranes and advanced control strategies all of which promise next-generation improvements for MF/UF membranes.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

KEYNOTE SPEAKERS

W1.15 PROFESSOR HIDETO MATSUYAMA IONIC LIQUID-BASED FACILITATED CO2 TRANSPORT MEMBRANE WITH HIGH PRESSURE RESISTANCE

HIDETO MATSUYAMA, FARHAD MOGHADAM, EIJI KAMIO, AYUMI YOSHIZUMI Center for Membrane and Film Technology, Department of Chemical Science and Engineering, Kobe University INTRODUCTION

Recently, we developed a new class of facilitated CO2 transport membranes containing CO2 reactive amine-functionalized ionic liquids as the CO2 carrier.1-3 Among several amine-functionalized ionic liquids, amino acid ionic liquids (AAILs) demonstrated superior CO2 permeation properties in wide relative humidity range including dry atmosphere at elevated temperature.2 To utilize the AAIL-based facilitated transport membranes under pressurized conditions, we also fabricated gel membranes containing a large amount of AAIL.4 Although AAIL-based gel membranes showed good CO2 separation performances, the mechanical strength of the AAIL-based gel membrane was not high enough. Because of the low mechanical strength of the gel membrane, it was hard to use the gel membrane under pressurized conditions. Moreover, the low mechanical strength of the gel membrane hinders the preparation of thin gel membranes. Although an AAIL-based gel membrane with good mechanical strength could be prepared by increasing the gel network composition in the membrane, there is a trade-off between the mechanical strength and the gas permeability of the gel membrane; i.e. the CO2 permeability decreased due to the enhancement of the diffusion resistance of the gel membrane when the gel network composition was increased to enhance the mechanical strength of the membrane. To overcome the trade-off and to fabricate a thin gel membrane with a large amount of AAIL, we propose the utilization of a specific gel network with excellent toughness, so-called double-network (DN).5 Here, we present the tough AAIL-based DN gel membrane with excellent mechanical strength and good CO2 separation performance which can be used under a pressurized conditions.6 EXPERIMENTAL

As the AAILs, tetrabutylphosphonium prolinate ([P4444][Pro]) and triethyl(pentyl) phosphonium prolinate ([P2225][Pro]) were used as the CO2 carriers of the DN gel membranes. The DN gel membranes were prepared via the following multi-step preparation method; a DN hydrogel film consisting of poly(2-acrylamido-2methylpropanesulfonic acid), (PAMPS) and polydimethylacrylamide (PDMAAm), was fabricated according to the procedure5 and it was immersed in an aqueous solution

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containing the AAIL ([P4444][Pro] or [P2225][Pro]) to impregnate AAIL in the DN gel matrix. The gel membrane containing the AAIL aqueous solution was finally dried at 373 K under vacuum for 8 h to completely remove the water in the gel. The CO2 permeability of the DN ion gel membranes was measured by a sweep method. RESULTS AND DISCUSSION

The DN ion gel membranes with different AAIL contents were prepared using aqueous solutions with different concentrations of AAILs. The AAIL content in the prepared gel membranes reached up to 80 wt% and became constant as the AAIL concentration in the aqueous solution increased. It is worth pointing out that even DN gel membranes containing up to 80 wt% AAIL were mechanically strong. The facilitated CO2 transport was confirmed based on the CO2 partial pressure dependency on the CO2 permeabilities for the [P4444][Pro]-based and [P2225][Pro]-based DN ion gel membranes with various AAIL contents. One of the most outstanding features of the AAIL-based DN gels is the extraordinary mechanical strength. We measured the fracture stress of the DN ion gels consisting of [P4444][Pro] and [P2225][Pro] with different contents. It is worth mentioning that even the DN ion gels with ca. 80 wt% of AAIL were not broken under compression stress of more than 25 MPa, which was more than 25 times higher than those previously fabricated [P4444][Pro]-based ion gels consisting of PVP and PDMAAm single networks.4 During compression, no AAIL leakage from the gel network was observed as a consequence of large gel osmotic pressure of the PAMPS network and good compatibility between PDMAAm and the AAILs. Fig. 1 demonstrates the pressure resistance of the AAIL-based DN gel membranes containing ca. 80 wt% of [P4444][Pro] and [P2225][Pro]. The pressure resistance was evaluated at 373 K and a constant permeate side pressure (atmospheric pressure) through changing the feed side pressure from 100 to 500 kPa. As clearly indicated in Fig. 1, the AAIL-based DN ion gel membranes withstood pressurized conditions due to their tough DN structure. The CO2 permeability, N2 barrier property, and CO2/N2 selectivity for both AAIL-based DN gel membranes remained constant at a high level for the whole range of trans-membrane pressure differences up to at least 400 kPa. The observed CO2 permeability and CO2/N2 selectivities were more than 4000 Barrer and 100, respectively. In addition, the AAIL-based DN ion gel membranes showed stable CO2 and N2 permeabilities for 5 days at elevated temperatures (at 373 K) under pressurized conditions (500 kPa at feed side). Owing to the excellent mechanical strength of the tough AAIL-based DN ion gel, it has the potential to be fabricated in a thinner form with high CO2 permeability. We prepared thinner AAIL-based DN ion gel membranes and measured the CO2 and N2 permeances. In the investigation, [P4444][Pro] was used as the carrier. The CO2 partial pressure dependency on the CO2 and N2 permeances (GPU) for the thinnest AAILbased ion gel membrane (58 mm) prepared in this study are shown in Fig. 2 along with those for the thick AAIL-based DN ion gel membrane (600 mm) and the supported ionic liquid membrane with [P4444][Pro] (37 mm). The CO2 permeance of the thinner

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AAIL-based DN ion gel membrane was much higher than that of the thick one. In addition, the CO2 permeance was almost identical to that of the SILM, although the ion gel membrane was thicker than the SILM. This result indicates that the diffusion resistance in the DN ion gel network is smaller than that of the porous support used for the AAIL-SILM owing to the low polymer content in the DN ion gel membrane. CONCLUSIONS

In this study, we demonstrated the advanced properties of AAIL-based DN ion gel membranes with respect to CO2 separation. The prepared membranes were tough and had high pressure resistance as well as high CO2 permeability and CO2/N2 selectivity. The high and selective CO2 permeation properties, the superior pressure resistance, and the long term durability of the AAIL-based DN ion gel membranes make them an attractive option for a broad range of CO2 capture applications. REFERENCES 1 S. Hanioka et al., J. Membr. Sci., 2008, 314, 1-4 2 S. Kasahara et al., Chem Commun., 2012, 48, 6903-6905 3 S. Kasahara et al., Ind. Eng. Chem. Res., 2014, 53, 2422-2431 4 S. Kasahara et al., Chem Commun., 2014, 50, 2996-2999 5 J. P. Gong et al., Adv. Mater., 2003, 15, 1155-1158 6 F. Moghadam et al., Chem Commun., 2015, 51, 13658-13661

HIDETO MATSUYAMA Professor Kobe University, Japan Phone: +81-78-803-6180 Fax: +81-78-803-6180 E-mail: [email protected] 1994-98

Lecturer, Okayama University.

1998

Associate Professor, Okayama University.



1998- 2004 Associate Professor, Kyoto Institute of Technology. Professor, Kobe University 2007

Director of Center for Membrane and Film Technology

Research interests: Membrane technology for water treatment and gas separation.

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The PoroluxTM range of instruments from PorometerTM for measuring pore size distribution, bubble point, gas and liquid permeability.

Membrane Characterisation

Capillary flow porometry technology (CFP) Gas/liquid pressure scan porometry Half-dry curve Bubble point Smallest pore size Mean flow pore diameter Gas permeability Cumulative filter flow (SUM) Differential filter flow (DIF) Pore size flow distribution (CDIF)

Measurement Methods The pressure scan method - pressure increases at a constant rate providing immediate continuous measurement of both pressure and gas flow - suited for quality control work for speed and reproducibility. The pressure step / stability method - pressure is increased in different steps, at each pressure step, both pressure and flow are monitored and data point taken when stabilisation criteria are met - suited for R&D work with complex pore structure samples for precision and accuracy.

Applications Flat sheet membranes, hollow fibre membranes, filters, nonwovens, papers, and ceramics, amongst other.

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www.scientex.com.au email [email protected] phone +61 3 9899 6100

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

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T3.1 DR KEN R MORISON MEMBRANES IN DAIRY, JUICE AND BEVERAGE PROCESSING Department of Chemical and Process Engineering, University of Canterbury, Christchurch, New Zealand Over about 4 decades many membrane filtration processes have been adopted by the dairy industry and to a less extent by other food and drink industries. Over this time the dairy industry has used a relatively small selection of membrane types, such as the spiral wound asymmetric polythersulfone for ultrafiltration of whey and the FT30 type aromatic polyamide spiral membrane for reverse osmosis concentration of various dairy liquids. The characteristics of these are well known and multistage processes have been designed for cost-effective separations such as near-farm concentration of milk and standardisation of the protein content of milk. Well-proven advances are probably required before significant changes are made by the industry. Several academic researchers have shown superior properties of fruit juices concentrated by reverse osmosis. However, the consumer move away from “not-from-concentrate” juices has reduced the demand for concentrates from existing evaporation-based processes, and hence there have been few opportunities for growth using membrane processes. In contrast the wine and beer KEN R MORISON Associate Professor Department of Chemical and Process Engineering, University of Canterbury, Christchurch, New Zealand E-mail: [email protected] 1980

BE (chem), University of Canterbury

1984

PhD (Lond) in process control at Imperial College

1984-1991

Research Engineer, NZ Dairy Research Institute

1991-1994

Senior Technical Officer, Anchor Products, Hautapu dairy factory

1994-present Senior Lecture/Associate Professor, University of Canterbury 2010-2016

Editor-in-Chief of Food and Bioproducts Processing

Research interests: Dairy process design, Evaporation, Membrane separations, Milk fouling, Cleaning, Concentrated solutions of sugars, Physical properties of foods.

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T1.8 DR KIM E. JELFS STRUCTURE PREDICTION OF AMORPHOUS MOFS AND POROUS ORGANIC POLYMER MEMBRANES

JAMES. W. BLOOD,1 QILEI SONG,2 THOMAS D. BENNETT,3 ANDREW G. LIVINGSTON,2 KIM E. JELFS,1 1 Department of Chemistry, Imperial College London, South Kensington, London 2 Department of Chemical Engineering, Imperial College London, South Kensington, London 3 Department of Materials Science and Metallurgy, University of Cambridge, Cambridge The synthetic search space for organic polymer membranes is enormous and many precursors can be costly and time-consuming to produce. Chemical intuition of precursors that can enhance free volume can fail,1 demonstrating the need for predictive modelling. Therefore, computational simulations to predict performance prior to synthesis are valuable and we have recently demonstrated their viability.1 Additionally, through analysis of the polymers, we can also provide insight as to how microscopic features of the polymers relate to observed membrane performance. We will discuss application of this modelling approach2 to the design of high-permeance porous organic polymers, related to polymers of intrinsic microporosity (PIMs) for separation applications as membranes.1 Here we have shown that simulations of the polymers can predict their separation performance through prediction of how monomer structure influences the interconnectivity of the pores formed, as shown in Fig. 1. Further, we explore the structural features such as the window sizes formed within the systems and also the degree to which dynamic motion of the structure can influence their performance. We believe the fundamental insight offered by studying this emerging class of materials is critical for uncovering their potential applications. In addition to discussing this series of organic polymers, we will discuss amorphous metalorganic frameworks. Amorphous MOFs can be obtained through melt-quenching the hybrid frameworks to obtain a glass. The porosity and properties of such MOF glasses is poorly understood compared to that of crystalline materials. In part, this is due to the difficulty in obtaining a molecular level understanding of their structure, as it is not possible to collect a X-ray diffraction crystal structure. Both the molecular modelling and positron annihilation lifetime spectroscopy found the porosity of agZIF-4 to be intermediate between the open and dense crystalline forms ZIF-4 and ZIF-zni.3 Here we will discuss the extension of this approach to a series of amorphous MOFs, including MOF-5, UiO-66, ZIF-8 GOLD SPONSOR

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Figure 1. The amorphous structure of a porous organic polymer (left), with voids shown in blue. The interconnectivity of the voids in the polymer model (right), interconnected voids for nitrogen are shown in green and disconnected voids in red.

and HKUST-1. This will allow us to explore the potential porosity of these systems and to understand the key structural features that can influence their potential application as hybrid glasses for electronic, thermal or ionic conduction or separation membranes. REFERENCES 1. M. F. Jimenez-Solomon, Q. Song, K. E. Jelfs, M. Munoz-Ibanez, A. G. Livingston, Nature Materials 2016 DOI: 10.1038/nmat4638. 2. L. J. Abbott, K. E. Hart, C. Colina, Theor. Chem. Acc. 2013 132 (3), 1334. 3. A. W. Thornton, K. E. Jelfs, K. Konstas, C. M. Doherty, A. J. Hill, A. K. Cheetham, T. D. Bennett, Chem. Commun. 2016 52, 3750

DR. KIM JELFS Department of Chemistry, Imperial College London, South Kensington, London, SW7 2AZ Phone: +44 2075943438 Fax: +44 2075943438 E-mail: [email protected]

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T3.8 PROFESSOR KARIN SCHROËN PARTICLE MIGRATION USED AS A BASIS FOR EFFICIENT SEPARATION AND FRACTIONATION -MEASUREMENTS, MICROSTRUCTURES, MODELING

KARIN SCHROËN1, I. DRIJER1,2, TIES VAN DE LAAR1,3, ANNA VAN DINTHER4, JORIS SPRAKEL3 1 Wageningen University, Food Process Engineering group, Bornse Weilanden The Netherlands. 2 Veco B.V., Karel van Gelreweg The Netherlands. 3 Wageningen University, Laboratory of Physical chemistry and Soft matter, Stippeneng 4 The Netherlands. 4 Danone Research, Uppsalalaan The Netherlands. It feels exaggerated to mention in an abstract for IMSTEC 2016, that microfiltration is important; but the point that we would like to make is that ‘microfiltration processes’ could be used much more efficiently if particle behaviour were taken as starting point of design, and unconventional approaches were considered. We concluded this based on experiments carried out with membranes, and microfluidic devices in which various mechanisms could be visualised, and computer modelling, which in turn lead to guidelines for process design. During filtration particles are carried toward a membrane by convective permeate flow, that is what everyone knows, but what is not that appreciated yet is that particles (also if they are > 1 micron) show diffusive behaviour that may facilitate filtration processes. This can be as an individual particle that is exposed to a velocity gradient in a laminar field (inertial lift) or as a ‘collective of particles’ in which they experience the movements of other particles (shear induced diffusion), and besides the particle can skim across a pore. We will elaborate on shear-induced diffusion1, inertial lift, and fluid-skimming2, and give examples for model systems (experimental and modelling), and also foods. The underlying mechanisms for particle movement are not that well understood, and this can be greatly facilitated through computer modeling. For the description of particle migration, complex modeling is applied, but here we use fluid dynamics software (STARCCM+), in which particle-particle interactions of monodisperse particles are incorporated by adding momentum terms to the general momentum equation3. We found that our model describes the experimental results, to a high level of detail (see figure 1; examples of velocity (a) and concentration gradients (b)). Our findings are also in reasonable agreement with other experimental and modelling studies from literature; the discrepancies most probably due to non-ideal behavior in the experiments. GOLD SPONSOR

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Figure 1a: Normalised particle volume fraction vs. relative channel height, for øbulk=0.5. Experimental results (□); model results (line)3. b, middle: Velocity vs. the relative channel height, for øbulk==0.3. Experimental results (□); model results (line)3. c, right: typical image obtained for a bi-disperse liquid flowing from left to right, in which the centre is enriched in large particles (green)4.

We also investigated bi-disperse gel beads, and monitored particle segregation in flow using micro channels in combination with fast imaging (figure 1c). Even at concentrations close to jamming, large particles preferentially move toward the middle of the channel, while small ones are much closer to the wall4. We tested if this effect could be used this using metal sieves with uniform pores [Stork BV, the Netherlands] (figure 2a5). For this, we used a closed channel to allow for particle migration to take place, followed by a porous region. The particles do not deposit on the membrane, and the pores (~20 micron) are much larger than the particles. This allows us to take out a certain amount of liquid either without removing particles, or only removing a certain size category. In this abstract we only show results of two concentration ranges: below 5% for skimming, and 20-55% for shear induced diffusion, but the presentation will cover the entire range. Our starting point was to use process conditions (cross-flow velocity / shear rate, and transmembrane pressure) that we identified as suitable for prevention of particle deposition based on theoretical considerations. This allowed us to control the size of the droplets/particles in the permeate at fluxes comparable as those used in regular microfiltration as described next. In experiments with suspensions of 20-50% (e.g. figure 2b), we found that shear-induced diffusion facilitates fractionation1 of particles that are very close in size (2 versus 3.5 micron). The transmission of 2 and 3.5 micron particles as function of Θ, which is the ratio of crossflow velocity and trans membrane velocity shows that it is possible to only separate small particles from the mixture. At low Θ, small particles are easily transmitted and large particles are retained completely. At high =Θ, the size of the permeate particles is equal to that in the feed1. For particle concentrations <5%2, all experimental data converged into a master curve typical for skimming behaviour2. When using raw milk (milk fat globules 0.1 to 15 micrometer) as a feed, also skimming occurred as illustrated in figure 2c, in which the 90% point of the milk fat globule distribution is plotted as function of the ratio of flux and cross flow velocity. The permeate contained considerably smaller particles than the feed

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Figure 2a. Metal sieves with uniform pores5. 2b. Example of particle fractionation with sieves: at low ratio of transmembrane flow and cross-flow (Θ), only small particles of 2 micron can be found in the permeate (open symbols) while the large ones (3.5 micron; filled symbols) are completely retained. 2c. Typical result obtained for fractionation of milk fat droplets (0.1-15 micron), with the ratio of flux and cross flow velocity on the x-axis, and the 90% point of the droplet size on the y-axis; the horizontal line denotes the droplet size in the feed.

(horizontal line), and although the size increased with increasing flux, it is considerably smaller than in the feed. Various other particles (e.g. yeast, emulsions, gel particles, hard particles) were also tested and we found that both shear-induced diffusion and fluid skimming have a positive effect on separation behavior. The conditions that we use are also less energy consuming, compared to regular microfiltration, and we are convinced that designing filtration-based separation technology using particle transport as a starting point can lead to a new generation of separation devices . To achieve this, modeling is an important tool not only to chart particle behavior, but also to derive guidelines for process and membrane design that we will share with you in Adelaide. REFERENCES 1. AMC Van Dinther, CGPH Schroën, RM Boom: Particle migration leads to deposition-free fractionation. Journal of Membrane Science 2013, 440:58-66. 2. AMC Van Dinther, CGPH Schroën, RM Boom: High-flux membrane separation using fluid skimming dominated convective fluid flow, Journal of Membrane Science, 2011, 371 (1-2). - p. 20 - 27. 3. I Drijer, T van de Laar, K Schroen: From highly specialised to generally available modelling of shear induced particle migration for facilitated microfiltration. Submitted for publication, 2016. 4. T Van De Laar, K Schroën, J Sprakel: Cooperativity and segregation in confined flows of soft binary glasses. Physical Review E - Statistical, Nonlinear, and Soft Matter Physics 2015, 92(2):022308. 5. Stork Veco: http://www.vecoprecision.com

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T4.8 DR OLGICA BAKAJIN FORWARD OSMOSIS: A NEW TOOL TO MINIMIZE WASTE AND REUSE WATER FROM CHALLENGING WASTE STREAMS Forward osmosis (FO) is the osmotically-driven purification of water using a semipermeable membranes. Although FO has been studied for decades, it has only recently obtained broader commercial adoption. FO has unique advantages for water reuse and ultra-high salinity desalination because it can operate reliably when processing challenging liquids that quickly clog or foul other types of membranes, such as RO. FO membranes are a new “tool” in the water treatment toolbox that are useful for multiple applications and processes. This new technology provides unique advantages in oil and gas, mining, food and beverage, and potable reuse applications. This talk will present: 1) an introduction to FO technology, 2) examples of energy saving applications, and 3) unique cost, environmental, and other benefits resulting from appropriate use of this technology.

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T1.9 PROFESSOR RYAN LIVELY LIGHT GAS SEPARATIONS USING PIM-1 HOLLOW FIBER SORBENTS AND MEMBRANES

SIMON PANG, MELINDA JUE, JOHANNES LEISEN, VICTOR BREEDVELD, CHRISTOPHER JONES, RYAN LIVELY* School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta GA, USA New materials for separations are constantly being developed to improve upon the current state-of-the-art. One emerging class of materials that has garnered sustained interest are microporous polymers. Polymers of intrinsic microporosity (PIMs) have highly rigid backbones that lead to a number of favorable properties, particularly for gas separation applications. Polymer of intrinsic microporosity 1 (PIM-1) is the prototypical microporous polymer that has been studied extensively due to its relatively high surface area, high gas permeabilities, good selectivities, and solution processability. Current research on PIMs has been exclusively performed on powders and flat sheet membranes to understand fundamental polymer and membrane properties. To bridge the gap between the development of new high performance polymers and actual molecular separation systems, more advanced membrane and adsorption contactor units need to be engineered. Hollow fiber membranes and sorbents fulfill this need by combining large surface areas, excellent pressure resistance, and highly scalable fabrication in small volume, modular units. In the membrane literature to date, only dilute PIM-1 containing hollow fiber membranes have been made, partly due to the somewhat unfavorable solubility properties of the polymer. We will first discuss the fabrication of defect-free hollow fiber membranes derived purely from PIM-1. These membranes have been characterized for their separation performance under a variety of conditions and are in good agreement with their flat sheet analogs. More broadly, this work details a method of going from synthesis of a non-commercially available polymer with limited solubility properties to spinning a hollow fiber membrane. In the second part of the talk, we will discuss the use of PIM-1 as a promising adsorbent material. A large body of work exists that seeks to (i) develop the science of supported amine adsorbent materials and (ii) deploy these materials in CO2 capture applications. The vast majority of this work has considered amine molecules or macromolecules supported on hard porous materials, such as porous silica or alumina. While such materials can give high CO2 uptakes and good adsorption kinetics, they are very difficult to utilize in practical adsorption applications due to difficulty in contacting large volumes of CO2-laden gases with powder materials without significant pressure drops or adsorbent attrition. A simple approach based on the impregnation of PIM-1 fibers with poly(ethylene imine) for CO2 capture from dilute streams such as flue gas or ambient air will be discussed. By using PIM-1, we completely remove the need for use of hard oxides such as silica or alumina. We will demonstrate that these new materials have comparable performance to traditional powder silica or alumina adsorbents, with the benefit that PIM-1 is soluble in common solvents, making it eminently more viable for processing into morphologies that can facilitate rapid heat and mass transfer and fabrication into low pressure drop contactors GOLD SPONSOR

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W2.9 ASSOCIATE PROFESSOR MAINAK MAJUMDER GRAPHENE-BASED MEMBRANES: SCALABLE MANUFACTURING AND TARGETED PRODUCT DEVELOPMENT Graphene-based membranes demonstrating ultra-fast water transport, precise molecular sieving of gas and solvated molecules shows great promise as novel separation platforms; however scale-up of these membranes to large-areas remains an unresolved problem. We have recently demonstrated that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industriallyadaptable method to produce large-area membranes (13 × 14 cm2 ) in less than 5 seconds1. The membranes have several potential applications such as softening of water as a pre-treatment to reverse osmosis membrane treatment, separation of natural organic matter as a means to reduce the formation of halogenated organics & desalting of lactose rich dairy waste streams. The critical advantages of the graphene membranes developed in this program are enhanced mechanical and chemical stability, ability to be cleaned and reused multiple times and very high flux compared to commercial membranes. Despite these advantages, critical challenges remain in establishing niche and high value applications, initiating manufacturing ventures in the Australian innovation system, product development from membranes to membrane modules through strategic partnerships with national and international alliances, and system-level demonstrations to meaningfully engage end-user industry. REFERENCES 1. Akbari, A. et al. Large-area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide. Nat. Commun. 7:10891 doi: 10.1038/ ncomms10891 (2016).

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T3.9 PROFESSOR XIA HUANG SYNERGISTIC INTERATION BETWEEN SOLUBLE MICROBIAL PRODUCTS AND MEMBRANE MATERIAL DURING FOULING EVOLUTION OF MBRS

XIA HUANG1, KANG XIAO1,2, HUIJU FAN1, YUEXIAO SHEN1 1 State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China 2 College of Resources and Environment, University of Chinese Academy of Sciences, Beijing 100049, China Membrane fouling remains a major challenge for the application of membrane bioreactor (MBR) to wastewater treatment and reclamation. A prime group of foulant is colloidal and soluble organics contained in MBR sludge supernatant, mainly contributed by soluble microbial products (SMPs). These organics can participate in the fouling evolution of membrane pore blocking and gel layer formation, and cause irreversible fouling. Hydrophilic/ hydrophobic fractions, molecular weight distribution, functional groups of SMPs are highly involed in the fouling evolution. On the other hand, membrane material properties should be of prime importance to membrane fouling evolution. The physicochemical property of membrane hydrophobicity, together with the structural properties of pore size and pore morphology, have been referred to as fouling factors in the literature1,2. The rapidity and irreversibility of fouling evolution is largely governed by interation between SMPs and membrane material. In order to obtain useful hints on fouling control, it would be of great importance if the interation could be systematically investigated. In this study, supernantant samples from full-scale MBR plants for municipal wastewater treatment were firstly fractionated as hydrophilic substances (HIS), hydrophobic acids (HOA), hydrophobic bases (HOB), and hydrophobic neutrals (HON)3,4. The properties of the fractions were further characterized in terms of mass composition, molecular size (weight), functional group, and metal complexing ability. The fouling evolution of SMP samples with different properties were systematically evaluated by using membranes with different hydrophobicity, pore size and pore morphology5,6. The mechanisms of synergistic interation between SMPs and membrane material during fouling evolution were finally elucidated. REFERENCES 1 K. Xiao, X. Wang, X. Huang, et al. J. Membr. Sci., 2011, 373, 140–151. 2 X. Xiao, Y. Shen, X. Huang, J. Membr. Sci., 2013, 427, 139–149. 3 Y. Shen, K. Xiao, P. Liang, et al. J. of Mem. Sci., 2012, 415–416, 336–345 4 J. Sun, K. Xiao, X. Yan, et al. Process Biochemistry, 2015, 50, 2224–2233. 5 K. Xiao, J. Sun, Z. Fang, et al. Desalination, 2014, 343, 217–225. 6 K. Xiao, Y. Shen, S. Liang, et al. J. Membr. Sci., 2014, 467, 206–216. GOLD SPONSOR

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T4.9 DR EDDY OSTARCEVIC HARVESTED WATER CHARACTERISTICS IN THE CSG INDUSTRY AND THE ROLE OF REAL TIME MEMBRANE INTEGRITY MONITORING Harvesting Coal Seam Gas (CSG) requires a significant volume of groundwater to be extracted and treated using brackish water desalination. Water characterisation is extensive and water industry practitioners examine the elements and compounds that are responsible for scaling and fouling in brackish water desalination applications. This is after all the most important criteria to determine the key design and operating parameters, isn’t it? What about the elements and compounds that can significantly impact the integrity of membranes, the hidden chemistry? How can membrane integrity be monitored on line and in real time to determine integrity challenges and be used as an operational tool to determine when membrane change out is required or identify discrete membrane failure. This presentation will provide an insight into the hidden chemistry pathways that practitioners need to include in their knowledge database and a recently developed real time integrity monitoring technique for high pressure membranes.

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T1.14 DR RUILAN GUO HIERARCHICALLY FUNCTIONAL IPTYCENECONTAINING POLYMERS FOR GAS SEPARATION MEMBRANES Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, USA New generations of robust polymeric membranes are needed by the chemical industry to perform fast and selective molecular separations in a wide range of environments with improved energy efficiency and cost effectiveness. The key to a successful membrane gas separation system is the membrane materials featuring ultra-fast and highly selective transport properties combined with good chemical, mechanical, and thermal stability in the complex feed stream and good processability. This talk will present our recent efforts of developing a new family of iptycene-containing polymers as gas separation membranes, based on a novel concept of internal free volume and supramolecular chain threading/interlocking mechanism that are uniquely associated with iptycene moieties. Iptycenes, such as triptycene and pentiptycene, are fused aromatic structures with rigid, shape-persistent configurations. The rich structural hierarchy and functionalization versatility of iptycenes offer unique opportunities for generating well-defined and tailorable molecular cavities as well as favorable supramolecular inter-chain interactions that enable fast and selective molecular transport to meet various separation needs. Representative series of iptycene-containing polymer membranes, each exploiting a unique structural/functional motif to achieve favorable transport properties, will be discussed. Specifically, size-selective iptycenebased glassy polyimides and polybenzoxazoles, and CO2-selective iptycene-PEO segmented copolymers will be presented, with a focus on how to exquisitely tune the molecular structure/architecture and the supramolecular interactions of iptycene units to promote selective and effective gas transport in these novel polymeric membranes.

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T2.14 PROFESSOR GREG LESLIE INTERFACES IN URBAN METABOLISM: THE ROLE OF MEMBRANES IN THE RECOVERY OF ENERGY, WATER AND NUTRIENTS IN THE URBAN WATER CYCLE UNESCO Centre for Membrane Science and Technology at the University of New South Wales The concept that cities and urban centre’s possess a metabolism comparable to cellular organisms is well established. Every day flux of energy, nutrients and water entering the environment is exchanged with stream of waste and emissions discharged from the environment. Adapting urban metabolism to the constraints imposed by the availability of land, water and essential nutrients such a phosphorous, coupled with limitations on emission of greenhouse gasses and the consumption of energy has forced urban communities to upgrade water and wastewater infrastructure to systems that occupy less space and can recover water, nutrients and energy. Engineered interfaces, including membranes, photocatalytic and adaptive surfaces are essential components of the infrastructure which underpins public health, economic activity and quality of life in our cities. This presentation will illustrate how numerical techniques including computational fluid dynamics, molecular simulations and life cycle assessment can be used to identify and optimize modern treatment systems that rely on engineered interfaces for water and wastewater treatment.

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T3.14 DR LISENDRA MARBELIA RECENT DEVELOPMENTS IN MEMBRANE FOR BIOREACTORS KU Leuven University, Belgium Two membrane applications will be presented in this talk, i.e. microalgae filtration and enzyme biocatalytic reactors. For microalgae, membranes have been explored to be applied in different stages for its cultivation and processing1. Membrane application in photobioreactors allows to limit the microalgae wash-out, so that higher biomass concentrations and volumetric productivities can be achieved2. Membrane fouling during microalgae filtration is influenced by the operation mode, the properties of the membranes (surface charge and porosity) and of the microalgal broth properties. It was also shown that fouling in microalgae filtration is dominated by the formation of a cake layer by the cells which is mainly influenced by cell shape and size, size distribution, and cell-wall rigidity3. For enzyme biocatalytic membrane reactor, a recent development using biofunctionalized magnetic nanoparticles and a magnetic responsive hybrid membrane is exploited to develop a nano-inspired, magnetic-responsive enzyme membrane (micro) reactor4. The novelty of the process lies in the use of superparamagnetic nanoparticles both as enzyme carrier to form bionanocomposites and as nanofiller to form organic– inorganic (O/I) hybrid membrane to render both reversibly magnetizable. This reversible magnetic force facilitates dispersion of the enzymatically active magnetic nanoparticles (bionanocomposites) over the membrane surface, allows retention of the enzyme by a large pore, i.e., high-flux membrane and renders enzyme recovery after use is very easy. The feasibility and versatility of the concept is demonstrated for membrane fouling prevention through in-situ enzymatic membrane cleaning, which reduced filtration resistance by more than 75%5,6. REFERENCES 1 Bilad, M.R., Arafat, H.A., Vankelecom, I.F.J., 2014. Membrane technology in microalgae cultivation and harvesting: A review. Biotechnol. Adv. 32(7), 1283-1300. 2

Marbelia, L., Bilad, M.R., Passaris, I., Discart, V., Vandamme, D., Beuckels, A., Muylaert, K., Vankelecom, I.F.J., 2014. Membrane photobioreactors for integrated microalgae cultivation and nutrient remediation of membrane bioreactors effluent. Bioresour. Technol. 163, 228–35.

3

Marbelia, L., Mulier, M., Vandamme, D., Muylaert, K., Szymczyk, A., Vankelecom, I.F.J., 2016. Polyacrylonitrile membranes for microalgae filtration: Influence of porosity, surface charge and microalgae species on membrane fouling. Algal Res. 19, 128–137.

4 Gebreyohannes, A.Y., Bilad, M.R., Verbiest, T., Courtin, C.M., Dornez, E., Giorno, L., Curcio, E., Vankelecom, I.F.J., 2015. Nanoscale tuning of enzyme localization for enhanced reactor performance in a novel magnetic-responsive biocatalytic membrane reactor. J. Memb. Sci. 487, 209–220. 5 Gebreyohannes A.Y., L. Giorno, I.F.J. Vankelecom, T. Verbiest, P. Aimar, 2017. Effect of operational parameters on the performance of a magnetic responsive biocatalytic membrane reactor, Chemical Engineering Journal 308, 853-862. 6

Gebreyohannes A.Y., R. Mazzei, T. Poerio, P. Aimar, I.F.J. Vankelecom, L. Giorno, 2016. Pectinases immobilization on magnetic nanoparticles and their anti-fouling performance in a biocatalytic membrane reactor, RSC Advances 6, 98737-98747. GOLD SPONSOR

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T4.14 PROFESSOR STEPHEN GRAY SMALL SCALE POTABLE WATER RECYCLING

JIANHUA ZHANG1, KATHY NORTHCOTT2, MICHAEL PACKER3, GRAEME ALLINSON4, MAYUMI ALLINSON5, MIKEL DUKE1, PETER SCALES5, STEPHEN GRAY1 1 Institute for Sustainability and Innovation, Victoria University, Melbourne, Victoria, Australia, 2 Veolia, Australia-New Zealand, Bendigo, Victoria, Australia, 3 Australian Antarctic Division, Kingston, Tasmania, Australia, 4 RMIT University, Victoria, Australia 5 The University of Melbourne, Victoria, Australia Wastewater discharge from Davis Station, Antarctica was shown to have an environmental impact on the pristine environment of the Antarctic Ocean1. Upgrading wastewater treatment to remove pathogens and chemicals of concern required an Advanced Water Treatment Plant (AWTP) following biological wastewater treatment, which presented the opportunity for recycling of the treated water to the drinking water supply. The small community at Davis Station lives in close proximity to each other, and there is the risk of a significant proportion of the station population becoming ill during a disease outbreak. A quantitative microbial risk assessment for Davis Station identified log removal values (LRV) of 10 - 12.4 for pathogens were required to meet the required health risk of 10-6 disability life adjusted years (DALY)2. A small scale potable water recycling plant was composed of ozone-ceramic membranes-biologically activated carbon- reverse osmosis – ultraviolet disinfection and chlorination was demonstrated at Self’s Point wastewater treatment plant, Hobart, Tasmania. The operating reliability of the demonstration plant, water quality (pathogens and chemicals of concern) of product water and discharge water, and energy requirements were monitored over 9 months of operation. Key issues for the plant were membrane fouling and on-line techniques to demonstrate reliable performance, and pressure decay testing of the reverse osmosis unit was used to increase the protozoa LRV to achieve the required treatment standard. REFERENCES 1. Environmental impact assessment of the Davis Station wastewater outfall, Australian Antarctic Division, 2011

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2. S. Fiona Barker, Michael Packer, Peter J. Scales, Stephen Gray, Ian Snape, Andrew J. Hamilton, Pathogen reduction requirements for direct potable reuse in Antarctica: Evaluating human health risks in small communities. Science of the Total Environment, 461-462 (2013) 723-733

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

INVITED SPEAKERS

W1.1 PROFESSOR GREG QIAO HIGH FLUX ULTRA-THIN COMPOSITE MEMBRANES FOR CO2 SEPARATIONS Department of Chemical and Biomolecular Engineering, Melbourne School of Engineering, The University of Melbourne One latest strategy in new membrane design is driven by the high performance CO2 gas membrane in the form of composite membranes with an ultra-thin, mechanical robust and high CO2 permeance selective layer. Our target performance is for the composite membrane with a CO2 gas permeance of more than 1000 GPU and a CO2/N2 selectivity of more than 20, desirable for an effective and economic operation for CO2 post-combustion capture at an industrial scale. The targeted performance is achieved by two key approaches. One is control of the morphology of the top selective layer by using either soft nano-particles additives, block copolymer assembly or multi-block polymer additives.1 The other approach is to utilising recently developed thin film technology, namely continuous assembly of polymers (CAP), to fabricate an active selective layer in less than 100 nm, with many cases less than 50nm, while chemically cross-linking the layer to maintain its mechanical robustness during the selective layer formation (Fig 1).2 Further improvement is achieved by adding nanoparticles in the CAP membrane layer.3 The talk will provide principle design concept behind these membrane with key examples from both approaches. 1

Q. Fu; E.H.H. Wong; J. Kim; J.M.P. Scofield; P.A. Gurr; S.E. Kentish; G.G. Qiao, J. Mater. Chem. A, 2014,2, 1775117756.

2 Q. Fu, J. Kim, P.A. Gurr, J. Scofield, S. Kentish, G.G. Qiao, Energy & Environmental Science, 2016, 9, 434-440. 3 Kim, J., Fu, Q., Scofield, J. M. P., Kentish, S. E., & Qiao, G. G. . NANOSCALE, 2016, 8(15), 8312-8323.

Figure 1. The permeance vs selectivity diagram indicates a desired target area with a CO2 gas permeance of more than 1000 GPU and a CO2/N2 selectivity of more than 20. It also indicates a performance position of a typical CAP membrane.

GREG QIAO, PROFESSOR The University of Melbourne, Australia Phone: +61 3 8344 8665 Fax: +61 3 8344 4153 E-mail: [email protected] 2010

Professor and Assistant Dean (Research)

2012-2015

Australian Research Council’s Professorial Future Fellow

2015

Chair, Polymer Division, Royal Australia Chemical Institute (RACI)

Research interests: polymeric membranes, composite membranes, polymer synthesis GOLD SPONSOR

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W2.1 PROFESSOR MIKEL C. DUKE NEW APPLICATIONS AND FUNCTIONS FOR UF AND MF USING INORGANIC AND INORGANIC/ ORGANIC COMPOSITE MATERIALS Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, Australia Microfiltration (MF) and ultrafiltration (UF) are now established industry operations thanks to low cost polymer membrane materials. MF and UF has been adopted primarily for drinking water and valuable food product separations, and more recently for waste water treatment and recycling. However wider realisation of their useful function to recover fats and proteins or as a barrier to suspended solids including pathogens is limited under more challenging environments. The durability limit of polymer materials can be addressed using inorganic materials, but high performance must be shown to offset the higher cost of inorganic materials. The two approaches to consider inorganic materials for MF and UF are purely inorganic membranes or inorganic/organic composite membranes. For purely inorganic membranes, commercial ceramic and metallic types were investigated. Ceramic membranes uniquely showed high fluxes during MF of secondary treated municipal waste water when combined with ozone and coagulant, where together with long life leads to lower overall plant life cost1-3. Other unique features include the ability to increase disinfection of the waste water and reduced fouling potential if reverse osmosis is applied downstream. Recent studies have shown that role of ozone on the membrane surface to generate hydroxyl radicals, while other mechanisms were found to alter by-product bromate formation. Metal membranes were applied for MF of waste waters from meat processing facilities, showing high sustainable fluxes at practical water recoveries, but also the prospect to capture valuable tallow. Valuable product recovery and the offset of trade waste costs showed potential cost viability. Inorganic/organic composite membranes were also shown to provide superior durability. Inorganic nanoclays added to the widely manufactured polyvinylidene fluoride (PVDF) membranes lasted 3-fold longer under simulated abrasive conditions3-4. Improved abrasion resistance was attributed to the hard inorganic filler as the change in phase of the PVDF from α to β as a result of the influence of the nanofiller on the host polymer structure. Recent work on the inclusion of magnetic iron oxide inorganic fillers into PVDF has shown improved resistance to fouling during filtration of oily emulsions as a result of the altered physical structure and increased hydrophilicity by adding the fillers. However the magnetic fillers were found to add a magnetic heating function, which facilitated flux return during chemical cleaning on membranes fouled with oily emulsions.

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Inorganic or inorganic/organic composite membranes can therefore expand the beneficial functions of MF and UF cost effectively into more challenging applications, but also exhibit novel features such as enhanced disinfection, altered by-product formation and magnetic effects unique to inorganic membranes. REFERENCES 1

N. Dow, D. Murphy, J. Clement & M. Duke 2013. AWA Water, 40(6), p45-51.

2

N. Dow, J. Roehr, D. Murphy, L. Solomon, J. Mieog, J. Blackbeard, S. Gray, N. Milne, B. Zhu, A. Gooding, J. Currie, G. Roeszler, J. Clement & M. Duke 2015. Water Practice & Technology, 10(4), p806-813.

3

Duke M. et al, 2014, AWRCoE Project Final Report (http://www.australianwaterrecycling.com.au/ ).

4

C. Y. Lai, A. Groth, S. Gray & M. Duke 2014. Journal of Membrane Science, 449(0), p146-157.

4

C. Y. Lai, A. Groth, S. Gray & M. Duke 2014. Water Research, 57(0), p56-66.

http://www.ausnano.net The Nanotechnology field is one of the fastest growing areas of research and technology. The Australian Nanotechnology Network (ANN), is dedicated to substantially enhancing Australia’s research outcomes in this important field by promoting effective collaborations, exposing researchers to alternative and complementary approaches from other fields, encouraging forums for postgraduate students and early career researchers, increasing nanotechnology infrastructure, enhancing awareness of existing infrastructure, and promoting industry and international links. The ANN will achieve these goals through its dedication to bringing together all the various groups working in the field of Nanotechnology and related areas within Australia. The International Conference on Nanoscience and Nanotechnology is the major forum designed to achieve these goals GOLD SPONSOR

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W1.10 PROFESSOR KLAUS-VICTOR PEINEMANN ADVANCED MEMBRANE STRUCTURES MADE BY “PHASE INVERSION” Advanced Membrane and Porous Materials Center, King Abdullah University of Science and Technology Advanced Membrane and Porous Materials Center, King Abdullah University of Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia The non-solvent induced phase separation (NIPS) and also the drying induced phase separation (DIPS) for membrane formation is since its first description by Zsigmondi and Bechold nearly 100 years old. But the process is still developing and nearly weekly we see new formulations for novel membrane structures. This membrane formation method gets especially interesting when combined with additional physical or chemical processes. The non-solvent induced phase separation can be coupled with self-assembly of nanometer-sized colloidal micelles resulting in asymmetric membranes with pores down to 2 nanometer; or the NIPS process can be accompanied by metal complexation or chemical reactions leading to skinned membranes with unique properties. When the drying induced phase separation invented by Zsigmondi and Bechold is applied to concentrated block copolymer solutions complex asymmetric structures with a hierarchical pore structures can evolve. A new generation of membranes with unique properties can be manufactured using these “hybrid” formation methods. Recent developments and challenges will be introduced and discussed in this lecture.

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W3.10 DR TOROVE LEIKNES BIOFOULING ASSESSMENT IN MEMBRANE FILTRATION SYSTEMS APPLYING IN-SITU NONDESTRUCTIVE METHODS

SANGHYUN JEONG, YIRAN WANG, DR. TOROVE LEIKNES, LUCA FORTUNATO Water Desalination and Reuse Center (WDRC), Biological and Environmental Science & Engineering (BESE), King Abdullah University of Science and Technology (KAUST), Kingdom of Saudi Arabia Membrane filtration systems have increasingly been used in the last decades to produce high-quality water. Biofilm formation is inevitable in all water treatment systems and is a key challenge in all membrane filtration systems applied to both saline and freshwater environments. Membrane fouling is an inherent phenomenon in membrane processes and is a complex issue caused by many mechanisms such as precipitation of inorganic salts (scaling), accumulation of organic substances (adsorption, concentration polarization), deposition of inorganic and organic particles as well as biofilm formation by the deposition and/or growth of microorganisms. The development of a biofilm on a membrane surface that causes an unacceptable decline in membrane performance is defined as biofouling. A key aspect of biofilm studies involves the analysis of biofilm structure, which can predict the biofilm behavior, and thus, the impact on membrane filtration performance. Biofouling is very dynamic in nature and difficult to assess in terms of what are the main behaviors and response, where the nature and structure of biofouling changes with time and is impacted by operating conditions. A detailed understanding of biofouling is necessary to develop good fouling control and mitigation strategies. Several approaches are reported in the literature to study biofilm formation in membrane systems, most of them requiring destructive procedures. There is therefore a need to develop biofouling characterization and monitoring tools that can asses the biofilm properties in real-time and as it evolves. Due to its ability to investigate biofilm formation in-situ, non-destructively and without additional preparation of the biofilm (e.g. staining procedures), optical coherence tomography (OCT) has recently been used to visualize/monitor biofilm growth in membrane filtration systems. OCT can capture biofilm images with micrometer-resolution in the meso-scale from which detailed biofilm structures can be constructed. 3D visualization and imaging also enables obtaining a clear view of the biofilm distribution allowing an easier measurement of the key properties such as biofilm porosity and average thickness which can then be related to the permeate flow and hydraulic resistance formed by the biofouling structure. The data collected from the OCT analysis can show the biofouling behavior under operation and when collected as a time series can show the evolution as function of the system operating conditions.

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Biofouling studies on a gravity-driven MBR using the OCT approach have been conducted. OCT image analysis was used as a tool to visualize and evaluate the biofilm spatial distribution in-situ under continuous operation1, 2. An experimental setup was designed to monitor a submerged membrane configuration operated under constant gravity pressure (Fig. 1). The OCT camera was mounted on a motorized frame, which allows positioning the camera at predefined positions thereby enabling multiple areas to be monitored throughout the course of the experiment. The biofouling was monitored over a 43 day period. A flux decline was observed during the operation and can be clearly defined as 4 phases as a function of the changing biofilm properties (e.g. thickness, roughness) (Fig. 2). At the end of the experiment the membrane module was removed for a membrane autopsy exercise to assess the biomass accumulated on the membrane and to determine the composition of the biomass (Fig. 3). This presentation will give the result and highlights of the case study done.

Figure 1. Schematic of experiential configuration: a) system with OCT camera, b) module coverage / autopsy

Figure 2. Biofilm thickness s a function of filtration phases and corresponding OCT images of the biofilm

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a) Biofilm descriptors, 75% of membrane area

b) Composition (LC-OCD analysis)

Figure 3. Biofilm properties and composition for all areas monitored, representing 75% of membrane area

TOROVE LEIKNES Director WDRC, Professor Affiliation, Country: Water Desalination and Reuse Center (WDRC), Biological and Environmental Science & Engineering (BESE), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia Phone: +966-12-808-2193 E-mail: [email protected] Personal History: 2013

KAUST, Saudi Arabia

1996-2016

NTNU, Norway

2013

Director WDRC, KAUST

Research interests: Integration of membrane technology in advanced water treatment processes coupled with physical/chemical/biological processes.

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W4.10 PROFESSOR LINDA ZOU USING RGO LAMINATE FILM AS AN ION SELECTIVE BARRIER OF COMPOSITE MEMBRANE FOR WATER PURIFICATION Masdar Institute of Science and Technology, Abu Dhabi, UAE A novel approach of sulphonation followed by mild reduction was employed first time to prepare well separated rGO laminate composite membranes. The combined multistep approach offers hydrophilic regions as well as suitable interlayer spacing of 0.63 nm and 0.74 nm for ion selectivity and water permeation. In-situ Crosslinking reaction has been conducted on the assembled rGO film to successfully improve the stability of the rGO film in water. The promising water permeability of 61.7 LMH/KPa was achieved from optimized rGO interlayer distance by carefully controlled sulfonation and partial reduction conditions (sample Low-R). It was found that the net surface charges Donnan exclusion mechanism played a significant role in the salt rejection efficiency, which was subject to the ratio of cationic and anionic species valency present in the solution. The prepared rGO membrane High-R achieved 80.5% rejection of Na2SO4, followed by 52.0% rejection of NaCl, and 13.7% rejection of MgCl2. It can be seen that there was an interplay between water flux and salt rejection performance, the balance can be achieved by adjusting the reduction conditions. Stronger reduction condition resulted in higher salt rejection rate, while the water flux would decrease to some extent, it was due to the less remaining surface functional groups and resulted in smaller interlayer distance. This research has tested and confirmed of using a novel approach, even a relatively small quantity of well prepared and assembled two-dimensional rGO laminates could form an integrated barrier for effective ion selectivity.

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W2.15 DR HOSIK PARK THE EFFECT OF POLYDOPAMINE/GRAPHENE OXIDE INTERLAYER FOR THIN-FILM COMPOSITE MEMBRANE PREPARATION IN FORWARD OSMOSIS

HYEON-GYU CHOI1, AATIF ALI1, YOU-IN PARK1, SEUNG-EUN NAM1, HEECHUL CHOI1,2, HOSIK PARK1* 1 Center for Membranes, Advanced Materials Division, Korea Research Institute of Chemical Technology (KRICT), Republic of Korea 2 School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), Republic of Korea Dr. Hosik Park received his Ph.D in Environmental engineering at Gwangju Institute of Science and Technology (GIST) in 2010. He joined Korea Research Institute of Chemical Technology (KRICT) as a senior research scientist in 2014. He has been an adjunct professor at the department of green chemistry and environmental biotechnology, University of Science and Technology (UST) since 2015. Before working at KRICT, he built up his academic and research carrier about nanomaterial synthesis and application for environmental remediation. His current research interests focus on hollow fiber membrane and nano-enhanced membrane for seawater desalination such as membrane distillation, forward osmosis and pressure retarded osmosis. Forward osmosis (FO) is considered as a next-generation desalination process which replaces with reverse osmosis due to no hydraulic pressure required and low fouling tendency. Thin-film composite (TFC) membrane, which consists of polyamide (PA) dense selective layer and polysulfone (PSf) support porous layer, has been actively utilized for FO application due to its great membrane performance. The PSf layer of the TFC membrane contributes to water molecule transport through the membrane, however, it also allows severe internal concentration polarization, resulting in high water flux and reverse solute flux both. Recent efforts have been focused on modification of the support layer of the TFC membrane. In this study, an additional hydrophilic interlayer was formed between polyamide selective layer and polysulfone support layer in order to control trade-off of water flux and reverse solute flux simultaneously. Polydopamine (PDA) and graphene oxide (GO) was selected as a promising material of the interlayer of the TFC membrane. In particular, the TFC membrane was prepared via 1) the PSf support layer fabrication on the non-woven fabric via nonsolvent induced polymer separation, 2) the PDA/GO interlayer coating on the PSf support layer using dopamine solution in tris-HCl buffer, 3) the PA selective layer fabrication via interfacial polymerization on the PSf support layer coated with PDA/GO interlayer. The synthetic membrane was characterized and operated in GOLD SPONSOR

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Figure 1. Schematic illustration of the TFC membrane with the PDA/GO interlayer.

lab-scale FO process in order to evaluate a role of the PDA-GO interlayer on membrane performance in FO mode. HYEON-GYU CHOI Title: PhD Korea Research Institute of Chemical Technology (KRICT), Republic of Korea Phone: +82-42-860-7527 Fax: +82-42-860-7283 E-mail: [email protected] 2016

Senior Research Scientist, Korea Research Institute of Chemical Technology (KRICT), Republic of Korea

2008-2016

MS & PhD, Gwangju Institute of Science and Technology (GIST), Republic of Korea

2000-2008

BS, Pusan National University, Republic of Korea

Research interests: environmental nanotechnology-based membrane and process for water purification, desalination, and gas separation

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W4.15 DR SIMON SMART INORGANIC MEMBRANES: NOVEL MATERIALS FOR PERVAPORATION AND MEMBRANE DISTILLATION

Y. T. CHUA, C. X. C. LIN, F. KLEITZ, S. SMART The University of Queensland, School of Chemical Engineering, Brisbane, Australia Fresh water scarcity is one of the major challenges facing global society into the foreseeable future. The situation is all the more serious when coupled with the changing rainfall patterns and increased volatility in extreme weather events that are predicted to accompany climate change. Technologies that enable climate resilient water supplies are therefore of utmost importance both in Australia and around the world. Desalination and/ or water recycling using reverse osmosis membranes are the gold standard technology in this space. However, there are a range of waste water and brine streams, particularly from the mining and resource industries, where RO cannot be applied. Membrane distillation and pervaporation provide ways of overcoming these typical limitations, particularly using inorganic membranes such as ordered mesoporous silica1,2 and silica/carbon composites3. Here we look at both experimental and theoretical aspects3 and report long-term testing data from coal seam gas applications. ACKNOWLEDGEMENTS

S.S would like to acknowledge funding from the Australian Research Council in the form of ARC-DP 110103440 and from the Queensland Government in the form of a Smart Futures Fellowship. REFERENCES 1. Chua, Y. T., Lin, C. X. C., Kleitz, F., Zhao, X. S. and Smart, S. (2013) Nanoporous organosilica membrane for water desalination. Chemical Communications 49 (40), 4534-4536. 2. Y. T. Chua, C. X. C. Lin, F. Kleitz, S. Smart, Mesoporous organosilica membranes: Effects of pore geometry and calcination conditions on the membrane distillation performance for desalination, Desalination 370 (2015) 53–62. 3. Y. T. Chua, C. X. C. Lin, F. Kleitz, S. Smart, Synthesis of mesoporous carbon–silica nanocomposite water-treatment membranes using a triconstituent co-assembly method, Journal of Materials Chemistry A, 2015, 3, 10480 - 10491 4. Y. T. Chua, G. Ji, G. Birkett, C. X. C. Lin, F. Kleitz, S. Smart, Nanoporous organosilica membrane for water desalination: Theoretical study on the water transport, Journal of Membrane Science 482 (2015) 56-66

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TH1.1 DR ANIL K. PABBY CONCENTRATION AND PRESSURE DRIVEN MEMBRANE PROCESSES IN CHEMICAL AND RADIOACTIVE WASTE PROCESSING: CURRENT SCENARIO AND FUTURE CHALLENGES Nuclear Recycle Board, BARC, Tarapur, Distt. Palghar, Maharashtra, India One of the major challenges of the closed fuel cycle in the nuclear power program is the management of large volumes of radioactive wastes emanating from recycle facilities . In the closed fuel cycle, the spent nuclear fuel undergoes processing and the process generates large volumes of liquid waste categorised as low, intermédiate and high level waste (HLW). Innovative approaches are being evolved internationally to treat the liquid waste to recover valuable radionuclides. Separation of long-lived radionuclides such as actinides and fission products from high level radioactive waste is a challenging task for the chemists and the engineers. The chemical engineering community is already paying significant attention to the quest for technologies that would lead us to the goal of technological sustainability. In this context, membrane based separation technology has come a long way over the past three decades from a simple laboratory curiosity to full fledged commercial environmentally friendly technology to answer the multifarious demands of industry. The growth of membrane science is largely due to the impressive developments in the field of membrane material science and the evolution of different membrane based equipments. Amongst the various separation techniques, membrane based separation methods are getting increasingly popular due to factors such as high efficiency, low power consumption and easy scale-up due to a compact design. Also, membrane contactors have proved to be efficient contacting devices, due to their high area per unit volume that results in high mass transfer rates. They are not only compact but also eliminate several of the problems faced in conventional processes such as ion exchange, solvent extraction and precipitation. Membrane contactor processes, in which phase contacting is performed or facilitated by the structure and shape of the porous membrane, provide a new dimension to the growth of membrane science and technology and also satisfy the requirements for process intensification. In the field of analytical applications, these techniques exhibit high selectivity and they concentrate analytes during the separation process. For this reason, these techniques have undergone significant development in the last decade and are used for analytical sample preparation, due to its advantages over conventional sample preparation techniques. This invited talk presents the overview of different membrane technologies and their commercial applications in chemical and nuclear industries including current scenario of these techniques applied world wide. Authors also cover some of the results obtained in laboratory using ‘concentration’ and ‘pressure driven’ based membrane techniques for treating waste generated by radiochemical plants. Attempts are made to focus future progresses in membrane engineering.

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TH3.1 ASSOCIATE PROFESSOR PIERRE LE-CLECH FACTORS INFLUENCING LOG REMOVAL OF PATHOGENS IN MEMBRANE BIOREACTORS, THE KEY FOR PROCESS VALIDATION

A/PROF PIERRE LE-CLECH, MR AMOS BRANCH, DR TRANG TRINH, PROF GREG LESLIE UNSW INTRODUCTION

Membrane bioreactors (MBR) are commonly used in water recycling schemes requiring consistent high quality effluent and small plant footprint. Validation is undertaken to ensure that a process can and will continuously meet required log removal value (LRV) of pathogens. In Australia, validation of MBRs has been undertaken on a case-by-case basis meaning for each water recycling scheme, equal management of health risk has not been applied. The Victorian department of health provided a guidance document to assist validation in 2013 but even this document acknowledged research gaps relating to MBR, which resulted in the requirement for highly conservative, detailed and expensive validation studies. In order to successfully validate a process it is necessary to understand what factors may influence LRV. Ideally influencing factors would be process operating conditions that could be controlled to some degree. Literature on LRV by MBR was critically assessed and as a result over 500 LRVs representing both bacteria and protozoa were collated. Even though a large number of LRVs for MBR had been reported there was limited detail on corresponding operating conditions, as a result no conclusions could be drawn regarding influence of operating parameters. The uncertainty of which factors contribute to MBR LRV has also led to limited confidence and highly conservative accreditation in Australia. The aim of this study was to gather a large data set of LRV and operating parameters for multiple full scale MBRs in order to shortlist key influencing factors and as a result, propose a streamlined and consistent validation methodology. METHODS

180 site visits were made to over 10 full-scale MBR installations. On each visit a multiple operating and bulk water quality parameters, as well as microorganism LRVs were assessed. LRV data were summarised by first fitting lognormal probability distributions to microorganism densities and then using Monte Carlo simulation to calculate LRV. The resulting distributions described the expected value and variability for LRVs corresponding to the operating range of the MBRs sampled. By separating the data into high and low categories and recalculating LRV distributions it was possible to determine the influence of operating parameters on LRV.

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RESULTS AND DISCUSSION

LRV distributions for Clostridium perfringens (CP), E. coli (EC), FRNA bacteriophage (FRNA) and somatic coliphages (SC) were included in Figure 1 A to D. 5th percentile LRV were 2.5, 4.8, 3.4 and 1.7 for CP, EC, FRNA and SC, respectively. For the operating range of MBRs assessed, these values provide a sound basis for the proposal of default LRVs. Standard deviation for CP was much larger than for other indicators due to the fact it was not detected in more than 80% of permeate samples. In addition, CP was highly resistant to biopredation in the activated sludge meaning the concentration against the membrane was higher than that in the influent. Consequently, if breakthrough occurred a large number of organisms could transfer across the membrane. These two factors contributed to a relatively low value for the 5th percentile. FRNA are typically favoured as virus indicators due to their smaller size range (20 – 30 nm) as indigenous species when compared with SC (27 – 200 nm). It has been previously suggested that FRNA presents a more conservative challenge for MBRs as it is typically smaller than the pore size used in MBRs (40 – 400 nm). The 5th percentile LRV from this study was 1.7 for SC, half that of FRNA (3.4). Although FRNA should theoretically be more conservative it was removed to such a large extent in the activated sludge that very low concentrations were present close to the membrane surface. SC presented a significant

Figure 1 – LRV distributions for CP (A), EC (B), FRNA (C) and SC (D).

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challenge to removal by the activated sludge, sometimes accumulating to densities higher than the influent. Analysis of all data concluded that operation under the following conditions would lead to a higher likelihood of a lower LRV: • Short hydraulic retention time (HRT) • High membrane flux • Low trans-membrane pressure • High permeability • Low mixed liquor suspended solids • High bioreactor dissolved oxygen High permeate turbidity also appeared to coincide with lower LRVs, supporting its use as a monitoring technique. In the range of 16 to 27°C temperature did not appear to significantly affect LRV. CONCLUSION

Factors have now been shortlisted that can be used to identify safe conditions for operation of MBRs. In addition, these factors have been used to recommend an appropriate operating envelope for validation testing of MBRs for inclusion in a National validation framework. As a result, the process of validating MBRs will become more streamlined and have an equal treatment of risk, benefiting end users, designers, membrane suppliers and health regulators. PIERRE LE-CLECH A/Prof, UNSW Australia E-mail: [email protected] Since 2011 A/Prof at the School of Chemical Engineering, UNSW Australia Research interests: Membrane bioreactors for wastewater treatment and recycling, membrane characterisation and integrity study, novel processes (Forward Osmosis) and optimisation for desalination pre-treatment.

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TH1.10 DR GUILLERMO ZARAGOZA MEMBRANE DISTILLATION: A REVIEW OF COMMERCIAL MODULES AND THEIR PERFORMANCE CIEMAT-Plataforma Solar de Almería, Spain Membrane distillation (MD) is a hybrid technology combining phase-change thermal distillation and microporous hydrophobic membrane separation. It can significantly reduce the footprint of conventional distillation processes and the capital and operational costs of membrane separation processes. Most importantly, it can treat water with very complicated quality which other membrane processes cannot. Also, the driving force of the process is a difference in partial vapour pressure across the membrane, which can be established with a source of low temperature heat and therefore using renewable or even waste energy. This is an important contrast with other membrane separation processes which require high mechanical pressure and therefore a source of high quality energy such as electricity. These advantages make MD prevail over other separation processes for an increasing number of niche applications (brine concentration, produced water treatment for gas and oil industry, industrial waste water concentration). However, despite the growing opportunities for deployment of MD, full commercial implementation of the technology is yet to be achieved. An examination of the literature shows that research on MD has been mostly focused on laboratory-scale studies, and works dealing with real-scale modules are still scarce. Recently, some prototypes modules of MD have been developed and commercial modules are already available in the market. Practically all of them have been evaluated at Plataforma Solar de Almería (SE Spain) over the past few years. An experimental assessment has been carried out of different commercial and pre-commercial MD technologies in a pilot scale using several test-beds operating with solar thermal energy. All the modules evaluated use flat-sheet membranes, but they have different configurations to implement the MD process. Scarab’s and Keppel-Seghers’ are plate and frame modules with air-gap and liquid-gap configuration respectively. On the other hand, Solar Spring and Aquastill commercialize spiral-wound modules with liquid-gap and air-gap configuration respectively. An additional technology, i.e., vacuum multi-effect membrane distillation, is also under evaluation using two units built by Aquaver based on Memsys modules.

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INVITED SPEAKERS

This presentation shows an analysis of commercial MD modules based on tests performed with real modules in pilot plant scale. A review of the works carried out at PSA is complemented with results of the few others available in the literature. The modules are compared in terms of their performance, analysing energy consumption, water production and quality. Numerical values of the distillate flux, energy efficiency and distillate salinity for a long range of experiments are examined, and the influence of several operational parameters like temperatures, flow rate and feed water salinity investigated. Operational issues encountered and resulting maintenance requirements are inspected to analyze the reliability and durability of each system. A comparative assessment of the different products is made and the challenges and opportunities for their commercial implementation are discussed. Resulting distillate fluxes are significantly lower than those obtained in the laboratory, confirming the difficulties associated to up-scaling the technology. Usually, these challenges are related to the consumption of energy, but also to the behaviour of the membranes. The intensive energy consumption as a result of inefficiencies is frequently counterpointed by the distillate productivity, so that a trade-off exists between both. Energy efficiency varies greatly, with spiral-wound modules and the vacuum multi-effect configuration showing the best results. Salt rejection achieved is generally larger than in other membrane separation processes, but the hydrophobicity of the pores can be affected by organic matter and scale formation on the membrane surface, leading to liquid penetration and deterioration of distillate quality. Finally, an economic assessment based on the costs of energy and the water produced is presented to determine the framework and possible scenarios for the technology to become cost effective.

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TH2.10 DR TAO HE INTEGRAL FORWARD OSMOSIS-MEMBRANE DISTILLATION PROCESS: RESEARCH HYPE OR SUSTAIN-ABLE SOLUTION FOR WATER REUSE?

TAO HE, YING CHEN, JIANFENG SONG, PENGJIA DOU, TINGTING XIAO, TONGHUI JIN, SHUWEI ZHAO, XUE-MEI LI Membrane Materials and Separation Technology, Shanghai Advanced Research Institute, China Water scarcity has been the growing concerns worldwide due to quick expanding in domestic, industrial, agricultural consumption, as well as climate change, water mismanagement, and water pollution caused by the human activities. Many countries and regions are now focusing on the non-conventional water source, such as seawater, wastewater from municipal, food and beverage, chemical, steel, mining and oil/gas industries. Conventional treatment technologies and processes, e.g. coagulation/ sedimentation, cyclone, media filter, are difficult to satisfy the more and more stringent environmental regulations. Membrane technologies, such as reverse osmosis (RO), nanofiltration are limited to desalinate low saline and extensively pre-treated feed due to constraints in the osmotic pressure, fouling/scaling. Forward osmosis (FO) is a desalination process driven by high osmotic pressure of a draw solution. Recent studies demonstrated that forward osmosis (FO) is intrinsically fouling reversible (compared to RO), suitable for high salinity feed, and requires low hydraulic pressure. However, the recovery of pure water from the draw cost much more energy than FO alone. Utilizing membrane distillation (MD) driving by the solar power or waste heat, FO-MD hybrid process has been used for a variety of wastewater streams. When treating high salinity feed, the internal concentration polarization of FO membrane is crucial because the draw efficiency is low. Therefore, design of the forward osmosis (FO) membrane is important. In this paper, we will discuss a systematic research on designing of hollow fiber FO membranes to achieve a high flux of 20 LMH at a feed solution of 10 wt.% total dissolved salt from oil/gas industry. On the MD part, the MD membrane is in direct contact with an engineered simple draw solution, frequently composed of water and salt. Therefore, fouling or scaling is in principal not a major concern. However, the membrane flux and salt leakage is critical. We will report the state-of-the-art development of superhydrophobic membrane as the potential candidate. The cost of FO-MD process will be evaluated in comparison to the distillation and RO processes.

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ABSTRACTS

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THEME: GAS SEPARATIONS T1.2 BURKHARD OHS IDENTIFYING OPTIMAL MEMBRANE MATERIALS AND PROCESS CONFIGURATIONS FOR GAS SEPARATION

BURKHARD OHS, JOHANNES LOHAUS, MATTHIAS WESSLING RWTH Aachen University, Chemical Process Engineering, Aachen, Germany Multi-stage membrane processes are usually required to achieve both high purity and recovery for industrial gas separation. As developing energy efficient and economic multi-stage processes is very challenging, heuristic methods often result in suboptimal process configurations. But appropriate process designs are especially crucial when only membrane materials with limited selectivity exist. Additionally, optimal membrane materials and properties can often not be chosen a priori to process development. Thus, we developed a mixed-integer non-linear programming (MINLP) model to identify optimal process structures and parameters. The model comprises equations to describe the process units, such as membrane modules and compressors, as well as equations to calculate investment and operation costs. To identify optimal membrane properties simultaneously to the process design, we incorporated the Robeson-Upper Bound in the MINLP model. This allows to choose between different membrane materials and also to target future material development to these optimal properties. As emerging separation tasks we analysed both H2/CO2 separation as well as nitrogen removal from natural gas. For these separation processes only materials with low selectivity exist, making an advanced process design crucial. Furthermore, selective materials for both gas components are available, providing an additional degree of freedom for the process development. With our work we could show that a systemic MINLP approach is able to identify process designs which result in up to 70% lower specific treatment costs.

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BURKHARD OHS Phone: +49 241 80 95142 Fax: +49 241 80 95142 E-mail: [email protected] RWTH Aachen University, Aachen 2007-2012

B.Sc. in Mechanical Engineering at RWTH Aachen (study abroad at University of New-South-Wales and Technical University of Denmark)

2012-2012

M.Sc. in Mechanical Engineering at RWTH Aachen University

9-2015-12/2015 Visiting Scholar at University of California, Berkeley Since 01/2013 Ph.D. candidate at RWTH Aachen University Research interests: gas separation, membrane processes, hybrid processes, simulation, microstructured devices

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T1.3 MATTHEW R. HILL A NEW USE FOR MOFS: STOPPING PHYSICAL AGING IN GLASSY POLYMERS FOR EXCEPTIONAL SEPARATION PERFORMANCE

CHER HON LAU1, PHUC TIEN NGUYEN,2 KRISTINA KONSTAS,1 CARA M. DOHERTY,1 1 LAURE BOURGEOIS,3 TIMOTHY J. BASTOW,1 ANITA J. HILL,1 DOUGLAS L. GIN,2 AND RICHARD D. NOBLE2 AND MATTHEW R. HILL*1 1 CSIRO, Private Bag 33, Clayton South MDC, Victoria 3169 Australia. 2 Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO USA. 3 Centre for Electron Microscopy, Department of Materials Engineering, Monash University, Clayton Victoria Australia Aging in super-glassy polymers such as poly(trimethylsilylpropyne) (PTMSP) prohibits it from being used in polymer membranes for separating gas mixtures. While these polymers are initially very porous and large amounts of gas can selectively pass through them, they quickly pack into a denser phase becoming much less porous and permeable. This age-old problem has been solved by the use of an ultraporous additive that allows PTMSP to maintain its low-density, porous initial state by absorbing a portion of the polymer chains within its pores, and holding them in position. This is the first time that this aging process has been stopped in PTMSP without diminishing its properties when prepared as a gas separation membrane.1,2 In fact, the membrane properties are enhanced with an additive,3 and over approximately one year of long-term measurements show that the performance is maintained. The addition of a very specific porous microparticle forms an interwoven nanocomposite with PTMSP, freezing the structure and hence stopping the aging process, but doing so whilst increasing the permeability and maintaining the selectivity. Porous Aromatic Frameworks (PAFs) are carbon-based structures formed by the self-condensation of tetrahedral monomer nodes to establish an ultraporous array.4 The regular nanopores of around 1.2 nm diameter are attractive for the intercalation of polymer side-chain components when incorporated within the PTMSP matrix, thereby freezing the as-cast lower-density polymer structure in place and stopping the aging process.5,6 This mechanism is distinct from the enhanced permeability effect of non-porous nanoparticle and porous nanoparticle additions to PTMSP that prop open the polymer chains at the nanoparticle/ polymer boundary but do not prevent aging.

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Figure 1. Structure within glassy polymers, as measured by gas permeability, can be controlled by unique tethering reactions within MOFs. REFERENCES 1. C. H. Lau, P. T. Nguyen, M. R. Hill,* A. W. Thornton, K. Konstas, C. M. Doherty, R. J. Mulder, L. Bourgeois, A. C. Y. Liu, D. J. Sprouster, J. P. Sullivan, T. J. Bastow, A. J. Hill, D. L. Gin, R. D. Noble, Forever Young: Ending Aging in Super Glassy Polymer Membranes, Angewandte Chemie. 2014, 126,21,5426. 2. Lyndon, R.; Konstas, K.; Ladewig, B. P.; Hill, M. R. GAS SEPARATION PROCESSES TW8699/AU/PROV, 26/7/12, 2012. 3. Thornton, A.W., Dubbeldam, D., Liu, M.S., Ladewig, B.P., Hill, A.J., Hill, M. R*. Feasibility of Zeolitic Imidazolate Frameworks for use in Gas Separation Membranes, Energ. Environ. Sci. 2012; 5:7637. 4. Konstas, K., Taylor, J.W., Thornton, A.W., Doherty, C.M., Lim, W.X., Bastow, T.J., Kennedy, D.F., Wood, C.D., Cox, B.J., Hill, J.M., Hill A.J., Hill, M. R*. Lithiated Porous Aromatic Frameworks with Exceptional Gas Storage Capacity, Angew. Chem. Int. Edit. 2012; 51:6639 5. C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F. Kennedy, S. C. Howard, A. J. Hill, M. R. Hill, Angew. Chem. Int. Ed. 2015, 10.1002/anie.201410684 6. C. H. Lau, X. Mulet, K. Konstas, C. M. Doherty, M. A. Sani, F. Separovic, M. R. Hill, C. D. Wood, Angew. Chem. Int. Ed. 2016, 55 (6), 1998-2001.

MATTHEW R HILL Title: A/Prof CSIRO, Monash University, Australia Phone: +61 3 9545 2841 E-mail: [email protected] 2016

Monash/CSIRO joiunt appointment

2006-2016 CSIRO Research interests: porous materials, separations, triggered release, commercial engagement

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T1.4 UPGRADING SEWAGE SLUDGE DIGESTION GAS QUALITY USING THE MEMBRANE SEPARATION METHOD

ASAMI SAITO, TAKUMA KATO NORIKO OSAKA Tokyo Gas Co., LTD. Given the increasing utility value of biomass as a source of renewable energy, there is increasing focus on finding effective ways to utilize biogas generated from biomass. Sewage sludge digestion gas, which is a type of biogas, has a composition of around 60 vol% methane (CH4), 40 vol% carbon dioxide (CO2) and other trace impurities. The applications of sewage sludge digestion gas are limited to boilers and Combined Heat and Power (CHP) generators with special specifications, because its calorific value is lower than that of city gas. These applications face issues relating to general versatility and cost. Therefore, it is necessary to upgrade the quality of the sewage sludge digestion gas in order to expand its range of application. The most popular technologies used to upgrade gas quality are the pressurized water scrubbing method and the pressure swing adsorption (PSA) method1. Recently, the membrane separation method has gained attention because this method is simple and compact. In addition, it is expected to require less capital and operating energy than the other methods. However, there are only a few instances of the adoption of the membrane separation method to upgrade biogas quality in Japan. It is therefore difficult to estimate the efficacy of the membrane separation method. Beginning in 2013, a long-term test of upgrading digestion gas quality has been carried out in collaboration with Yokohama City. Digestion gas generated at the North Yokohama Sludge Recycling Center was provided for the test. Commercial polymer membranes were used under basic conditions as shown in Table 1. The flow diagram of the process employed to upgrade the digestion gas quality is shown in Fig.1. An outlet port of a medium pressure gas tank was branched off in order to feed the test unit. The compositions of permeated gas (off gas), which was CO2-rich, and non-permeated gas (upgrading gas), which was CH4-rich, were analysed. Separated gas was returned to a low pressure gas tank after mixing and decompression. This test unit was operated continuously for 24 h. Several filters were installed on the primary side of the membranes to remove trace impurities such as siloxane and hydrogen sulphide (H2S). Table1. Basic conditions of a long-term test of upgrading digestion gas quality

90

Pressure after compression

Flow rate of feed gas

Controlled temperature of heater

Target of accumulated operation time

Target of accumulated flow rate of feed gas

kPaG

Nm3/h



h/year

K Nm3/year

900

3.7

35

8,000

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Off gas 550kPaG ~ 700kPaG

Cleaning of siloxane

900kPaG heater

Compressor Desulfurization

Upgrading gas Primary membrane

Secondary membrane

Recycled gas Fig.1. Flow diagram of the process of upgrading digestion gas quality

A long-term continuous test and an accelerated test were performed. The flow rate of feed gas under the accelerated condition was four times as much as that under the continuous condition. The accelerated test enabled quicker acquisition of membrane history data than the continuous test. These conditions were periodically reverted to continuous conditions in order to compare the capability of the membranes with early performance. The capability of membranes was evaluated with respect to CH4 concentration of upgrading gas and CH4 recovery rate. CH4 recovery rate indicates how much CH4 can be collected from feed gas. It was calculated according to the following equation. CH4 recovery rate (%) = (Cu × Fu) / (Cf × Ff) (a) Cu (%); CH4 concentration of upgrading gas Cf (%); CH4 concentration of feed gas Fu (NL/min); flow rate of upgrading gas Ff (NL/min); flow rate of feed gas Target values of CH4 concentration of upgrading gas and CH4 recovery rate were over 98 vol% and 90%, respectively. Fig.2 shows the capability of membranes under continuous and accelerated tests. When the history of membranes exceeded 2.1 years, CH4 concentration in the improved gas was around 99 vol% and CH4 recovery rate was around 94%. It was clear that the durability of these membranes lasted over two years. In addition, their capability in the long-term test was NOT affected by ambient air temperature, which differed by over 15 °C from summer to winter. It was suggested that the durability of membrane separation did not show any significant relation to temperature. The data was accumulated to contribute to the commercialization of the system to upgrade digestion gas quality using the membrane separation method. Development to find effective applications for the gas recovered from this system is ongoing.

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Gas separation capability of membrane (%)

99.1 99.8 98.5 100 95 97.0 90 94.6 93.6 85 80 75 70 65 60 55 50 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 History of membrane(year) Methane concentration of upgrading gas Methane recovery rate

Fig.2. Gas separation capability of membranes

ASAMI SAITO Title: Research worker Affiliation, Country: Tokyo Gas Co., LTD., Japan Phone: +81-45-500-8821 Fax: +81-45-500-8790 E-mail: [email protected] 2011-present

Tokyo Gas Co., LTD.

2009-2011

M.S. in Tokyo University of Science Graduate School

Research interests: Renewable energy, Biomass technology, Gas separation

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THEME: GAS SEPARATIONS

T1.5 ÁLVARO A. RAMÍREZ-SANTOS GAS SEPARATION OF STEELMAKING EMISSIONS WITH COMMERCIAL POLYMERIC DENSE MEMBRANES FOR GAS VALORIZATION AND CARBON FOOTPRINT REDUCTION: PROCESS DESIGN, LABORATORY TEST RESULTS, AND PERSPECTIVES FOR PILOT PLANT TRIALS

ÁLVARO A. RAMÍREZ-SANTOS, ERIC FAVRE, CHRISTOPHE CASTEL LRGP (UPR CNRS 3349), Université de Lorraine, 1 Rue Grandville, Nancy, France Iron and steel production is the largest industrial source of CO2, accounting for around 30% of direct industry emissions and 6-7% of global anthropogenic CO2 emissions1. Primary steel production route, in which steel is produced from raw materials, i.e. iron ore, dominates global manufacturing with over 70% of world’s steel being produced by this route. This is typically achieved by integrated steel mills based on the blast furnace-basic oxygen furnace (BF-BOF) process in which iron ore is reduced in the presence of coke. Three main gas emissions are present in an integrated steel mill: Blast furnace gas (BFG), Coke oven gas (COG), and blast oxygen furnace gas (BOFG). BFG emissions are the most important in volume and represent around 69% of the emitted CO2. BFG is mainly composed of 20-28% CO, 17-25% CO2, 50-55% N2 and 1-5% H2. It is typically burned for heating and power generation often being mixed with natural gas, coke oven gas or blast oxygen furnace gas to increase its heating value. COG is mainly composed of 40-65% H2, 20-40% CH4, 4-7% CO, and 1-3% CO2 while BOFG gas is mainly composed of 55-80% CO, 10-12% CO2, 8-26% N2+Ar and 2-10% H21. Past research projects have studied carbon capture and storage technologies for emissions reduction of the steelmaking sector2. New programs, like the French VALORCO project, are studying carbon capture and utilization alternatives in order to reduce emissions by the production of new materials from these carbon emissions. Instead of being burned and later emitted to the atmosphere, these emissions could be regarded as potential industrial sources of feed gases for the production of added-value products such as chemicals, biomass and biofuels by means of chemical or biological transformation processes. One of several alternatives are catalytic processes for the production of industrial relevant chemicals like methanol, urea, and ethanol among others. However, a gas separation step is necessary to adjust the concentration of the emissions to the feed gas conditions required for most of the available transformation processes3. Membrane gas separation is now a commercial alternative for many industrial separations, like CO2 and N2 separation from natural and biogas, H2 purification and recovery from process streams, H2/CO ratio adjustment in syngas, and it is also the center of active research concerning CO2 recovery from flue gases for CCS applications4,5. This is supported by the many advantages offered by this technology over more classical processes such as reduced environmental impact due to the absence of chemical systems, easy up and GOLD SPONSOR

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down scaling, ease of operation and control, no moving parts, no additional energy required besides the one required for gas flow, among others4. However, very few works have been published dealing with the application of membrane separation to steelmaking off-gases. This study addresses the question of the application of commercially available gas separation membranes for BFG, COG and BOF gas separation for CO2, H2 and CO valorization and aims to illustrate current opportunities and challenges, and provide input on the interest of a pilot scale membrane unit. Data for two commercially available membranes, a H2 selective glassy polyimide membrane from UBE industries and a CO2 selective rubbery composite membrane from MTR Inc. have been used for the simulation of blast furnace gas, coke oven gas and blast oxygen furnace gas separation, first in a one stage process and then in a multistage architecture by means of an in-house developed gas permeation simulation tool exported to the Aspen plus software. Gas permeance was validated at our laboratory-scale permeation unit for the glassy polyimide membrane under mixed-gas conditions and varying temperature and pressure. The effect of operating parameters (pressure ratio, membrane surface, stage cut) on separation performances was studied and a general mapping of gas compositions attainable with the available commercial membranes is presented and discussed under a gas valorization scenario (Fig.1). Energy and surface requirements are taken into consideration by a cost model implemented within the simulation allowing process optimization to reach the minimum separation costs depending on product specifications and separation architecture. This approach allows also the identification of key parameters during cost calculations, which are a valuable input for designers of costeffective gas membrane separations (Fig.2). Given the diversity and complexity of carbon dioxide capture, large efforts are required in order to better estimate the best place and role of membranes in the steel manufacturing industry. Some leads have been given in this work. Field tests on real flue gases, in order to determine the impact of trace components, humidity and the stability of membrane module performances is also necessary and is the focus of the next stage of the project. The preliminary conclusions offered by this exploratory study suggest however that a concentration tuning box based on membranes and applied on steelmaking emissions could be of interest in order to achieve simultaneously emissions valorization and carbon footprint reduction.

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Figure 1. Ternary gas compositions possibly achievable by membrane gas separation of a blast furnace feed mixture thanks to a Ube or MTR Polaris membrane. Permeate product stream (a) and the retentate product stream (b). Each dot on one composition path corresponds to a given pressure ratio and stage cut.

Figure 2. Sensitivity analysis of CO2 separation cost for a one stage separation under feed compression. Each cost parameter is varied supposing a +/- 50% difference from the reference value. Separation cost calculated with the reference values for permeate vacuum and feed compression is 26 EUR/Ton CO2. Pressure ratio 0.01. CO2 product stream with 70% purity and 85% recovery is considered in both cases. REFERENCES 1 A. Carpenter, IEA Clean Coal Centre. 2012, 1-119 2 J.P Birat, UNIDO Global technology roadmap for CCS in industry – Sectoral experts meeting. 2010, 1-65 3 R. Cuéllar-Franca, A. Azapagic, J. of CO2 Utilization. 2015, 9, 82-102 4 E. Favre, Chemical Engineering Journal. 2011, 171, 782-793 5 C. Scholes, M. Ho, A. Aguiar, D. Wiley, G. Stevens, S. Kentish, Int. J. of Greenhouse Control. 2014, 24, 78-86 GOLD SPONSOR

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ALVARO RAMIREZ-SANTOS Title: Chemical engineer (Colombia-France) and phD candidate at U. de Lorraine Affiliation, Country: LRGP CNRS, France Phone: +330383175384 E-mail: [email protected] 2014-2017

phD Student LRGP – Université de Lorraine (Nancy-France)

2013-2013

Intern at Total’s CRES research center – Total (Solaize-France)

2011-2013

Master in process and product engineering – ENSIC (NancyFrance)

2009-2011

Project engineer for the Colombian petroleum institute (Colombia)

2003-2009

Bachelor in chemical engineering – U. de Santander (Colombia)

Research interests: Gas membrane separation, CO2 capture, natural gas, gas treatment

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THEME: GAS SEPARATIONS

T1.6 DR. LUCA ANSALONI MEMBRANE CONTACTOR WITH HIGH CO2/AMINE SELECTIVITY: A VIABLE SOLUTION FOR THE USE OF ENERGY-EFFICIENT CO2 ABSORBENTS WITH HIGH VOLATILITY

DR. LUCA ANSALONI, MR. RUNE RENNEMO, DR. HANNA KNUUTILA, DR. LIYUAN DENG Norwegian University Of Science And Technology (NTNU) In post-combustion CO2 capture amine-based absorption is the benchmark technology, but the development of a more cost-effective technology is required in order to make the capture step more economically feasible. Recently, a new category of absorbents forming two liquid phases upon CO2 loading (phase change or 3rd generation solvents) has been developed, and one promising family is represented by blends of DEEA and MAPA1-3, with an energy requirement in the desorption step that can go below 2.5 MJ/ kgCO2 in real process conditions. However, the main drawback of this new class of promising solvent is related to the high volatility, which is currently threating their use at the industrial scale. In fact, besides the larger vapour pressure compared to traditional solvent, such as MEA, a very peculiar behaviour is reported for the tertiary amine (i.e., DEEA) when in water mixture4. Differently from MEA, the activity coefficient of DEEA increases in the low amine concentration in the aqueous solution, producing an evaporation of organic components that does not meet the emission standards. In order to optimize the use of this promising class of CO2 absorbents, membrane contactor technology is proposed, since if the membrane interface is designed in order to ensure certain CO2/amine selectivity, the membrane contactor is able to prevent the evaporation of the amine towards the purified flue gas to a large extent. Even though porous materials are frequently used in membrane contactor applications, their nonselective nature makes them not particularly attractive to this purpose. On the contrary, better results can be expected using thin composite membranes5, where the dense layer is chosen accordingly to its ability of ensuring high CO2 flux but low amine transport towards the gas phase. Furthermore, the presence of the dense layer can be beneficial to prevent wetting phenomena, which can be responsible of significant efficiency loss of the contactor on long term operations6. According to initial screening tests7, Teflon AF 2400 and porous polypropylene (PP) can be used to prepare the compatible thin composite membrane. Thus in the present work, the transport properties of a dense AF2400 membrane have been tested in terms of both CO2 and DEEA-MAPA permeation in order to verify its ability to give CO2/amine selectivity. Humid permeation tests have been performed on a self-standing sample (20 µm thick) in order to verify the effect of water vapour on the CO2 permeability coefficient, as significant effects have been reported in case of hydrophobic materials8. Furthermore, pervaporation test on a self-standing sample (10 µm thick) of AF2400 were performed in GOLD SPONSOR

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order to investigate the permeation of different amines. Various concentrations of two different amines in aqueous solutions have been considered: MEA, considered as reference for CO2 absorbents, and the DEEA-MAPA blend, considered as reference system for the phase change solvent class. The CO2/amine selectivity has then been calculated according to the fluxes expected for both CO2 (calculated for the real flue gas conditions, i.e. 13 vol% CO2 at atmospheric pressure) and the amine flux (obtained from pervaporation experiments carried out with the real absorbent solutions).

Figure 1. Effect of water vapour on the gas transport properties of Teflon AF2400 at ambient conditions.

In view of the hydrophobic nature, the presence of water vapour in the gaseous stream has a limited effect on the gas transport properties of AF2400 (Fig. 1). Such a reduced effect can be beneficial in preventing possible solvent dehydration due to the water permeation through the membrane layer. The membrane contactor can thus be operated with humidified flue gas with a small effect on the overall CO2 mass transfer resistance, reducing the water permeation from the liquid to the gas phase. Furthermore, pervaporation tests showed that the AF2400 membrane is able to reach high CO2/amine selectivity in the temperature range 25 to 60 °C, typical of the absorption step (Fig. 2). It appeared clear the increase of DEEA concentration in the liquid absorbent decrease the membrane selectivity, but the value remained always larger than 100, showing promising results for the membrane contactor configuration.

Figure 2. CO2 vs amine selectivity for different DEEA-MAPA concentration in the liquid absorbent.

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Membrane contactor tests are now currently undergoing for a hollow fibers membrane module, and simultaneous data on CO2 mass transfer coefficient and amine concentration in the CO2-lean flue gas stream will be obtained. These data will be used to validate a model able to evaluate the real prevention of the amine evaporation achievable by using the membrane contactor in comparison with traditional absorption columns. The entire project is financed by the Norwegian Research Council through the CLIMIT program, (Ground-breaking New Concepts for CO2 Capture, Project No. 239789). REFERENCES 1

Monteiro, J. G. M. S.; Majeed, H.; Knuutila, H.; Svendsen, H. F., Chem.Eng.Sci. 2015, 129, 145-155.

2

Arshad, M. W.; Svendsen, H. F.; Fosbøl, P. L.; von Solms, N.; Thomsen, K., J.Chem.Eng.Data 2014, 59, (3), 764-774.

3

Arshad, M. W.; von Solms, N.; Thomsen, K.; Svendsen, H. F., Energy Procedia 2013, 37, 1532-1542.

4

Hartono, A.; Saleem, F.; Arshad, M. W.; Usman, M.; Svendsen, Chem.Eng.Sci. 2013, 101, 401-411.



Nguyen, P. T.; Lasseuguette, E.; Medina-Gonzalez, Y.; Remigy, J. C.; Roizard, D.; Favre, E.,

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J.Membr.Sci. 2011, 377, (1–2), 261-272.

7

Scholes, C. A.; Kentish, S. E.; Stevens, G. W.; Jin, J.; deMontigny, D., Sep.Pur.Tech. 2015, 156, Part 2, 841-847.

8

Ansaloni, L.; Arif, A.; Ciftja, A. F.; Knuutila, H.; Deng, L., Membrane contactors using phase change solvents for CO2 capture: Material compatibility study. Sep.Pur.Tech. 2016, Submitted.

9

Ansaloni, L.; Minelli, M.; Giacinti Baschetti, M.; Sarti, G. C., J.Membr.Sci. 2014, 471, 392-401.

LUCA ANSALONI Title: PhD, Postdoctoral Fellow Norwegian University of Science and Technology (NTNU), Norway Phone: +4773591807Fax: +4773594080 E-mail: [email protected] 2011-2013

PhD student at University of Bologna

2014-2015

Postdoctoral fellow at University of Bologna

Since 2015

Postdoctoral fellow at NTNU

Research interests: CO2capture, gas separation membranes, membrane contactors, glycol dehydration

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T1.7 SUNEE WONGCHITPHIMON POLYMER-FLUORINATED SILICA COMPOSITE HOLLOW FIBER MEMBRANES FOR THE RECOVERY OF BIOGAS DISSOLVED IN ANAEROBIC EFFLUENT

SUNEE WONGCHITPHIMON1,RONG WANG1,2,TAE-HYUN BAE1,3 1 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore 637141, Singapore 2 School of Civil and Environmental Engineering, Nanyang Technological University, Singapore 639798, Singapore 3 School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 637459, Singapore Biogas, which is known as a clean energy, can be produced in anaerobic digestion processes that are widely used for treating wastewater with high-concentration of organic pollutants. Although many efforts have been devoted to recover methane from biogas mixtures to complete the waste-to-energy conversion, the portion dissolved in the effluent has been discharged without any recovery process. The concentration of methane dissolved in the effluent, which is proportional to the partial pressure of methane in the gas phase of anaerobic reactor, was reported to be 10 - 25 mg/l . Cookney et al . also reported that more than 50% of the methane produced during the anaerobic treatment of municipal wastewater could be dissolved in the anaerobic effluent under certain conditions. Thus, the implementation of an energy-efficient process for the recovery of dissolved methane can maximize the production of clean energy in anaerobic digestion processes. A hollow fiber membrane contactor that facilitates the transport of gas in a liquid to a gas phase via a large mass transfer area can be a promising technology to recover such dissolved methane. For this operation, a hydrophobic membrane is highly desirable to ensure a rapid methane transport for a prolonged operation time. In this work, porous hollow fiber membranes were fabricated with two commercial polyimides. Subsequently, the surfaces of hollow fiber membranes were hydrophobized via depositing fluorinated silica nanoparticles and applied to the membrane contactor system for the recovery of methane from anaerobic effluent. Fig. 1 shows the morphology of hollow fiber membranes made of polyetherimide (PEI) and polyimide (Matrimid®, MT).the dope compositions as well as spinning conditions were adjusted to tailor the structural properties resultant membranes. Finger-like macrovoids were developed underneath both inner and outer surfaces for PEI-A and MT-A membranes which were fabricated from the dope solution containing lithium chloride. In

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contrast, a sponge-like structure was observed for PEI-B and MT-B membranes for which both lithium chloride and polyethylene glycol (MW = 200) were used as the additives. Further characterization revealed that MT substrate membranes have lower pure water flux than PEI membranes, indication higher porosity and/or pore size in skin layers. However, no obvious difference was observed in the sublayer morphologies of both membranes. The contact angles and mean pore sizes of the four membrane substrates were ranged in 74.09 – 75.57° and 46.50 57.50 nm, respectively.



A

B

C

D

Figure 1. Cross-sectional morphologies of hollow fiber membrane substrates. (A): PEI-A, (B): PEI-B (C): MT-A and (D): MT-B

To render a high hydrophobicity to hollow fiber membrane substrates, fluorinated silica nanoparticles were deposited on to the hollow fiber surface using the procedure reported elsewhere. The SEM images of such surface modified hollow fiber membranes are shown in Fig. 2. A significant increase in hydrophobicity was confirmed by water contact angle which increased from 75.00° to 120.00°.



a

b

c

d

Figure 2. Outer surface morphologies of modified hollow fiber membranes. (a): PEI-A, (b): PEI-B, (c): MT-A and (d): MT-B

Modified membranes were applied to test the performance in membrane contactor process as illustrated in Fig. 3. Hollow fiber module was prepared by sealing fibers into a stainless steel tube. Pure nitrogen was used as the carrier gas, while synthetic biogas dissolved in anaerobic effluent with different concentrations was used as a feed solution. The recovered gases were analysed on bubble flow meter and gas chromatography. In contrast, dissolved methane gas concentrations inside feed and retentate solutions were measured by the methane sensors. GOLD SPONSOR

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Figure 3. Schematic diagram of Figure 4. Recovered methane fluxes of modified membrane contactor setup. hollow fiber membranes.

Fig. 4 shows the effect of feed velocity on the recovered methane flux. Among the modified membranes, the recovered flux of methane gas increased with an increase in liquid velocity. Modified MT membranes have higher recovered methane flux than modified PEI membranes.

SUNEE WONGCHITPHIMON Title: Dr. Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore Phone: +65 84020827 Fax: +65 67910756 E-mail: [email protected]

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2012-now

Research fellow Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore

March, 2012

Ph.D, Chemical Engineering, King Mongkut’s University of Technology Thonburi, Thailand

Research interests: Gas separation, membrane distillation, membrane development and characterization, novel materials and surface modification

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T1.10 SHINJI KANEHASHI EFFECT OF IMPURITIES ON GAS SEPARATION PERFORMANCE IN MIXED MATRIX MEMBRANES

SHINJI KANEHASHI1,2, ALITA AGUIAR1, JINGUK KIM1, SANDRA KENTISH1 1 Peter Cook Centre for CCS Research, Department of Chemical and Biomolecular Engineering, the University of Melbourne, Victoria 3010, Australia 2 Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16, Nakacho, Koganei, Tokyo 184-8588, Japan Mixed Matrix Membranes (MMMs) combine the benefits of both polymer substrates and inorganic fillers and have become attractive materials for gas separation in recent years. The filler can improve membrane properties such as thermal stability, mechanical strength, and gas separation performance. Furthermore, fillers can restrict the physical aging of glassy membranes 1. We have reported dry gas separation performance of MMMs consisting of a commercial aromatic polyimide, Matrimid ®5218 and poly(ltrimethylsilyl)-l-propyne) (PTMSP) as a host matrix and several types of commercial and/or synthesized nanoparticles as a filler phase 1,2. In addition, we have shown that water vapor can cause a significant loss of CO2 separation performance in hydrophilic MMMs due to the high water solubility and the resulting competitive sorption 3. In the present study, we investigate the resistance of MMMs to flue gas impurities such as NO, SO2 and H2S and the impact of these impurities on the CO2 separation performance at 35oC. All membranes were formed from Matrimid®5218 and contained 20 wt% of the relevant nanoparticle. The nitrogen permeability of fresh membranes was first tested for mixtures of 1000 ppm NO, SO 2 and H2S in nitrogen. For the pure Matrimid polymer, there was a slight increase in N2 permeability when NO and H2S are both present. While this may reflect only experimental error, it may also indicate plasticisation of the membrane structure - this is often reported for polymers exposed to H 2S. Conversely, a decline in permeability in the presence of SO2 probably reflected competitive sorption, where the SO2 displaces N2 from sorption sites. Within the MMMs, all three penetrants resulted in a net decline in permeability, with H2S clearly having the greatest effect upon permeability. This is somewhat surprising, as competitive sorption is usually related to the critical temperature of the penetrant. The membranes were then exposed to the same gas mixtures for up to 80 days. Again, while the performance of the pure Matrimid was relatively stable over this period, significant declines in permeability were observed for all mixed matrix structures. These results will be discussed in terms of the properties of both the membrane and nanoparticles. GOLD SPONSOR

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REFERENCES 1

C. Lau, K. Konstas, C. Doherty, S. Kanehashi, B. Ozcelik, S. Kentish, A. Hill, M. R Hill, Chem. Mater. 2015, 27, 4756-4762.

2 S. Kanehashi, G. Chen, C. Scholes, B. Ozcelik, C. Hua, L. Ciddor, P. Southon, D. D’Alessandro, S. Kentish, J. Membr. Sci. 2015, 482, 49-55. 3 S. Kanehashi, G. Chen, C. Scholes, B. Ozcelik, C. Hua, L. Ciddor, P. Southon, D. D’Alessandro, S. Kentish, J. Membr. Sci. 2015, 492, 471-477.

SHINJI KANEHASHI Title: Dr. Affiliation, Country: Japan Phone: +81-42-388-7404 Fax: +81-42-388-7404 E-mail: [email protected] 2009-2012

Research Associate, Meiji University, Japan.

2012-2015

Research Fellow, the University of Melbourne, Australia

Since 2015

Assistant Professor, Tokyo University of Agriculture and Technology

Honorary Fellow, the University of Melbourne Research interests: Membrane, Separation, Composites

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T1.11 DEISY MEJIA MASS TRANSFER IMPROVEMENT BY DEAN VORTEX: APPLICATION TO CO2 CAPTURE USING HOLLOW FIBER MEMBRANES CONTACTORS

DEISY MEJIA, CECILE LEMAITRE, ERIC FAVRE, CHRISTOPHE CASTEL Laboratory of Reactions and Process Engineering (LRGP), (UMR 7274) ENSIC. 1, rue Grandville – BP 20451. 54001 Nancy Cedex, France. Nowadays CO2 capture has become one of the major issues due to the increase of environmental conscience. Various technologies attempting to solve this problem have emerged, mostly gas liquid contactors with reacting or physical solvents able to separate CO2. Among these technologies, membrane contactors have proved their capacity and good performance. Membranes provide various advantages which make them more attractive: no phase change, continuous operation without a regeneration step, limited fouling, and increase of interfacial area, among others. 1”container-title”:”Journal of Membrane Science”,”page”:”61-106”,”volume”:”159”,”issue”:”1–2”,”source”:”ScienceDire ct”,”abstract”:”A membrane contactor is a device that achieves gas/liquid or liquid/liquid mass transfer without dispersion of one phase within another. This is accomplished by passing the fluids on opposite sides of a microporous membrane. By careful control of the pressure difference between the fluids, one of the fluids is immobilized in the pores of the membrane so that the fluid/fluid interface is located at the mouth of each pore. This approach offers a number of important advantages over conventional dispersed phase contactors, including absence of emulsions, no flooding at high flow rates, no unloading at low flow rates, no density difference between fluids required, and surprisingly high interfacial area. Indeed, membrane contactors typically offer 30 times more area than what is achievable in gas absorbers and 500 times what is obtainable in liquid/liquid extraction columns, leading to remarkably low HTU values.\n\nAlthough a number of membrane module geometries are possible, hollow fiber modules have received the most attention. In general, tube side mass transfer coefficients can be predicted with reasonable accuracy; on the other hand, shell side coefficients are more difficult to determine, and several research groups are currently addressing this problem.\n\ nMembrane contactor technology has been demonstrated in a range of liquid/liquid and gas/liquid applications in fermentation, pharmaceuticals, wastewater treatment, chiral separations, semiconductor manufacturing, carbonation of beverages, metal ion extraction, protein extraction, VOC removal from waste gas, and osmotic distillation. This paper provides a general review of hollow fiber membrane contactors, including operating principles, relevant mathematics, and applications.”,”DOI”:”10.1016/S03767388(99 There are however some challenges in membrane technology that should be overcome in order to increase their performance and enlarge the fields of applications. When working with hollow fiber membranes contactors (HFMC) a well-known phenomenon takes place, GOLD SPONSOR

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namely the concentration polarization phenomenon. This refers to the increase of concentration gradients at the membrane/solution interface as a result of the membrane preferential mass transfer rate for some species. Consequently, a boundary layer appears at the wall interface decreasing the mass transfer through the membrane. 2 3 Several authors have tried to find a solution to this problem, especially by the use of turbulence promoters, either by adding tailor made spacers to the system or by changing the geometry of the fibers.4 Twisted, helical or waved geometries have been tested in order to increase the contactor efficiency. By changing the geometry, we are able to modify the hydrodynamics next to the membrane interface creating a secondary flux that enhances mass transfer and thus limits concentration polarization. In order to prove the interest of Dean Vortices for the improvement of CO2 mass transfer in HFMC, a CFD study using Ansys Fluent is carried out for fibers with a helical geometry; parameters such as the diameter, the pitch of the helix and the velocity inside the fibers were modified and each of these configurations was then compared to the conventional straight hollow fiber module. The results from simulations were then validated experimentally. Nuclear magnetic resonance (NMR) technology allowed us to visualize the velocity fields, longitudinal and transversal, and compare them to those obtained from simulations (Fig. 1). Measurements of CO2 flux transferred in helical modules are carried out to validate the improvement of mass transfer predicted by simulations. NMR Longitudinal velocity

FLUENT Longitudinal velocity 0.14

5

0.12

10

0.1

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0.06

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0.04

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35 10

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800 1000

0.02 200

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Figure 1. Longitudinal velocity fields for a helix of pitch = 7mm and diameter=16 mm. Left: Experimental NMR measurements. Right: Simulation from Fluent

Promising results have been found, a 70% improvement in CO2 mass transfer is found with a relatively small pressure drop. Local mass transfer coefficients for helical fibers are 3 to 4 times larger than those obtained for straight configurations (Fig. 2). We also conclude that parameters such as helix diameter and pitch do not play an important role in the interval studied. Mass transfer is indeed improved as soon as a helical form is used. Velocity plays a more important role as it influences the pressure drop and to a certain point the mass transfer improvement is no longer interesting due to the extra pressure drop generated. Fig. 2. Liquid mass transfer coefficient. Comparison of a straight fiber to a helix fiber.

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REFERENCES 1

Gabelman, A. & Hwang, S.-T. J. Membr. Sci. 1999, Vol 159, 61–106.

2

He, G., Mi, Y., Lock Yue, P. & Chen, G. J. Membr. Sci. 1999 Vol 153, 243–258.

3

Mourgues, A. & Sanchez, J. J. Membr. Sci. 2005, Vol 252, 133–144.

4

Yang, X., Wang, R., Fane, A., Tang, C. Y. & Wenten, I. G. 2013, Vol 51, 3604-3627

DEISY LIZETH MEJIA MENDEZ Title: PhD student Laboratoire Réactions Chimiques et Génie des Procédés, Country: France Phone: +33 609834454 E-mail: [email protected] 2015

PhD student Subject: Dean vortices and their influence in mass transfer: application to CO2 capture and water desalination.

2013-2014

Master 2 Mechanics, Energy, Processes and Products



Ecole Nationale Supérieure des Industries Chimiques ENSIC

2012-2014

Chemical Engineering degree Ecole Nationale Supérieure des Industries Chimiques ENSIC Jul.-Dec.2014 TOTAL –PERL Engineering internship: sizing and optimization of a stirred tank for the production of HPAM

Jan.-Jun.2014 CNRS –Laboratoire Réactions Chimiques et Génie de Procédés Master Intership: Improvement of a pilot unit for the production of super insulating aerogels. Research interests: Gas permeation, dense membranes, Computational Fluid Dynamics, process intensification.

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T1.12 HIEP T. LU THE IMPACT OF HYDROGEN SULFIDE AND ETHYLENE GLYCOL ON THE PERFORMANCE OF CELLULOSE TRIACETATE MEMBRANE FOR CO2 SEPARATION

HIEP T. LU1, COLIN A. SCHOLES1, SHINJI KANEHASHI1,2, SANDRA E. KENTISH1* 1 Department of Chemical and Biomolecular Engineering, University of Melbourne, Parkville, Victoria, 3010, AUSTRALIA. 2 Department of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo, 184-8588, JAPAN. Natural gas is a primary energy resource that will occupy over 25% of the global electricity market in the next decades, as well as acting as a transport fuel and direct heating resource. The composition of raw natural gas varies widely and contains several impurities such as nitrogen, carbon dioxide (CO2), water and hydrogen sulphide (H2S) that require removal to meet pipeline specifications. Membrane separation has been used for many decades for acid gas removal, known as natural gas sweetening, with advantages in energy efficiency, land footprint and a lack of chemical consumption. Although many new membrane materials have been developed, cellulose triacetate (CTA) membranes still retain the bulk of this separation market because of their high CO2/CH4 selectivity, commercial readiness and acceptance as a low risk option by the industry. Raw natural gas is usually saturated with water. However, this water is generally removed upstream of the membrane unit to avoid pipeline corrosion and hydrate formation. Glycols (monoethylene glycol (MEG), diethylene glycol (DEG) and triethylene glycol (TEG)) are the most common solvents utilised for this purpose1. This glycol solution may enter the membrane separation unit due to occasional flooding which may alter the permselectivity of the membrane and hence impact the gas separation performance. In this work, CTA membranes were aged in two common glycols, MEG and TEG, respectively. It was observed that the permeation of helium (He) and CH4 declined significantly after the membrane absorbed the glycol solutions. While the permeability of He dropped continuously as the glycol uptake increased, the permeation of CH4 initially fell and then increased again, indicative of the methane permeating through the glycol phase in addition to the polymer. Subsequently, the aged membranes were washed by methanol to remove the glycols absorption and retested. The methanol wash allowed the CTA membrane performance to be recovered with only a slight plasticisation observed with increasing aging time. Hydrogen sulphide is another common species that will enter the membrane unit with the natural gas. Many studies have been conducted on the performance of CTA membranes

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in the presence of H2S – CO2 and H2S – H2O mixtures2,3. However, the impact of temperature and pressure on H2S permeation through the CTA membrane have not been well studied. Furthermore, studies on the long term effect of these impurities on CTA gas separation performance is also limited. Thus, this presentation also investigates the permeation of H2S through a CTA membrane at different pressures and temperatures. It is found that the presence of H2S at 80oC plasticised the membrane and enhanced the gas transport through the membrane. However, long term aging in the presence of 1000ppm H2S at 7.5 Bar and 25oC showed comparable behaviour to that from aging in a comparable pressure of pure nitrogen. REFERENCES 1 Kohl, A. L., & Nielsen, R. B. (1997). Chapter 11 - Absorption of Water Vapor by Dehydrating Solutions Gas Purification (Fifth Edition) (pp. 946-1021). Houston: Gulf Professional Publishing. 2 Funk, E., S. Kulkarni, and A. Swamikannu. Effect of impurities on cellulose acetate membrane performance. in Recent Adv. in Separation Tech. AIChE Symposium Series. 1986. 3 Heilman, W., et al., Permeability of Polymer Films to Hydrogen Sulfide Gas. Industrial & Engineering Chemistry, 1956. 48(4): p. 821-824.

HIEP THUAN LU Title: Mr. Department of Chemical and Biomolecular Engineering, School of Engineering, University of Melbourne, Australia Phone: + 61 3 8344 8806 E-mail: [email protected] 2005 - 2010

Bachelor of Chemical Engineering – Ho Chi Minh City University of Technology – Vietnam National University - Vietnam

2012 - 2014

Master of Chemical Engineering – University of Melbourne - Australia

Since 2014

PhD of Engineering – University of Melbourne - Australia

Research interests: membrane, cellulose acetate, carbon capture

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T1.13 TAE-HYUN BAE, HEQING GONG MIXED-MATRIX MEMBRANES CONTAINING ENGINEERED NANOPOROUS MATERIALS FOR BIOGAS PURIFICATION

TAE-HYUN BAE1, 2, HEQING GONG1, TIEN HOA NGUYE1 1 School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 2 Singapore Membrane Technology Centre, Nanyang Technological University, Singapore Biogas produced in anaerobic digestion process has been considered as a renewable energy source. For the recovery and the purification of biogas, various processes for CO2 separation including amine-scrubbing and adsorption have been employed. Although membrane-based gas separation is an ideal platform for the biogas recovery/purification, the applications have been limited by the unsatisfactory performance of commercial polymeric membranes under the biogas separation conditions such as low CO2 partial pressure. Thus, improving the performance of current polymeric membranes, which are inexpensive and mechanically stable, may facilitate the application of membrane technology in large-scale biogas upgrading processes. To this end, various porous materials that can selectively transport CO2 can be incorporated into polymer matrices to design CO2-selective mixed-matrix membranes. Among various porous materials, metal-organic frameworks which comprise metal center and organic linkers to form three-dimensional porous structure have attracted vast research interests in the recent years as potential fillers for mixed-matrix membrane fabrication owing to their large pore volumes and tunable functionalities. In this work, a submicron-sized Zn(pyrz)2(SiF)6 metal-organic framework crystal possessing both an optimum pore size for selective CO2 permeation and a strong affinity for CO2 molecule was synthesized and incorporated into various polymer membranes to design mixed-matrix membranes for biogas upgrading. CO2/CH4 mixture gas permeation tests revealed that the separation properties of mixed-matrix membranes, especially selectivities, were significantly improved compared to those of pure polymeric membrane owing to the selective CO2 uptake and transport in the metal-organic framework crystals (Figure 1). Recently, our research group have developed hierarchical mesoporous Ca-A zeolites with amine-appended mesoporous domain for application in post-combustion CO2 capture. Owing to the contributions of both the active sites in Ca-A zeolites and the amine groups in mesoporous surfaces, the material exhibited an excellent CO2 uptake property even at low CO2 partial pressure. Moving forward, amine-appended hierarchical Ca-A was employed as a filler for mixed-matrix membranes to improve CO2 selectivity. Gas permeation testing revealed that the amine-appended hierarchical Ca-A is highly efficient in enhancing CO2/CH4 selectivity of polymeric membranes.

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Figure 1. Enhanced CO2/CH4 separation property of mixed-matrix membranes containing submicronsized Zn(pyrz)2(SiF6) crystals. REFERENCES 1

H. Gong, T. H. Nguyen, R. Wang, T. H. Bae, Separations of binary mixtures of CO2/CH4 and CO2/N2 with mixed matrix membranes containing Zn(pyrz)2(SiF)6 metal-organic framework, J. Membr. Sci. 2015, 495, 169-175

2

T. H. Nguyen, S. Kim, M. Yoon, T. H. Bae, Hierarchical LTA zeolites with amine-functionalized mesoporous domain for carbon dioxide capture, ChemSusChem, 2016, 9, 455-461

3

T. H. Nguyen, H. Gong, S. S. Lee, T. H. Bae, Amine-appended hierarchical Ca-A zeolite for enhancing CO2/CH4 selectivity of mixed-matrix membranes, submitted

TAE-HYUN BAE Title: Assistant Professor Nanyang Technological University Phone: +65 9295 6476 E-mail: [email protected] 2010

Ph. D in Chemical Engineering, Georgia Institute of Technology

2010-2013

Postdoctoral fellow, UC Berkeley

Since 2013

Assistant professor, Nanyang Technological University

Research interests: porous material, membrane, separation

GOLD SPONSOR

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T1.15 ZE-XIAN LOW ACCELERATED AGING OF MEMBRANES MADE FROM POLYMERS OF INTRINSIC MICROPOROSITY WITH SUPERCRITICAL CARBON DIOXIDE

ZE-XIAN LOW1,*, SARA SORRIBAS2, MARIOLINO CARTA3, PETER BUDD2, NEIL MCKEOWN3 AND DARRELL ALEC PATTERSON1* 1 Centre for Advanced Separations Engineering and Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, U.K. 2 School of Chemistry, University of Manchester, Manchester, M13 9PL, U.K. 3 School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Edinburgh, U.K. Hundreds of polymers have been evaluated for many different gas separations, but fewer than 10 membrane materials have been adopted into commercial applications. This is mainly due to two phenomena: plasticization and physical aging. Polymers of intrinsic microporosity (PIMs), discovered by Budd and McKeown, have a unique rigid and contorted macromolecular backbone structure which induce poor molecular packing, resulting in an interconnected irregularly shaped free volume that effectively behaves like a microporous material (which have a pore diameter < 2 nm: IUPAC). The result is a film with a high permeability paired with a high enough selectivity that it redefined the Robeson upper bound in 2008. However, PIMs, like other high free volume polymers, also suffer from physical aging. The changes often occur rapidly in the first few weeks, followed by gradual changes over the years. Consequently, to obtain a better understanding of how to design aging resistant PIMs (and other aging debilitated gas separation membranes), a rapid aging test needs to be developed to enable rapid and economic development and evaluation of aging within a reasonable timeframe. In this work, we have developed and evaluated one approach to solve this problem, through the application of supercritical CO2 (scCO2) to accelerate the aging of two PIMs (PIM-1 and PIM-EA-TB(H2); Fig. 1).

Figure 1. Molecular structures of PIM-1 and PIM-EA-TB(H2).

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The aging that occurred along with plasticization by CO2 molecules was compared to that without plasticization by using a non-plasticizing gas molecule. Both pristine and aged PIMs were characterized by their gas permeability in H2, N2, CO2, and O2 by means of a constant pressure variable volume gas permeation test. ScCO2 was generated and flowed into the membrane cell at 80 bar and 35°C, where the PIM film was secured. Preliminary results showed that scCO2, coupled with high temperature and pressure, could accelerate the aging of PIMs as demonstrated by the decrease in gas permeability and increase in ideal gas selectivity (Fig. 2). On the other hand, reducing the supercritical CO2 aging treatment time lead to the increase in permeability and decrease in ideal gas selectivity, an indication of plasticization. Interestingly, we also noticed that after scCO2 treatment both the PIM films showed sign of brittleness potentially caused by the more effective removal of absorbed solvent or impurities from the films. Further work is currently undergoing to investigate the effect of scCO2 aging time, temperature and pressure on the gas separation performance of the PIM films in single and binary gas mode.

Figure 2. (a) Gas permeability and (b) ideal gas selectivity of fresh PIM-1 and aged PIM-1.

ZE-XIAN (NICHOLAS) LOW Title: Postdoctoral Research Associate Centre of Advanced Separations Engineering, University of Bath, U.K. E-mail: [email protected], Website: www.nicholaslow.com 2012-2015

Ph.D. in Chemical Engineering, Monash University

Research interests: gas separation, engineered osmosis, 3D printing

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T1.16 SALMAN SHAHID NOVEL APPROACH TO PREPARE HIGHLY-LOADED ASYMMETRIC MOFMIXED MATRIX MEMBRANES USING PARTICLE FUSION TECHNIQUE

SALMAN SHAHID1,2,3, DAMIEN QUEMENER2, IVO VANKELECOM3 1 Centre for Advanced Separation Engineering and Department of Chemical Engineering, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom 2 Univ Montpellier 2, Institut Européen des Membranes, UMR CNRS ENSCM UM2 5635, Pl E Bataillon, F-34095 Montpellier, France 3 Centre of Surface Chemistry and Catalysis, KU Leuven, Box 2461, B-3001 Leuven, Belgium CO2 capture and gas separation through membranes has emerged as an important technology with several advantages over conventional separation processes such as cryogenic distillation and adsorption. However, performance of polymeric membranes is limited by a trade-off between membrane permeability and selectivity1. Among various novel materials, mixed matrix membranes (MMMs), incorporating molecular sieving materials within polymeric substrates, have received considerable attention over pristine polymeric membranes. The mixed matrix membranes approach, could potentially provide economical high performance gas separation membranes if defects at the filler/polymer matrix interface can be eliminated. MMMs incorporating conventional fillers e.g. zeolites, carbon materials etc., frequently suffer from insufficient adhesion between the polymer matrix and the fillers. This often result in the formation of voids at the filler/polymer interface, which degrades the performance of the membrane. Recently, Metal Organic Frameworks (MOFs) have been identified as attractive fillers. Due to the high flexibility of the MOF design, they allow to specifically tune the properties of the MOF towards high selectivity and permeability for specific separations. At the same time, it is with the current MOF chemistry possible to some extent to improve the embedding of the MOF in polymer matrix slightly. Nevertheless, still nonselective voids at the MOF/polymer matrix interface are frequently formed2,3. In addition to formation of non-selective voids, higher MOF loadings result in better separation behaviour, but cause agglomeration of filler and poor filler distribution. In this work, we introduce a breakthrough in development of MOF based asymmetric MMMs by using particle fusion of polymer matrix and MOF as the additive particles, that improves the MOF polymer interaction and eliminates the MOF compatibility, agglomeration and distribution problems, even at high loadings of MOF. Polyimide polymer particles are first prepared by emulsifying the Matrimid® polyimide polymer solution into a non-solvent. The surface of these particles are modified by giving them

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imidazole functionality. The ZIF-8 particles are then grown into this modified polymer particles suspension by addition of the precursors for ZIF-8 synthesis. The resulted suspension was dried in solvent-vapour environment for two days to dissolve the polymer particles around the ZIF-8 particles, to obtain an asymmetric MMMs (Fig. 1). These membranes were characterized by XRD, TGA and DSC. Scanning electron microscopy (SEM) showed excellent distribution of particles covering the whole cross-section of the matrix, forming a percolating pathway, without any agglomeration, even at 40 wt.% loading of the ZIF-8 (Fig.1). Prepared asymmetric MMMs have a huge improvement in CO2 permeability and CO2/CH4 selectivity. The permeability of the MMMs showed an increase of 250 % for CO2 permeability and CO2/CH4 selectivity got doubled compared to native polymer. The presented route is a very versatile MMM preparation route, not only for this specific ZIF and polymer but for a wide range of combinations.

Figure 1. Surface and cross-sectional transformation from particulate morphology to asymmetric MMM morphology (at 30 wt% ZIF-8 loading) over a period of 2 days.

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REFERENCES 1 L.M. Robeson J. Membr. Sci., 2008, 320, 390-400. 2 T.T. Moore, W.J. Koros, Journal of Molecular Structure, 2005, 739, 87-98. 3 R. Mahajan and W. J. Koros, Polymer engineering and science, 2002,42, 1420-1431.

SALMAN SHAHID Title: Dr. Centre of Advanced Separation Engineering and Department of Chemical Engineering, University of Bath, United Kingdom. Phone: +00447467910467 E-mail: [email protected] 2010

University of Catholique Louvain, Belgium

2011-2012

University of Twente, Netherlands

2012-2013

University of Montpellier-2, France

2013-2014

University of Leuven, Belgium

2014-2015

Technical university of Delft, Netherlands

Since Dec 2015

PDRA at University of Bath, UK

Research interests: Membranes, Liquid separations, Gas separation, MOFs, Catalysis

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T1.17 INORGANIC NANOPARTICLES/ MOFS COMPOSITE MEMBRANE REACTORS FOR CO2 SEPARATION AND CONVERSION

J. W. MAINA1*, ELISE DES LIGNERIS1, C. POZO-GONZALO1, L. KONG1, J.SCHÜTZ2, MIHAIL IONESCU3, L. F. DUMÉE1 1 Institute for Frontier Materials, Deakin University, Pigdons Road, 3216 Waurn Ponds, Victoria, Australia 2 Commonwealth Scientific and Industrial Research Organisation 75 Pigdons Road Waurn Ponds Vic 3216 3 Australian Nuclear Science and Technology Organization (ANSTO) Abstract Summary: We report the fabrication of inorganic nanoparticles/metal organic frameworks (MOFs) composite membranes reactors, for simultaneous separation and conversion of CO2. The MOF membranes were fabricated across highly porous metal substrates through solvothermal synthesis, after which they were systematically doped with catalytic inorganic nanoparticles. The composite membranes were characterized using scanning electron microscopy (SEM), small angle X-ray scattering (SAXS), Rutherford backscattering spectrometry (RBS) and particles induced X-ray emission (PIXE). Gas permeation studies will be curried out using single gas permeation rig, while the efficiency of the membrane reactors in the conversion of CO2 will be assessed under UV irradiation. Introduction: Increased emission of Carbon dioxide (CO2) from the combustion of fossil fuel is the primary cause of global warming, leading to adverse climatic changes and ocean acidification.1 CO2 capture and storage (CCS) technology, where CO2 is captured from a large point source and then injected to an underground reservoir, has been proposed as a potential solution, to limit emission of the greenhouse gas. However, the high cost associated with CO2 transport to the storage site make the process cost prohibitive.2 In addition, ensuring that the large amounts of CO2 stored underground do not leak back to the atmosphere require complex infrastructures, and frequent monitoring.3 Utilization of CO2 as a raw material to produce valuable chemicals and fuels is a sustainable approach for mitigating the adverse effect of global warming. In the presence of a suitable catalyst, CO2 may be converted to valuable products such as methanol, methane and formic acid through photocatalysis and electrocatalysis. Furthermore, membrane reactor based catalytic systems have potential to facilitate direct conversion of CO2 from flue gas stream, due to their ability to facilitate concurrent separation and chemical reactions, thus providing a potential economical solution, by eliminating the cost associated with CO2 transport and storage. This work seeks to develop inorganic nanoparticles/metal organic frameworks (MOFs) hybrid membrane reactors, for simultaneous separation and conversion of CO2. Metal organic frameworks (MOFs), hybrid materials composed of metal ions coordinated to GOLD SPONSOR

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organic ligands, were selected due to their exceptionally high surface area (1000 – 10,000 m2/g) and tunable pore size distributions (0.3 to 10 nm).4 The MOFs used in this work are zeolitic imidazolate frameworks ZIF-8 and ZIF-7, which have pore apertures of 3.4 Å and 3 Å respectively, and exceptional thermal and chemical stability.5 ZIF-8 membrane layer was first fabricated across highly porous metal substrates through solvothermal synthesis, and then modified with a second layer of ZIF-7 via rapid thermal deposition, to heal any defective sites within the membrane and enhance CO2/N2 selectivity. The MOFs membrane were then systematically doped with catalytic TiO2 nanoparticles via postsynthetic secondary growth, to introduce catalytic activity towards CO2 reduction. Schematic illustration of the cross-section of the inorganic nanoparticles doped MOF membrane is represented in Scheme 1. Successful doping of the MOF membranes with the TiO2 nanoparticles was confirmed by SEM, where the inorganic nanoparticles could be observed embedded on the surface of the membrane (Fig. 1 a). This was further confirmed by the observation Ti spectra from the energy dispersive x-ray spectroscopy (EDX) analysis (Fig. 1b). Preliminary permeation studies show gas diffusion rate across the composite membranes was dependent upon the molecular weight of the gas. The dispersion of the inorganic nanoparticles across the MOF membranes will be assessed using small angle x-ray scattering (SAXS), while the quantification and depth profile distribution of the inorganic nanoparticles will be characterized using Rutherford backscattering (RBS) and particles induced x-ray emission (PIXE). The co-relation of the hybrid membrane reactors composition with the conversion efficiency of CO2 as well as the product selectivity will be assessed under UV irradiation, while gas permeation studies will be carried out using single gas permeation rig.

Scheme 1. Cross-section of inorganic nanoparticles doped MOF membrane.

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Fig. 1. (a) SEM image of the surface of TiO2 doped ZIF-8 membrane (b) EDX spectra for the surface of the hybrid membrane reactor. REFERENCES 1. (a) Li, J.-R.; Ma, Y.; McCarthy, M. C.; Sculley, J.; Yu, J.; Jeong, H.-K.; Balbuena, P. B.; Zhou, H.-C., Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks. Coordination Chemistry Reviews 2011, 255 (15–16), 1791-1823; (b) McDonald, T. M.; Mason, J. A.; Kong, X.; Bloch, E. D.; Gygi, D.; Dani, A.; Crocella, V.; Giordanino, F.; Odoh, S. O.; Drisdell, W. S.; Vlaisavljevich, B.; Dzubak, A. L.; Poloni, R.; Schnell, S. K.; Planas, N.; Lee, K.; Pascal, T.; Wan, L. F.; Prendergast, D.; Neaton, J. B.; Smit, B.; Kortright, J. B.; Gagliardi, L.; Bordiga, S.; Reimer, J. A.; Long, J. R., Cooperative insertion of CO2 in diamine-appended metal-organic frameworks. Nature 2015, 519 (7543), 303-8. 2. Agarwal, A. S.; Zhai, Y.; Hill, D.; Sridhar, N., The Electrochemical Reduction of Carbon Dioxide to Formate/Formic Acid: Engineering and Economic Feasibility. ChemSusChem 2011, 4 (9), 3. Maginn, E. J., What to Do with CO2. The Journal of Physical Chemistry Letters 2010, 1 (24), 3478-3479. 4. Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M., The chemistry and applications of metal-organic frameworks. Science 2013, 341 (6149), 1230444. 5. (a) Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M., Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proceedings of the National Academy of Sciences 2006, 103 (27), 10186-10191; (b) Li, Y.; Liang, F.; Bux, H.; Yang, W.; Caro, J., Zeolitic imidazolate framework ZIF-7 based molecular sieve membrane for hydrogen separation. Journal of Membrane Science 2010, 354 (1), 48-54.

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T1.18 COLIN A. SCHOLES POLYMERIC MEMBRANES FOR HELIUM SEPARATION Department of Chemical & Biomolecular Engineering, University of Melbourne, VIC, Australia Helium is a non-renewable resource, whose primary source is natural gas. Currently, only those natural gas fields with relatively high helium concentration (>2 %) are economically viable for helium production; through cryogenic fractional distillation and pressure swing adsorption. Membranes are an alternative gas separation technology that has potential in the helium purification and processing industry because of its ability to selectively separate out one or more gases. Hence, lower quality natural gas fields can become commercially viable through the combination of membrane gas separation and cryogenic distillation. This paper will explore the potential for polymeric gas separation membranes in helium production, particularly how polymeric membranes can be modified to have improved He permselectivity against a range of gases. The approach focuses on taking advantage of He’s small kinetic diameter and chemical inertness relative to other gases. Hence, for non-porous membranes’ He permeability is strongly diffusivity controlled. As such, the membrane morphology can be altered through additives so that the permeability of other gases, such as CH4 and N2, are reduced within polymeric membranes while also ensuring He permeability is unaffected. This leads to a significant improvement in He selectivity. However, it is recognized that gas separation membranes alone will have difficulty in being competitive for direct separation from natural gas. As such, some of the discussion will focus on how membranes can be incorporated into existing He recovery processes, and the level of separation performance needed to be viable against existing He recovery technologies. Hence, this study will draw on both experimental and simulation research into helium selective membranes.

COLIN SCHOLES University of Melbourne, Australia Phone: +61390358289 Fax: +61383444153 E-mail: [email protected] Senior Lecturer, University of Melbourne Research interests: Gas and vapor separation, polymeric membranes, polymer films, process simulations

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T1.19 ASIM LAEEQ KHAN MIXED MATRIX MEMBRANES COMPRISING OF FLUORINATED AND SULFONATED PEEK AND FUNCTIONALIZED MESOPOROUS COK-12 FOR CO2 SEPARATION

ASIM LAEEQ KHAN1, SREEPRASANTH P. SREE2, JOHAN A MARTENS2, XIANFENG LI3 AND IVO F. J. VANKELECOM2 1 Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Pakistan 2 Center for Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, KU Leuven, Belgium 3 Lab of PEMFC Key Materials and Technologies, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China The excessive use of fossil fuels such as coal and petroleum products is one of the primary sources of CO2 emissions. CO2 thus emitted is a major contributor to the greenhouse effect of earth, resulting in increase in global warming. Membrane technology is an attractive choice to perform this task due to its many advantages over other separation techniques such as environment friendly, cheap and energy efficient1. Mixed matrix membranes (MMMs) comprising of an inorganic filler and a polymer matrix have shown the potential to increase the performance of gas separation membranes1. In this study, new types of MMMs composed of novel polymer, a fluorinated and sulfonated aromatic poly (ether ether ketone) (FSPEEK) and –SO3 functionalized mesoporous silica spheres were prepared by solution casting method. The dispersion of the fillers in the polymer matrix was improved by employing solution blending and probe sonication techniques. The thickness of the membranes was controlled at 50-65 µm. Sulfonated polymers have shown their potential to surpass the Robeson upper bound2-3. The incorporation of bulky fluorinated groups in the polymer is expected to further increase the separation performance due to inhibition of chain packing and increased steric hindrance4. The presence of C2F6 type fluorinated groups improves the fractional free volume by the inhibition of chain packing. These bulky groups also restrict the torsional motion of the polymeric chains and simultaneously increase the rigidity of polymer resulting in strong ability of size sieving. The degree of sulfonation was fixed at 50% for all the synthesized MMMs. CO2 permeation and SEM images of the synthesized MMMs suggest that the fillers adhered well to the polymer matrix. The non-functionalized COK-12 based MMMs showed up to 26% increase in CO2 permeability at 30% filler loading. The selectivity values however decreased upon addition of more COK-12. In contrast, the –SO3 functionalized filler showed a 35% and 29% higher CO2/CH4 and CO2/N2 selectivity respectively at the 30 wt. %. GOLD SPONSOR

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This behavior resulted from the increase in the content of polar –SO3 sites, the introduction of fixed mesopores by the filler and disruption of chain packing by the addition of fillers. The performance of the synthesized MMMs were also tested under mixed gas conditions to evaluation their commercial application. The results showed slightly lower permselectivity values in comparison to pure gas tests. This was attributed to the competitive sorption effect of the permeating gas molecules. The effect of pressure was also studied to evaluate the plasticization performance. The observed increase in permeability and selectivity along with good anti-plasticization properties make this novel fluorinated and sulfonated polymer with -SO3 based mesoporous COK-12 a promising candidate for gas separation membranes. (b)

(a)

Fig. 1. SEM images of cross-sections of MMMs containing (a) 20 and (b) 30% loading of COK-12 particles. REFERENCES 1

S. Basu, A.L. Khan, A. Cano-Odena, C. Liu, I.F. Vankelecom, Chemical Society reviews, 2010, 39, 750-768.

2 L.M. Robeson, J. Membr. Sci. 2008, 320, 390-400. 3 A. L. Khan, X. Li and I. F. J. Vankelecom, J. Membr. Sci. 2011, 372, 87-96. 4 T. Suzuki, Y. Yamada and Y. Tsujita, Polymer, 2004, 45, 7167-7171.

ASIM LAEEQ KHAN Title: Dr. Affiliation, Country: COMSATS Institute of Information Technology, Pakistan. Phone: +92-3245676868 E-mail: [email protected] Personal History: 2008-2011: PhD Candidate at KU Leuven, Belgium 2011-2012: Post-Doc Research Fellow at KU Leuven, Belgium Since year 2012: Assistant Professor at COMSATS Institute of Information Technology Research interests: Membrane based Gas Separation, Mixed Matrix Membranes

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THEME: NOVEL MATERIALS AND SURFACE MODIFICATIONS T2.2 JONGMAN LEE IMPROVING THE ANTIFOULING PROPERTIES OF CERAMIC MEMBRANES VIA SURFACE MODIFICATION

JONGMAN LEE, JANG-HOON HA, AND IN-HYUCK SONG Korea Institute of Materials Science, Republic of Korea We have endeavored to prepare organosilane-grafted alumina membranes with enhanced antifouling surface properties through a simple silanization process. To better understand the antifouling mechanisms, three representative organosilanes presenting neutral (-CH3), positive (-NH2), and negative (-SO3) charges were allowed to graft onto pristine alumina membranes. The surface morphologies of the organosilane-grafted membranes were almost identical to those of the pristine alumina membranes. However, a small decrease in the average pore size was observed due to the new formation of organosilane layers. The stable chemical binding of organosilanes was successfully confirmed through Raman spectra or X-ray photoelectron spectroscopy (XPS). A schematic diagram of organosilane-grafted alumina membranes and feasible interactions with humic acid (as a model foulant) on the uppermost layers is presented in Figure 1. A membrane filtration test using humic acid was then conducted to evaluate the effect of surface charges on fouling resistance. As shown in Figure 2, the neutral and negatively charged membranes maintained higher flux patterns for 60 min. However, the pristine alumina and positively charged membranes led to a noticeable flux decline. Notably, the negatively charged membranes achieved the most remarkable flux behavior during entire fouling procedure. This result is primarily attributed to the electrostatic repulsion force between the organosilane-grafted membranes and negatively charged humic acid (IEP: 4.7). The negatively charged membranes were also confirmed to exhibit the greatest performance because they presented the lowest flux decline ratio (%), the highest flux recovery ratio (%), and the lowest membrane fouling (%). The effect of organosilane-grafted ceramic membranes on the antifouling properties were further investigated in terms of humic acid concentration and organosilane concentrations. As a result, two findings are highly anticipated. First, the membrane fouling became apparently worsened with an increasing concentration of humic acid. Second, the fouling resistance was made more efficient as combining with higher negative organosilane concentrations. Overall, this presentation will discuss the notable effectiveness of negatively charged alumina membranes for improving fouling resistance.

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Figure 1. Schematic diagram of organosilane-grafted alumina membranes and feasible interactions with negatively charged humic acid (HA) on the uppermost layers during membrane fouling procedures.

Figure 2. Time-dependent flux behaviour during membrane fouling procedures (step 1 to step 4) using humic acid as a model foulant.

JONGMAN LEE Title: Senior Researcher Korea Institute of Materials Science, Republic of Korea Phone: +82-55-280-3292 Fax: +82-55-280-3289 E-mail: [email protected] 2012-present

Senior Researcher in Korea Institute of Materials Science

Research interests: Ceramic membrane, Surface modification, Water treatment

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T2.3 YUAN LIAO DESIGN AND FABRICATION OF SUPERHYDROPHILIC THIN FILM COMPOSITE NANOFIBROUS MEMBRANES FOR RECALCITRANT ORGANICS REMOVAL IN AN EXTRACTIVE MEMBRANE BIOREACTOR PROCESS

YUAN LIAO1, RONG WANG1, 2, ANTHONY G. FANE1, 2 1 Singapore Membrane Technology Center, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore 2 School of Civil and Environmental Engineering, Nanyang Technological University, Singapore A mixture of organic compounds, presenting in complex waste streams that often generated by chemical, petrochemical, pharmaceutical, pulp and paper industries, are toxic to human and ecosystem even at low concentration.1 It is essential to remove these toxic organic compounds from wastewater before discharge via an energy-efficient, environment friendly and reliable method. Extractive membrane bioreactor (EMBR), which combines an aqueous-aqueous extractive membrane process and a biodegradation process, is considered as an attractive option to separate and degrade recalcitrant organics from wastewater simultaneously.2 As shown in Fig. 1, in an EMBR process, the target organic pollutants are extracted from an inhibitory system through a non-porous membrane to a downstream bio-medium by solution-diffusion mechanism, driven by concentration gradient across the membrane. Then the organic pollutants are biodegraded by specific microorganisms.

Figure 1. Schematic illustration of an extractive membrane bioreactor (EMBR) and the as-designed superhydrophilic thin film composite (TFC) nanofibrous membrane GOLD SPONSOR

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In an EMBR process, the membrane plays an important role to transfer recalcitrant organics and separate inhibitory feed and bio-medium receiving sides. The main requirements of the membrane are: (1) the membrane should be highly permeable to organics and impermeable to acid, caustic, inorganic salts and water; (2) the membrane should be stable under harsh conditions in long-term usage. Most commercial membranes used in this application are silicon rubbers such as Polydimethysiloxane (PDMS). The small organic molecules can transport through free volume of PDMS due to its Si-O units.3 The commercial silicon rubber tubes usually has a high thickness (>0.2 mm), which increases membrane resistance significantly. A possible strategy to reduce membrane resistance is to design and develop thin film composite (TFC) membranes, which consist of a thin PDMS selective layer and a highly porous support. Additionally, as conventional MBR processes, membrane performance in EMBR process decreases inevitably with operation time due to the deposition of bio-fouling layer on membrane surface.4 This remains one of the most challenging issues facing further EMBR development. As shown in Fig. 1, superhydrophilic TFC nanofibrous membranes have been designed and developed for EMBR process by electrospinning and further modification in this work. A dual-layer polyvinylidene fluoride (PVDF) nanofibrous support with an open, interconnected and highly porous structure was developed by electrospinning. A highly rough nanobeads structure was constructed on the membrane biomass-facing surface by electrospinning. Then a thin and homogenous PDMS layer was coated on the PVDF nanofibrous surface by spray-coating. The as-prepared TFC nanofibrous membrane was then modified to be superhydrophilic by dopamine surface activation and grafting of polyethylene glycol (PEG) with different molecular weights (800 and 6000). The modification is convenient because of mild reactions and wild applicability. The membranes are designed to prevent or reduce bio-fouling by providing surface with hydrophilic networks (PEG) and topographical complexities (highly rough nanobeads structure), which are expected to discourage any favourable interactions between membrane and the adhesive biomacromolecular segments. To the best of my knowledge, no research has been published regarding fabrication of superhydrophilic TFC nanofibrous membranes with satisfied performance for organics removal in EMBR process by electrospinning and further modification. It is also the first time to coat a thin PDMS layer on the nanofibrous membrane surface by spray-coating. Moreover, this work firstly investigated the effects of different hydrophilic macromolecular weights on membrane antifouling properties in EMBR process. These novel TFC nanofibrous membranes have been characterized by a series of measurements. The XPS characterization revealed that the modifications have been carried out on the membrane surface successfully. It altered the biomass-facing membrane surface from superhydrophobic (water contact angle over 150°) to superhydrophilic (water contact contact is 0°) due to its hierarchical structure and hydrophilic chemical groups. The surface and cross-sectional morphologies of as-prepared membranes were observed by FESEM. The images confirmed that the TFC nanofibrous membranes were composed of a uniform PDMS surface layer with a thickness of 5 µm, a PVDF nanofibrous support with a thickness of 20 µm and a rough nanobeads bottom layer with a thickness of 5 µm. The mechanical strengths of these membranes were provided by

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a non-woven support between the PVDF nanofibrous support and the nanobeads layer. The three different TFC nanofibrous membranes, which are the membrane without modification (#1-TFC), membrane modified by PEG with molecular weight of 800 (#2-TFC) and 6000 (#3-TFC), showed similar the overall mass transfer coefficient (k0) for phenol removal in an aqueous-aqueous process (10.2 × 10-7 m/s, 12.5 × 10-7 m/s and 11.9 × 10-7 m/s, respectively). The membrane showed stable k0 and maintained low inorganic flux in a 14 days continuous testing in an aqueous-aqueous process. In over 250 hours of cross flow EMBR operation, the biofilm growth on the PEG-modified TFC membranes was delayed. Both #2-TFC and #3-TFC membranes showed higher k0 of 9.5 × 10-7 m/s and 9.0 × 10-7 m/s in the first three days while the performance of #1-TFC membrane decreased to 6.2× 10-7 m/s in the first day. Compared with #3-TFC modified with high molecular weight PEG, the #2-TFC showed better antifouling performance in 250 hours EMBR operation, which should be attributed to its brush-like surface structure. After 250 hour EMBR testing, #2-TFC possessed k0 of 4.8 × 10-7 m/s while #3-TFC showed k0 of 3.5 × 10-7 m/s. The TFC nanofibrous membranes prepared in this work outperformed the existing commercial PDMS tubular membrane in an EMBR process with over 4 times higher k0 for phenol removal. Thus, such superhydrophilic TFC nanofibrous membranes emerged as promising candidates for EMBR process. REFERENCES: 1

B. J. L. Yeo, S. Goh, J. Zhang, A. G. Livingston, A. G. Fane, J. Chem. Technol. Biotechnol. 2015, 90, 1949-1967.

2

A. G. Livingston, J. Chem. Technol. Biotechnol. 1994, 60, 117-124.

3

C. H. Loh, Y. Zhang, S. Goh, R. Wang, A. G. Fane, J. Membr. Sci. 2016, 500, 236-244.

4

P. Le-Clech, V. Chen, T. A. G. Fane, J. Membr. Sci. 2006, 284, 17-53.

YUAN LIAO Title: Dr. Research Fellow, Singapore Membrane Technology Center, Nanyang Technological University, Singapore 637141 Phone: +65 9087 1506 Fax: +65 6791 0756 E-mail: [email protected] Since 2015

Postdoctoral Research Fellow Singapore Membrane Technology Center (SMTC), Singapore

2014 – 2015

Research Associate Singapore Membrane Technology Center (SMTC), Singapore

2010 – 2014

PhD in Environmental Engineering Nanyang Technological University (NTU), Singapore

2007 – 2010

Master in Material Science and Engineering School of material science and engineering, Beijing University of Chemical Technology (BUCT), Beijing, P. R. China

2003 –2007

Bachelor in Polymer Science and Engineering School of material science and engineering, Beijing University of Chemical Technology (BUCT), Beijing, P. R. China

Research interests: Membrane fabrication and modification for water treatment GOLD SPONSOR

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T2.4 KIRSTEN REMMEN APPLICATION AND STABILITY OF LAYER-BY-LAYER MODIFIED MEMBRANES IN ACIDIC ENVIRONMENT FOR PHOSPHORUS RECOVERY

KIRSTEN REMMEN1 , DANIEL MENNE2, THERESE KRAHNSTÖVER1, THOMAS WINTGENS1, MATTHIAS WESSLING2 1 University of Applied Sciences and Arts Northwestern Switzerland, Institute for Ecopreneurship, Gründenstrasse 40, 4132 Muttenz, Switzerland 2 RWTH Aachen, Lehrstuhl für Chemische Verfahrenstechnik, Turmstraße 46, 52064 Aachen, Germany INTRODUCTION

Phosphorus is an essential nutrient for all living organisms. However, phosphorus deposits are limited and located in only a few regions worldwide. In the near future phosphorus recovery will be necessary to ensure food security worldwide. Current studies have shown that nanofiltration (NF) is a suitable technique for the recovery of phosphorus from acidic disintegrated sewages sludge1,2. However, these studies have also shown that the currently commercially available membranes are not suitable for this separation task. The phosphorus recovery is too low for an economically feasible application. Moreover, most membranes are not stable in low pH-ranges. Schütte et al. 2 showed that membranes with high pH resistances will lead to lower fluxes. One possible option to overcome the mentioned drawbacks are layer-by-layer (LbL) modified membranes. Polyelectrolytes (PE) are deposited on an acid resistant polyethersulfone (PES) or sulfonated polyethersulfone (SPES) ultrafiltration membrane. Several studies have shown that LbL-modification can be used for tailoring the filtration properties of NF3,4. However, the behaviour of PE deposited on PES membranes in an acidic environment has not been studied in detail yet. Acid resistant NF LbL membranes would lead not only to an advanced phosphorus recovery from sewage sludge, but to many applications in acid and nutrient recovery. Therefore this study is aiming at demonstrating new possibilities for phosphorus recovery using modified membranes and additionally showing new options for membrane application in an acidic environment. MATERIALS AND METHODS

Sewage sludge was disintegrated using sulphuric acid. The pH was adjusted to pH= 1.5. The pre-treatment, membrane testing and analytics were carried out according to Schütte et al.2. The membranes for phosphorus recovery from sewage sludge were modified as described in Menne et al.3. Acid resistance of the membrane were tested using UF hollow fibre membranes based on PES. The membranes were provided by Pentair X-Flow. Four bi-layers of PDADMAC/PSS were deposited through filtration on the membrane at 3 bar. The accumulated PE on the

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membrane was 2g/m2 for each layer. Afterwards in the hollow fibres were immersed in 15% phosphoric acid for 2,4 and 16 hours. Magnesium retention was tested at 4 bar before and after the acid treatment to assess acid stability. RESULTS AND CONCLUSION

Figure 1 shows that LbL-modified membranes proved to be well applicable for phosphorus recovery from sewage slugde. Phosphorus retention is around 0.2 for a permeate recovery of 50%. Metals such as aluminium and iron are almost fully retained in the retentate. The flux decreases from 40 L/m2/h at 0% permeate recovery to 35 L/m2/h at 50% recovery. Compared to other studies this is an increase in flux and phosphorus recovery, while still reaching very high metal retentions1,2. The flux is 10 times higher compared to the results from Schütte et al., when reaching phosphorus retention values of 0.32.

Figure 1: Flux and retention values for filtration at a TMP of 7 bar

Figure 2: Magnesium retention of LbL modified membranes after immersed into 15% phosphoric acid (n=?) GOLD SPONSOR

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In a second step the acid stability was tested by exposure to 15% phosphoric acid. The results are shown in Figure 2. It can be seen that the magnesium retention increases after the deposition of 4 bi-layers. However, the retention decreases after 4 and 16 h of acidic exposure of the membrane. This might lead to the conclusion that parts of the applied layers were altered due to acidic treatment. Further steps will be a variation in the number of layers, testing different UF-membrane materials and combinations of PE to identify a possible combination for application in acidic environment. It could be successfully shown that LbL modified membranes are suitable for the separation of phosphorus from acidic water streams contaminated with metals. REFERENCES 1

Niewersch, C., (2013) Nanofiltration for Phosphorus Recycling from Sewage Sludge. Verlagshaus Mainz GmbH Aachen

2

Schütte, T., Niewersch, C., Wintgens, T., Yüce S., (2015). Phosphorus recovery from sewage sludge by nanofiltration in diafiltration mode, Journal of Membrane Science, 480, 74–82

3

Menne, D., Kamp, J., Wong, J.E., Wessling, M., (2016). Precise tuning of salt retention of backwashable polyelectrolyte multilayer hollow fiber nanofiltration membranes, Journal of Membrane Science, 499, 396-405

4

De Grooth, J., Haakmeester, B., Wever, C., de Vos., W.M., Potreck, J., Nijmeijer, K., (2015) Long term physical and chemical stability of polyelectrolyte multilayer membranes Journal of Membrane Science, 489, 153-159

KIRSTEN REMMEN Title: Diplom-Ingenieur University of Applied Sciences and Arts Northwestern Switzerland, Switzerland Phone: +41 61 467 43 89 E-mail: [email protected] 2013

Graduated Dipl.-Ing

Since 2013

Research assistant, PhD-Candidate

Research interests: nanofiltration, membrane modification, phosphorus recovery, acid recovery

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T2.5 WENWEI ZHONG BIO-INSPIRED MEMBRANE SURFACE WITH PEI/PDA ASSISTED MINERALIZATION FOR SUPERHYDROPHOBIC MODIFICATION

WENWEI ZHONG1,HAOCHENG YANG2, JINGWEI HOU1 AND VICKI CHEN1 1 UNESCO Centre for Membrane Science and Technology, UNSW Australia 2 MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Zhejiang University, China Membrane distillation (MD) for water treatment is driven by the water vapour pressure difference across a hydrophobic membrane. Due to the usual applications in treatment of highly concentrated salty effluents, fouling and scaling are highly likely to take place in the MD process. Therefore, the study of anti-fouling for MD process is essential for a wider application. Anti-fouling techniques often include physical cleaning, chemical cleaning and surface modification. Strong interests have been shown on improving the hydrophobicity of membranes to improve its fouling and wetting resistance. Commonly applied techniques include sol-gel methods, electrospinning, plasma etching and solution-immersion for the production of a superhydrophobic surface4. The key to improve the surface hydrophobicity is to introduce a surface with low surface energy and nano-scale roughness. This can be achieved by the coating of inorganic nanoparticles like silica and titania and subsequent surface superhydrophobic functionalization. In terms of the supporting membrane, polypropylene (PP) membranes were proven to have better performances in MD application than PTFE and PVDF membranes5. However, due to the lack of functional group, the surface modification of PP can be a challenge. We discovered that by simple immersing hydrophobic PP hollow fibre membranes into polyethylenimine and dopamine (PEI/PDA) solution for a designated time, a thin, uniform PEI/PDA coating layer can be achieved. In addition, the PEI/PDA modification depth (against the thickness of the whole membrane wall) can be tuned by controlling the deposition time. Subsequently, the presence of catechol and amine groups on the PEI/PDA layer can induce the mineralization of inorganic silica nanoparticles6, which can be further modified to achieve superhydrophobicity. Compared with conventional surface functionalization process, this method is relatively facile and easy to control. The aim of this study is to understand the effect of superhydrophobic layer thickness on the membrane MD performance. Comprehensive characterizations of the virgin and modified membranes are carried out, including surface morphology, contact angle, and liquid entry pressure. In addition, the MD performance is measured with both Milli-Q water, 35g/L sodium chloride and complex brackish groundwater concentrates as feeds. The flux and salt rejection are measured with a submerged vacuum membrane distillation (VMD) setup. GOLD SPONSOR

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Preliminary result has shown great promise in operational stability compared to the virgin membrane. Severe wetting took place within 8 hours of operation for the virgin membrane, while very low permeate conductivity (<5µS/cm) was maintained for more than 24 hours with the modified membrane. As shown in Fig.1, salt rejection for the modified membrane remained high at a cumulative volume of 140L/m2 while severe salt breakthrough occurred at a cumulative volume of 60L/m2 for the virgin membrane. Silicon and fluoride elements were identified across the modified membrane (Fig.2). Distinct nanoparticles were also observed on the outer surface of the modified membrane (Fig.3), indicating an increase of surface roughness.

Figure 1. Permeate conductivity profile for the virgin membrane and modified membrane (6hrs deposition time in PEI/PDA) in in submerged VMD, feed as 4L 35g/L NaCl at 70˚C

Figure 2. SEM and EDS analysis of the cross-sections of the modified membrane (upper) and virgin membrane (lower)

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Figure 3. SEM images of the modified membrane (left) and virgin membrane (right)

WENWEI ZHONG Title: Miss UNSW, Australia Phone: +61 405257735 E-mail: [email protected] 2010-2014

Bachelor of Chemical Engineering (1st class honours), UNSW Australia

2014-2017

PhD student in Chemical Engineering

Research interests: MD, Fouling, Wetting, Surface modification

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THEME: GAS SEPARATIONS

T2.6 LILIANA PÉREZ-MANRÍQUEZ ULTRATHIN MUSSEL-INSPIRED SOLVENT RESISTANT NANOFILTRATION MEMBRANES

LILIANA PÉREZ-MANRÍQUEZ,1 ALI R BEZHAD,2 KLAUS-VIKTOR PEINEMANN1 1 King Abdullah University Of Science And Technology (kaust) 2 Imaging Core Lab, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia. Many efforts have been devoted to improve nanofilt- ration membrane performance and extend their ap- plication via surface engineering. Inspired by the composition of adhesive proteins in mussels, dopa- mine has been utilized as a versatile and intriguing starting material for surface modification under mild conditions.1,2 In this work, we report for the first time the use of dopamine/terephtaoyl chloride for the fabrication of a smooth ultra-thin film composite membrane (~5.4 nm thickness) for solvent resistant nanofiltration ap- plications by optimizing the interfacial polymerization and crosslinking techniques. We achieved excel- lent permeation and rejection performance using di- methylformamide solutions. The ease of chemical modification and preparation makes this bio-inspired membranes potentially easy to scale up at low cost. The chemical crosslinking of PAN on polypropylene non-woven support with hydrazine hydrate3 followed by interfacial polymerization using dopa- mine and terephtaoyl chloride, resulted in a new type of PAN solvent resistant nanofiltration membrane with an extremely thin and smooth selective layer. A solvent resistant composite nanofiltration membrane with a coating thickness below 8nm was never been reported before4 . Moreover, no change in the mor- phology of the thin film composite membrane was observed in DMF even after several days of being immersed in such a harsh environment. The resulting thin-film composite membrane showed permeances up to 5 L/m2 h bar combined with a molecular weight cut-off below 800Da.

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Figure 1: SEM images of surface and cross-section of cross-linked PAN (A, C), after surface modifica- tion by interfacial polymerization of dopa- mine/terephtaoyl chloride (B, D). TEM image of do- pamine/ terephtaoyl chloride thin film composite membrane (top) and contrast histogram of the select- ed area (bottom) showing a thickness of ~ 5.4nm for the selective layer. Boundaries were defined as the positions where a drastic contrast change takes place. REFERENCES: 1

H. Lee, S. M. Dellatore, W. M. Miller, P. B. Messersmith, Science 2007, 318, 426.

2

J. Zhao, Y. Su, X. He, X. Zhao, Y. Li, R. Zhang, Z. Jiang. J. Membr. Sci. 2014, 465, 41.

3

L. Pérez Manríquez , J .Aburabi’e, P. Neelakanda, K-V. Peinemann. React Funct Polym. 2015, 86, 243.

4

S. Karan, Z. Jiang, A. Livingston. Science. 2015, 348, 1347.

LILIANA PÉREZ-MANRÍQUEZ Title: PhD student Affiliation: KAUST, Saudi Arabia Phone: +966558504866 Graduate Researcher 2012-present Reseach interest: Solvent resistant nanofiltration, Polymeric membranes, Membrane modification, Aromatic Compounds, Medicinal Chemistry

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T2.7 EMMANUELLE FILLOUX DEVELOPMENT OF A NEW ULTRAFILTRATION MEMBRANE WITH LOW ADHESIVE SURFACE FOR DIRECT PRE-TREATMENT OF SEAWATER: BENCH SCALE AND PILOT STUDIES.

EMMANUELLE FILLOUX1, MORGANE GUENNEC1, ANNE BREHANT1, REYNALD BONNARD1, MARTIN HEIJNEN2, DAVIS ARIFIN3 1 Suez, CIRSEE, 38 rue du président Wilson, 78230 Le Pecq, France 2 Inge GmbH, Greifenberg, Germany 3 BASF SE, Ludwigshafen, Germany Ultrafiltration (UF) is an alternative to conventional technologies (coagulation and direct filtration on dual media filters) for seawater pre-treatment, due to its ability to remove suspended solids, bacteria and algae. UF membranes supply constant and high quality feedwater for downstream RO processes, regardless of raw seawater variability1. They even became a preferred solution to treat challenging seawater from surface intakes with highly variable quality2, allowing a stable and high performance of RO processes. However, like any other filtration technologies, fouling propensity needs to be controlled. Typically, UF membrane plants run conservative flux levels in order to limit fouling and chemical cleaning frequency and consequently control the operating costs. BASF/Inge chemically modified standard polyethersulfone (PESU) membranes in order to develop a new generation of ultrafiltration membranes with anti- or lowfouling properties3. The main objective is to operate the new fibers at higher flux rates and with lower chemical usage as compared to their counterparts. The new generation UF membranes were prepared by using either hydrophilic polyethersulfone-polyethylene oxide copolymers or polysulfonepolyethylene oxide–polysiloxane copolymers in order to synthesise membranes with different hydrophilic-hydrophobic balance. Three of the 500 original formulations, so called the lead candidates (LC), were selected based on short-term filtration tests using small flat-sheet membranes and surface analysis, such as atomic force microscopy technique to measure the anti-adhesive behaviour of the new materials3. In order to qualify and validate the three best formulations (so called, lead candidates: LC1, LC2 and LC3) multi-cycle fouling tests were first carried out at Suez-CIRSEE’s laboratories with 0.03 m2 bench-scale modules. This efficient approach (i.e. reliable and fast method) consists in performing several successive filtration tests on lab-scale modules4. The runs were conducted under constant flux and the cycles were done with a constant filtered volume. The backwashes (BW) were performed without chemicals. Runs were ended when the transmembrane pressure (TMP) reaches the upper value of 0.8 bar or when the filtered volume reached around 1200 L/m². A chemical enhanced backwash (CEB) was performed every 10 h, successively with NaOH and acid (H2SO4). The tests were conducted with four different seawaters to benchmark the performance of the three lead

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candidates against the standard PESU membrane taken as the reference. The four membranes were discriminated using four key discriminating factors: reversible fouling, irreversible fouling, BW recovery and permeate quality. Results obtained on North Sea at Dunkerque (France), the most challenging of the four seawaters, are presented in Figure 1. Out of the four tested membranes, LC2 membrane had the lowest fouling propensity, in terms of both reversible and irreversible fouling and showed the best BW efficiencies (88%). Membrane

Std.

LC1

LC2

LC3

Number of cycles before 20 reaching TMP of 0.8 bar

7

27

15

Backwash efficiency (%) 87

78

88

82

Reversible fouling coefficient (x 10-12/m²)

10.2 11.8 4.8

11.3

Irreversible fouling coefficient (x 10-12/m²)

1.3

2.1

2.3

0.6

Figure 1. Fouling propensity of four membranes on North Sea

The best candidate from the bench-scale tests (LC2 membrane) was then tested at pilot scale (effective filtration surface area of 60-70 m2 per module) on two different seawaters: • A seawater from a plant intake situated on the northern Spanish Mediterranean coast, with low turbidity (< 1 NTU) and low organic content (TOC < 1 mg/L); • A surface intake seawater from North Sea, with high turbidity (10-20 NTU) and quite high level of organic matters (average TOC of 1.9 mg/L). During the filtration trial, no coagulants/flocculants were dosed. The parameters taken into account for the water quality characterisation are the suspended solids, turbidity, fouling tendency, organic matters and algae content. The filtration trials conducted with the Mediterranean seawater showed that at same and constant flux, the LC2 module showed higher permeability than the STD module (Fig. 2). In a second phase, LC2 membrane was operated at a significant higher flux than the SDT module; the permeability of the LC2 module remains higher. LC2 can be operated at a higher permeability and then a lower TMP, resulting in lower energy consumption and running costs. During the filtration trials with the challenging seawater from North Sea, the LC2 membrane performances showed to be sensitive to change of algae concentration. However, they showed good recovery after CEB.

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Figure 2. Permeability comparison of two modules operated at same flux. Tests conducted with seawater from a plant intake situated on the northern Spanish Mediterranean coast.

The modifications made of PSU-PEO-Polysiloxane in the formulation of the LC2 membrane results in a significantly lower fouling tendency. The results were validated at both bench and pilot-scale on different seawaters. This is likely due to the reduction in the adhesion properties of foulants (mainly organics) to the membrane surface. REFERENCES 1 A. Jezowska, A. Bottino, G. Capannelli, C. Fabbri, G. Migliorini, Desalination. 2009, 245, 723-729 2 A. Brehant, V. Bonnelye, M. Perez, Desalination. 2002, 144, 353–360 3 R. Krüger, D. Vial, D. Arifin, M. Weber, M. Heijnen, Desalination and Water Treatment. 2016, 1-11 4 E. Filloux, PhD thesis. 2011.

EMMANUELLE FILLOUX Title: PhD, Process Engineer SUEZ, CIRSEE, France Phone: +33(0)1 34 80 89 17 Fax: +33(0)1 30 53 62 07 E-mail: [email protected] 2008-2012

Research Engineer at Veolia (France) and PhD student at The University of Queensland, AWMC (Australia) and the University of Poitiers, LCME (France)

2012-2015

Postdoctoral Research Fellow at The University of Queensland, AWMC

Since 2015

Process Engineer at SUEZ, CIRSEE (France)

Research interests: membrane technologies, desalination, wastewater reuse, organic matter, fouling

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THEME: NOVEL MATERIALS AND SURFACE MODIFICATIONS

T2.10 HUIYUAN LIU FREESTANDING ULTRATHIN GRAPHENE-BASED MEMBRANES FOR WATER PURIFICATION

HUIYUAN LIU1, HUANTING WANG1, XIWANG ZHANG1* 1

Department of Chemical Engineering, Monash University, Australia

Graphene-based membranes, consisting of two-dimensional (2D) graphene oxide (GO) or reduced graphene oxide (rGO) nanosheets, have recently attracted increasing attention in separation of liquid mixtures.[1-4] The nanochannels of these membranes, formed between 2D GO or rGO nanosheets, allow gases and ions with smaller sizes than those of the channels to permeate, while blocking all other larger species. However, hydration of GO in aqueous solution enlarges the channels, making it more challenging to be used in various exciting applications, such as desalination, energy production and hydrofracking water treatment. Although the hydration effect can be inhibited by reduction, a substantial loss in membrane permeability inevitably occurs. In this research, we aim to develop a next generation of high-flux and energy-efficient membranes based on graphene materials, and at the same time maintain their superior selectivity for precise ionic and molecular sieving in aqueous solution. Preliminary work has demonstrated the fabrication of freestanding ultrathin rGO membranes which are more selective and permeable than the state-of-the-art membranes in forward osmosis process.[5] Future work will include further enhancement of the performance of graphene-based membranes in terms of permeability and understanding the mechanisms of mass transport in graphenebased membranes. REFERENCE 1

H. Li, et al., Science 2013, 342, 95.

2

B. Mi, Science 2014, 343, 740.

3

H. W. Kim, et al., Science 2013, 342, 91.

4

R. K. Joshi, et al., Science 2014, 343, 752.

5

H. Liu, H. Wang, X. Zhang, Adv. Mater. 2015, 27, 249.

HUIYUAN LIU Title: Mr. Affiliation, Country: Monash University, Australia Phone: +61 3 9905 3440 E-mail: [email protected] 2006-2010

Bachelor (Powder Metallurgy) Central South University, China

2010-2013

Master (Materials Science) Central South University, China

Since 2013

PhD (Chemical Engineering) Monash University, Australia

Research interests: 2D membrane, water purification, nanomaterials.

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T2.11 LUDOVIC F. DUMEE GRAPHENE FUNCTIONALIZED MACRO-POROUS METAL FRAMEWORKS WATER DESALINATION BY MEMBRANE EVAPORATION

LUDOVIC F. DUMEE12, ZHIFENG YI1, LINGXUE KONG1, PETER HODGSON1 1

Deakin University, Institute for Frontier Materials, Waurn Ponds 3216, Victoria, Australia

Membrane evaporation (ME) is a novel desalination process, whereby a heat-conductive membrane is used to evaporate water in contact with the material. Similarly to membrane distillation, the difference of liquid vapour pressure across the pores of the membrane leads to vapour transport from the feed side to the permeate side, where vapours are thereafter condensed. In contrast to other desalination techniques such as nanofiltration and reverse osmosis, ME offers a potentially low energy and high rejection route to the desalination of highly dirty or salty waters. However, to become competitive with other desalination technologies, specific membrane materials must be developed and tailored to allow for high flux, low fouling tendency and long term stability. Specifically, in order to achieve efficient vapour transport from the hot to the cold side, a ME membrane must be highly porous, as thin as possible and not wettable by the process liquids. The pores need therefore to be large enough to facilitate vapour transport, while having sufficiently small dimensions to avoid liquid wetting and formation of a direct liquid bridge between the feed and the permeate sides. In addition, the membrane material must be heat conductive to allow for direct heating and evaporation of water in direct contact with the material surface. Most previous studies have investigated low porosity membrane materials formed from sintered stainless steel powders. While these materials are highly hydrophobic, they are also expensive and difficult to process. It is consequently important to investigate other alternatives as well as techniques for improving the process efficiency by modifying the membrane properties and structure. Here, novel metal based scaffolds were decorated for the first time with ultra-thin layers of graphene materials by a direct electroplating. The micron-sized pores across the metal scaffolds were found by micro-Raman analysis to be entirely covered with controllable thicknesses of graphene, which latter was used for seeding specific functionalization and provide a strong interface as well as a corrosion protection barrier against chloride anions present in water. Both sides of the membranes were then specifically modified to alter the water evaporation and vapour diffusion and condensation characteristics. A Janus structure was produced by (i) grafting on one side of the membrane fluorosilane chains, used to generate a super-hydrophobic interface, while (ii) the second side of the membrane was coated with a nanoscale but yet thermally insulating and semi-hydrophilic

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alumina layer by Atomic Layer Deposition (ALD). The macro-properties of the materials, including their wettability, thermal conductivity, mechanical strength, as well as their surface charge and morphologies were systematically investigated and correlated to the electroplating conditions. The performance of the membranes for desalting model 3.5 wt% NaCl solutions were also linked to process parameters, including the liquid velocity within the module and the temperature difference between both sides of the membranes, as well as to the materials properties, fluorosilane functional groups densities and morphology of the alumina layer deposited. In short, the membranes were found to exhibit Janus behaviours in nearly all aspects of their behaviours. The water contact angle values ranged from 160o to 60o, while the thermal conductivity of the alumina-coated side was found to be up to 25 times lower than that of the fluoro-silane grafter graphene side. In addition, >99.99% desalination performance were achieved for flux > 100 LMH for a feed to permeate temperature difference of only 50oC. The hybrid Janus membranes were also found to be extremely stable and desalination tests for up to 5 consecutive days were performed without loss of performance. This work demonstrates the feasibility of hybrid materials with controlled porosities and pore distributions for the competitive desalination of brines. LUDOVIC F. DUMEE Dr Deakin University, AUSTRALIA Phone: +61410131312 E-mail: [email protected] Now - 2012 Research Fellow / Lecturer – Deakin University 2012 - 2011 Post-doctoral Research Fellow – The University of Melbourne 2011 – 2007 PhD student - CSIRO and Victoria Univeristy Research interests: nano-porous materials, surface coatings, 2D nanomaterials, Plasma surface modifications, wettability control

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T2.12 MS YAOXIN HU NOVEL 2D HYBRID MOF/GRAPHENE OXIDE SEEDING FOR SYNTHESIS ULTRATHIN MOLECULAR SIEVING MEMBRANES

MS YAOXIN HU, DR JING WEI, PROFESSOR HUANTING WANG Department of Chemical Engineering, Monash University Clayton, Victoria 3800 (Australia) Metal–organic framework (MOF) films have been studied for a wide range of applications, such as sensors, low-k dielectrics, and separation membranes. In particular, MOF membranes have shown great potential for energy-efficient gas separation compared with traditional polymer membranes.1 Despite various fabrication methods being developed, the fabrication of ultrathin MOF membranes remains a challenge owing to the difficulty in controlling heterogeneous nucleation and growth on porous substrates. 2 Only until very recently, Yang and co-workers made breakthroughs in the preparation of ultrathin molecular sieving membranes by using two-dimensional (2D) exfoliated MOF.3 However, the synthesis of crystalline nanosheets from non-layered MOFs remains a significant challenge. 2D nanocomposites, such as graphene oxide (GO) nanosheets and MOFs, have been the focus of recent research owing to their unique properties.4 It is feasible to prepare GO hybrid nanosheets from different MOFs to build up ultrathin molecular sieving membranes. Herein, we reported an innovative strategy to fabricate ultrathin and defect-free MOF membranes on various porous substrates using 2D hybrid MOF/GO seeding layer.5,6 Zeolitic imidazolate framework-8 (ZIF-8), an important MOF used for fabrication of gas separation membranes, was chosen to demonstrate the 2D nano-hybrid seeding strategy. The ZIF/GO/ZIF sandwich-like structure with ultrasmall ZIF nanocrystals fully covering the GO as seeds is prepared via a homogenous nucleation followed by a uniform deposition and confined growth process as shown in Scheme 1a. The uniform coating of ZIF nanocrystals on the GO layer can effectively inhibit the agglomeration of GO during seeding on the porous support. A defect-free ZIF-8/GO membrane with a thickness of 100 nm was prepared on a porous substrate using 2D ZIF-8/GO hybrid nanosheets as seeds, followed by secondary growth using the interfacial synthesis (Scheme 1b). In addition, such hybrid nanosheets with a suitable amount of ZIF-8 nanocrystals were essential for producing a uniform seeding layer that facilitated fast crystal intergrowth during membrane formation. Furthermore, the seeding layer acted as a barrier between two different synthesis solutions, and self-limited crystal growth and effectively eliminated defects during the contra-diffusion process. SEM image of ZIF/GO nanosheets revealed the uniform nanosheet coated with ultra-small ZIF-8 nanoparticles (Fig.2a). To our knowledge, this is the first example of GO sheets fully covered by ZIF nanocrystals with ultra-small diameter (<50 nm). As shown in the Fig.2b-d, thickness of ZIF-8/GO membranes was one of the thinnest ever reported and its

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separation performance was amongst the best ZIF -8 membranes reported thus far, with a high CO2/N2 selectivity of 7. This 2D nano-hybrid seeding strategy can be readily extended to fabricate other defect-free and ultrathin MOF or zeolite molecular sieving membranes for a wide range of separation applications.

Scheme 1 Illustration of a) the ZIF-8 growth in the confined space to get ultra-small ZIF-8 nanocrystals fully covered on the GO nanosheets5 and b) the synthesis process of ultrathin ZIF-8/GO membrane: coating of flexible ZIF-8/GO nanosheets on a porous support, such as anodic aluminium oxide (AAO), and subsequent secondary growth by the contra-diffusion method.6

Figure 1 SEM images of a) the ZIF-8/GO seeds-3h powder, and the surface b) and cross-section c) of ZIF-8/GO membrane (M-3h-3h) on the AAO substrate. The inset in b is a high-magnification surface view, and c is a high-magnification cross-sectional view. d) Single gas permeances of different gases through ZIF/GO membrane (M-3h-3h) at 25 °C and 1bar as a function of the kinetic diameter 6

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REFERENCES 1 S. Qiu, M. Xue, G. Zhu, Chem. Soc. Rev. 2014, 43, 6116-6140 2 N. Rangnekar, N. Mittal, B. Elyassi, J. Caro, M. Tsapatsis, Chem. Soc. Rev. 2015,44, 7128 – 7154 3 Y. Peng, Y. Li, Y. Ban, H. Jin, W. Jiao, X. Liu, W. Yang, Science 2014, 346, 1356 – 1359. 4 J. Wei, Y. Hu, Z. Wu, Y. Liang, S. Leong, B. Kong, X. Zhang, D. Zhao, G. P. Simon, H. Wang, J. Mater. Chem. A 2015, 3, 16867 – 16873 5 J. Wei, Y. Hu, Y. Liang, B. Kong, J. Zhang, J. Song, Q. Bao, G. P. Simon, S. P. Jiang, H. Wang, Adv. Funct. Mater. 2015, 25, 5768 – 5777 6 Y. Hu, J. Wei, Y. Liang, H. Zhang, X. Zhang, W. Shen, H. Wang, Angew. Chem.-Int. Edit. 2016, 55, 2048-2052

YAOXIN HU Title:Ms Monash University, Australia: Phone: +61 0450360803 E-mail: [email protected] 2004-2008

Bachelor, Nanjing Tech University, China

2008-2011

Master, Nanjing Tech University, China; Victoria University, Australia

Since 2014

PhD Candidate, Monash University, Australia

Research interests: MOF membrane, gas separation, water treatment

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THEME: NOVEL MATERIALS AND SURFACE MODIFICATIONS

T2.13 EFFECTIVE GRAPHENE-BASED SURFACE MODIFICATION OF FORWARD OSMOSIS MEMBRANES FOR IMPROVING THEIR PROPERTIES

HANAA M. HEGAB 1,2, AHMED ELMEKAWY 3,4, THOMAS G. BARCLAY 5 , ANDREW MICHELMORE 5, LINDA ZOU 1,6, CHRISTOPHER P. SAINT 1, MILENA GINIC-MARKOVIC 5 1

Natural & Built Environments Research Centre, University of South Australia, Adelaide, SA 5095, Australia

2

Institute of Advanced Technology and New Materials, City of Scientific Research and Technological Applications, Borg Elarab, Alexandria, Egypt

3

Genetic Engineering and Biotechnology Research Institute, University of Sadat City (USC), Sadat City, Egypt

4

School of Chemical Engineering, University of Adelaide, Adelaide, Australia

5

Future Industries Institute, University of South Australia, Adelaide, SA 5095, Australia

6

Department of Chemical and Environmental Engineering, Masdar Institute of Science and Technology, Abu Dhabi, United Arab Emirates.

The potential for attaching the unique biocide graphene oxide (GO) nanosheets onto desalination membrane surfaces has recently gained much attention, because of their superior anti-biofouling properties. However, effective coating strategies to assemble GO nanosheets onto the membrane surface are still required. To address this challenge, we adopt a novel single-step in-situ surface modification approach where the polyphenol tannic acid, cross-linked with polyethylene imine, was applied as a versatile platform to immobilize GO nanosheets to the surface of polyamide (PA) thin film composite (TFC) forward osmosis (FO) membrane (Fig. 1A). The membranes were analysed by transmission electron microscopy (TEM), water contact angle (WCA) and adenosine triphosphate bioluminescence test (ATP). TEM images of pristine and coated cross-sections (Fig. 1B) show changes of the membrane morphological structures with surface modification; creating a tighter and smother active layer compared to the pristine one. The surface modification layer also enhanced membrane hydrophilicity from 50° to 19° (Fig. 1C). Furthermore, the modified membrane significantly mitigated biofouling by 33%, due to its extraordinary synergetic antibacterial properties (99.9%), compared to the pristine membrane.

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HANAA HEGAB Title: PhD Candidate Affiliation, Country: Natural & Built Environments Research Centre, University of South Australia, Adelaide, SA 5095, Australia Phone: +61 470258748 E-mail: [email protected] Bachelor of Science 2005 Master of Materials Science 2012 PhD Candidate since 2014, University of South Australia Research interests: Graphene, wastewater treatment, membrane

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: WINE, FOOD AND DAIRY APPLICATION

THEME: WINE, FOOD AND DAIRY APPLICATION T3.2 DABESTANI, S PROTEIN RECOVERY FROM POTATO PROCESSING WATER: FOULING MINIMIZATION AND FUNCTIONAL PROPERTIES OF RECOVERED PROTEIN

DABESTANI, S.1,2, ARCOT, J.2,3, CHEN, V.1,3 1 UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, UNSW Australia, Sydney 2052, Australia 2 ARC Training Centre for Advanced Technologies in Food Manufacture, School of Chemical Engineering, UNSW Australia, Sydney 2052, Australia 3 Food Science and Technology Group, School of Chemical Engineering, UNSW Australia, Sydney 2052, Australia Waste treatment has been a challenge for the potato processing industry for many years. The wastewater effluent with high concentrations of potassium and Chemical Oxygen Demand (COD) caused by the presence of starch, proteins, amino acids and sugars, imposes expensive treatment processes for industry. However, this waste effluent contains high amounts of valuable by-products. Starch content of this waste stream, ranging from 15 to 20%, is being recovered using simple separation systems such as hydro-cyclones in some manufacturing sites, but the commercially valuable protein (primarily patatin) ranging from 1-1.5 g/L is still being discharged into the waste stream. Protein recovery was investigated using membrane process via two different module configurations. The methods were assessed based on recovery yield, fouling performance, reusability of the membrane and the quality and functionality of recovered protein. Using the dead-end apparatus, in this study, pretreatment method including a combination of centrifugation, filter paper 2.5 µm, polyvinyl difluoride (PVDF) microfiltration (MF) were investigated prior to ultrafiltration with 10kDa molecular weight cut-off polyethersulfone (PES) membranes. Recovery of protein up to 70% was achieved. Denaturation of protein was avoided by not using additional chemicals, heat treatment or pH change. High cleaning efficiency (97%) and sustainable cleaning were achieved with 100 ppm sodium hydroxide cleaning. Using cross-flow module resulted in 75% improvement in fouling compared to dead-end configuration while the same concentration of protein was achieved (5g/L). The steroidal glycoalkaloids are naturally occurring toxins compounds of potato and the main reason for bitterness of potato proteins. Limiting the concentrations of glycoalkaloids is critical in the recovery and purification of potato proteins. The two major glycoalkaloids present in potato α-solanine and α-chaconine comprise about 95% of total potato glycoalkaloids 1-3 . Low levels of total glycoalkaloids (TGA) (20-150 mg/kg fresh tubers) can GOLD SPONSOR

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always be found in commercial potatoes while this amount is limited to 12-20 mg/kg fresh tubers for normal potatoes 4. However, this low concentration can be elevated quickly in potatoes which have been stressed, greened, damaged, exposed to light or stored for prolonged periods2, 5-10. TGA contents higher than 200 mg/kg fresh weight potatoes have been found to be toxic, causing illness and death in humans in some cases 7, 11-13. In the current research TGA content of recovered protein was studied using HPLC method. The level of TGA was found to be 16.5 mg/kg protein, indicating that the product is safe to be used for human consumption from this aspect. Functional properties and the nutritional quality of protein determine its use in food processing applications. For example casein and whey, two milk proteins, can be used in different food applications or used as whole dried milk. The protein extracted from wheat and egg white can also have a multitude of functional applications as well as nutritional value. Foaming capacity (FC) and stability (FS) of the product were investigated against commercial potato and pea proteins. The obtained FC was almost 2.5 times higher than the one for commercially produced potato protein that was produced by other techniques However, FS was comparable for both after 120 minutes. Pea protein showed lower FC than both potato proteins produced in this study (65%) and the commercial potato protein (15%). This means that the protein is suitable to be used in food applications that require high FC and FS. Water absorption capacity (WAC) was achieved at 65% for the recovered proteins which was more than 2 times higher than the one for commercial potato protein (28%). However, the WAC achieved for pea protein was 500%. Oil absorption capacity (OAC) was obtained as 202% which was comparable to the OAC for commercial potato protein (220%) and 160% for pea protein. These indicate that the protein product provides good digestibility specification. REFERENCES

148

1

M. Friedman, G. M. McDonald, and M. Filadelfi-Keszi, “Potato glycoalkaloids: Chemistry, analysis, safety, and plant physiology,” Critical Reviews in Plant Sciences, vol. 16, pp. 55-132, 1997/01/01 1997.

2

M. Friedman and C. E. Levin, “Analysis and biological activities of potato glycoalkaloids, calystegine alkaloids, phenolic compounds, and anthocyanins,” in Advances in potato chemistry and technology, J. Singh and L. Kaur, Eds., ed Burlington: Academic Press, 2009, pp. 127-162.

3

M. Friedman, F. F. Bautista, L. H. Stanker, and K. A. Larkin, “Analysis of potato glycoalkaloids by a new ELISA kit,” Journal of Agricultural and Food Chemistry, vol. 46, pp. 5097-5102, 1998/12/01 1998.

4

I. Shaw, Is it safe to eat? Enjoy eating and minimize food risks. Berlin: Springer, 2005.

5

L. Dao and M. Friedman, “Chlorophyll, chlorogenic acid, glycoalkaloid, and protease inhibitor content of fresh and green potatoes,” Journal of Agricultural and Food Chemistry, vol. 42, pp. 633-639, 1994/03/01 1994.

6

M. S. Y. Haddadin, M. A. Humeid, F. A. Qaroot, and R. K. Robinson, “Effect of exposure to light on the solanine content of two varieties of potato (solanum tuberosum) popular in Jordan,” Food Chemistry, vol. 73, pp. 205-208, 5// 2001.

7

P. Slanina, “Solanine (glycoalkaloids) in potatoes: Toxicological evaluation,” Food and Chemical Toxicology, vol. 28, pp. 759-761, 1990/01/01 1990.

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: WINE, FOOD AND DAIRY APPLICATION

8

M. Friedman and L. Dao, “Distribution of glycoalkaloids in potato plants and commercial potato products,” Journal of Agricultural and Food Chemistry, vol. 40, pp. 419-423, 1992/03/01 1992.

9

M. Friedman, “Potato glycoalkaloids and metabolites: Roles in the plant and in the diet,” Journal of Agricultural and Food Chemistry, vol. 54, pp. 8655-8681, 2006/11/01 2006.

10 R. M. D. Machado, M. C. F. Toledo, and L. C. Garcia, “Effect of light and temperature on the formation of glycoalkaloids in potato tubers,” Food Control, vol. 18, pp. 503-508, 5// 2007. 11 D. G. Barceloux, “Potatoes, tomatoes, and solanine toxicity (solanum tuberosum L., solanum lycopersicum L.),” Disease-a-Month, vol. 55, pp. 391-402, 6// 2009. 12 S. F. Osman, “Glycoalkaloids in potatoes,” Food Chemistry, vol. 11, pp. 235-247, 1983/01/01 1983. 13 D. B. Smith, J. G. Roddick, and J. L. Jones, “Potato glycoalkaloids: Some unanswered questions,” Trends in Food Science & Technology, vol. 7, pp. 126-131, 4// 1996.

SHIRIN DABESTANI UNSW Australia Phone: +61 2 9385 4339 E-mail: [email protected] 2006

BSc in Chemical Engineering, Azad University of Tehran, Iran

2006-2008

Project Engineer, NMK Company, Tehran, Iran

2008-2010

Project Engineer, Dyna mic Global Trends Company, Tehran, Iran

2010-2012

M. Eng. In Chemical Process Engineering, UNSW Australia

2012-2013

Petroleum Chemist, Australian Laboratory Services, Sydney

2013-Present

PhD candidate in Chemical Engineering, UNSW Australia

Research interests: Water and wastewater treatment, Bioseparation, Recovery of valuable byproducts from industrial wastewater, Membrane fouling optimization and cleaning, Innovative food processing technologies using membrane technology

GOLD SPONSOR

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T3.3 G. CHEN THE CHALLENGES OF EFFLUENT TREATMENT IN THE DAIRY INDUSTRY

G. CHEN1, J. CHANDRAPALA2, K. KEZIA1, S. GRAS1,3, S. KENTISH1 1

The ARC Dairy Innovation Hub, Department of Chemical and Biomolecular Engineering, University of Melbourne, Victoria 3010, Australia

2

3

Advanced Food Systems Research Unit, College of Health and Biomedicine, Victoria University, Werribee 3030, Australia

Bio 21 Molecular Science and Biotechnology Institute, The University of Melbourne, Victoria 3010 Australia

Dairy processing is the third largest rural industry in Australia where almost 10 billion litres of milk is produced annually, generating $13 billion in turnover. Despite its critical contributions to economic growth, the size and the treatment challenges of the effluent generated from the dairy industry should not be overlooked. On average, processing one litre of milk generates about 2 litres of effluent, leaving behind a huge volume of wastewater that must be treated appropriately. Much of the effluent generated by cheese manufacturing and whey processing is high in salt. The treatment of such effluent is beyond the capabilities of most of the commercial membrane processes that have been widely implemented in wastewater treatment. Here, a brief review will be presented on the commercial and emerging membrane technologies that may potentially be suitable for establishing a sustainable and cost-effective approach to both reduce the costs of salty wastewater treatment and to improve the recoveries of dairy products. Further, this presentation will showcase the use of nanofiltration, electrodialysis and membrane distillation for processing two major types of dairy effluent, namely acid whey and salty whey. Acid whey is a byproduct of cream cheese and strained yoghurt manufacture, containing proteins, lactose and minerals. This protein source is currently treated as a waste product due to the lactate content, which results in a sticky powder with undesirable flavor after spray drying. Nanofiltration and electrodialysis have been investigated to reduce the ratio of lactate to lactose below 0.04g/g, which would allow the recovery of acid whey into a free flowing powder. Using nanofiltration, only ~50% of the lactate anions could be removed. Due to the surface characteristics of the NF membranes, selective removal of lactate relied on lactic acid remaining uncharged. Thus performance improved as the pH was lowered. However, the pore size of the membrane had little impact on the separation of lactate from lactose. In contrast, more than 80% of lactate ions could be removed during electrodialysis of the acid whey. The energy consumption (~0.014 kWh/kg whey processed) for achieving 90% demineralization of the acid whey was comparable to the energy requirement reported for sweet whey demineralization using electrodialysis. The

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glass transition temperature of the resulting dried powder increased from ~80°C to ~95°C, indicating that spray dryer operation would be significantly improved. Another variety of saline effluent, salty whey, is produced from making semi hard or hard cheese such as Cheddar. Salt is added to the protein-rich cheese curd to reduce the water activity within the curd, but only 35-50% of the added salt is retained in the curd. Therefore, the sodium content in salty whey is up to ten times higher than that in acid whey, making its disposal environmentally difficult. Membrane distillation has been employed to concentrate salty whey of <10% w/w total solids. A final total solids concentration of ~30% w/w with water recovery of up to 83 % was achieved, well exceeding the achievable brine concentration of reverse osmosis. Although a decline in water flux in the presence of trace protein in the feed was observed, membrane fouling was found to be primarily governed by the precipitation of a calcium phosphate salt. It can be concluded that membrane distillation has potential for concentrating dairy salty wastewater to produce a highly concentrated brine for downstream solid-liquid separation processes such as crystallisation. These results can be valuable for the design and optimisation of a zero liquid discharge system for the dairy industry in the future. GEORGE CHEN Title: Dr Affiliation, Country: The ARC Dairy Innovation Hub, Department of Chemical and Biomolecular Engineering, University of Melbourne, Victoria 3010, Australia. Phone: +61 3 8344 4365 E-mail: [email protected] 2014-

Research Fellow, The ARC Dairy Innovation Hub, Department of Chemical and Biomolecular Engineering, the University of Melbourne

2012-2013

Process Engineer, ThyssenKrupp Industrial Solutions (Australia) Pty Ltd

2008-2012 PhD Candidate, Department of Chemical and Biomolecular Engineering, the University of Melbourne Research interests: membrane technologies for dairy processing, water & wastewater treatment, gas separatio

GOLD SPONSOR

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THEME: WINE, FOOD AND DAIRY APPLICATION

T3.4 MILTON CHAI VIBRATING HOLLOW FIBRE MEMBRANE SYSTEM FOR MILK PROTEIN SEPARATION AND CONCENTRATION

MILTON CHAI, YUN YE, VICKI CHEN UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, The University of New South Wales, Sydney, Australia Currently, membrane-based separation processes have been widely used in the dairy industry for the fractionation of milk. Milk contains valuable components such as dairy proteins that can be isolated and further processed into ingredients with a wide range of functional characteristics, thereby adding value to milk. In the membrane separation and concentration process of milk protein, membrane fouling remains a key issue which becomes more severe with the increase of protein concentration and viscosity. Fouling not only affects the system productivity, but is also detrimental to the separation efficiency of the process. Conventional strategies employed to limit fouling include high cross-flow velocities or gas sparging. However, these are less effective when high viscosity solutions are involved such as high concentration milk solutions. Although the use of membrane vibration is less common, such systems are capable of producing high permeate flux owing to the high shear rates generated at the membrane surface. A recent study on the transverse vibrating hollow fibre system showed the benefit of transverse vibration on fouling limitation when handling highly concentrated and viscous yeast solutions1. Therefore, opportunities exist to further explore this system for the fractionation of milk protein concentrates which presents a significant challenge to conventional cross-flow filtration. In addition, a novel rotational vibration system will also be explored. In this study, 0.04 µm polyvinylidene fluoride hollow fibre membrane was used for the separation of casein micelles from whey protein, lactose, and other soluble components. The feed solutions used were skim milk and milk protein concentrate (MPC) solutions including MPC60, MPC66 and MPC71 solutions to simulate different stages of the concentration process. The vibrating hollow fibre membrane systems were investigated for the separation of casein and whey proteins at a low operating temperature of 10ᵒC, and the separation efficiency of casein, whey proteins and lactose were analysed. Fractionation analysis of the fouling layer was conducted at the end of selected experiments to investigate the reversibility of fouling and the foulant composition was analysed. In addition, the fouling control performance and separation efficiency of the vibrating membrane systems were compared to that of traditional cross-flow. It was observed that the submerged vibrational membrane system can maintain very high transmission of whey proteins (α-Lactalbumin and β-Lactoglobulin) while fully rejecting casein micelles. A low transmembrane pressure (TMP) rise was observed during MPC60

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filtration (12.93 cP at 10ᵒC) at 10 L/m2 h using the transverse vibration system. Interestingly, in a supra-critical flux experiment conducted for the filtration of MPC60 at 17-19 L/m2 h, the TMP was observed to rise and then stabilize at a relatively low TMP of 18 kPa. This indicates that membrane vibration can prevent further membrane fouling. The corresponding whey protein transmission was determined to be 73.8% while the casein rejection was observed to be 100%. The transmission of both α-Lactalbumin and β-Lactoglobulin, and the rejection of casein micelle were also confirmed through SDS-PAGE analysis. Fractionation analysis of the fouling layer showed that a significant portion of the fouling is reversible and can be removed through simple rinsing. Furthermore, casein was found to be the dominant foulant. A comparison of the vibrational membrane system with traditional cross-flow also showed that the vibration system had significantly better fouling performance and separation efficiency. REFERENCES 1

Kola, A., Ye, Y., Ho, A., Le-Clech, P., & Chen, V., Journal of membrane science. 2012, 409, 54-65

MILTON CHAI Title: Mr. UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, The University of New South Wales, Sydney, Australia Phone: +61420389630 Fax: N/A E-mail: [email protected] 2015-now

PhD (Research) in Chemical Engineering, University of New South Wales

2011-2014

Bachelor of Chemical Engineering, University of New South Wales

Research interests: Vibrating hollow fibre membrane systems for bioseparation applications

GOLD SPONSOR

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THEME: WINE, FOOD AND DAIRY APPLICATION

T3.5 JORIS SPRAKEL VISUALIZATION OF PORE BLOCKING WITH THE ‘CLOGGOTRON’

TIES VAN DE LAAR1,2, STEN TEN KLOOSTER1,2, JORIS SPRAKEL2, KARIN SCHROËN1 1 Wageningen University, Food Process Engineering group, Bornse Weilanden 9, 6708 WG Wageningen, The Netherlands. 2 Wageningen University, Laboratory of Physical chemistry and Soft matter, Stippeneng 4, 6708 WE Wageningen, The Netherlands. Clogging is one of the main failure mechanisms encountered in industrial processes such as membrane filtration. Preventing clogging is an immense challenge due to its often severe, costly and energy consuming consequences, yet remains difficult to date as our understanding of the factors that govern the build-up of fouling layers and the emergence of clogs remains incomplete. To study these phenomena, a microfluidic system was developed, the so-called ‘cloggotron1’, in which quantitative real-time imaging is used to explore the influence of pore geometry and particle interactions (see figure 1). We fabricated the microfluidic device following standard soft lithography methods, and used a glass cover slide. The system was operated at constant pressure drop and the flow velocity per channel was constant prior to clogging and did not correspond to possible clogging events in neighboring channels. The flow was imaged with bright field microscopy (Zeiss Axiovert 200) at one frame per second, and examples can be found in figure 1b. To extract quantitative data we processed the images with home-built Matlab scripts; due to the distinct change in light transmission upstream and downstream from a clog, the location of clogs can be identified relative easily. We found a distinct dependence of the clogging rate on the angle to the pore (see figure 1a); the clogging rate being higher for pores that are more perpendicular to the direction of flow. Besides we found that the interaction between the particles determines the clogging rate to an even greater extent, with attractive particles clogging much faster. The observed effects could be explained with a model that describes the effect of viscous forces on the rate with which particles accumulate at the channel walls. With the same model we can also predict the effect of the particle interaction on the clogging rate. In both cases we find very good agreement between experimental data and theory. While the micromodel presented in figure 1 represents a highly idealized picture of a deadend filtration membrane, it does shed important light on the phenomena that occur in membrane systems. Besides, several extensions are considered to include complexity that is found in more realistic membrane systems. For example, wall roughness, polydispersity in pore sizes or distance between pores, and polydispersity of particles2 must be expected to have significant effects on the rate and spatial correlations of clogging, and these effects

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THEME: WINE, FOOD AND DAIRY APPLICATION

can be incorporated in the microfluidic device. Moreover, with the microfluidic approach we use, introducing a fluid crossflow across the membrane surface is feasible; since such a crossflow will in affect particle migration in flow3 and the filter cake build-up, it is expected to have strong effects on the cooperativity in clog events. Extending this approach, combining experimental observation on well-defined model systems and analytical theory, will lead to a deeper understanding of membrane pore failure and in the future provide new design rules for novel membrane systems with improved operational lifetime.

Figure 1: Overview of the layout of the ‘cloggotron’ with the different pore geometries that were investigated (left); over overall image of all parallel pores (middle), and the ‘cloggotron’ in action on the right, with blocked pores turning white, and pores that are still in operation as grey REFERENCES 1

T Van de Laar, S Ten Klooster, K Schroën, J Sprakel: Transition-state theory predicts clogging at the microscale, Scientific Reports 2016, Article number 28450.

2

T Van De Laar, R Higler, K Schroën, J Sprakel: Discontinuous nature of the repulsive-to-attractive colloidal glass transition. Scientific Reports 2016, Article number: 22725.

3

T Van De Laar, K Schroën, J Sprakel: Cooperativity and segregation in confined flows of soft binary glasses. Physical Review E - Statistical, Nonlinear, and Soft Matter Physics 2015, 92(2):022308.

KARIN SCHROËN Title: Prof. dr. ir. Wageningen University, Department of Agrotechnology and Food Sciences, Food Process Engineering Group, The Netherlands Phone: +31-317 483396 E-mail: [email protected] 1994-1996

Post-doctoral researcher, Chemical and Biochemical Engineering group, University College London.

1996-2001

Post-doctoral researcher / project leader. Food and Bioprocess Engineering group. Wageningen Agricultural University.

2001-2010

Assistant Professor, Laboratory of Food Process Engineering, Wageningen University.

2010-2012

Associate Professor, Laboratory of Food Process Engineering, Wageningen University.

2012-now

Personal Professor, Food Micro Technology, within the Food Process Engineering Group of Wageningen University.

Research interests: Membranes, modeling, microfluidic devices, membrane emulsification, emulsions, capsules. GOLD SPONSOR

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THEME: WINE, FOOD AND DAIRY APPLICATION

T3.6 THOMAS BARCLAY ARE POLYDOPAMINE MODIFIED FILTRATION MEMBRANES DURABLE ENOUGH FOR DAIRY PROCESSING?

THOMAS BARCLAY1, EMMANUELLE BOURDEAUX1, GURPREET KAUR1, STEPHEN CLARKE1 AND MILENA GINIC-MARKOVIC1 1 Future Industries Institute, University of South Australia Polydopamine adhesive layers have been used extensively in the modification of a wide range of filtration membranes to improve performance.1 To do this the dopamine monomer is deposited onto the membranes through self-assembly and oxidative crosslinking from mild pH aqueous solution. This results in a durable, nanoscale, conformal and hydrophilic coating on almost any surface that can be readily further modified as desired to introduce specific surface chemistry for a particular application.2-6 The attachment of these thin coatings can balance any pore blockage by increasing the wettability of the membrane surface,7 promoting increased aqueous flux.8, 9 Increased affinity to water of the membrane coating also discourages attachment of both biomacromolecules and cells and has been used to reduce biofouling.10-12 Finally, the use of this general, simple, gentle method to modify the surface chemistry of membranes saves time compared to case-by-case solutions,13 and can also be used to coat all components in an assembled filtration module in-situ.14-16 Despite a number of laboratory results that illustrate the value of polydopamine based membrane coatings, there is also evidence from experiments designed to mimic industrial fouling conditions that both polydopamine and modified polydopamine coatings are unable to maintain their biofouling performance over the longer term.16 In our recent project we coated membranes with polydopamine modified with polyzwitterions and mimicked ultrafiltration used in dairy processing. Initially we investigated some of the properties of the polydopamine coatings on ultrafiltration membranes and found that polydopamine coats more slowly onto polysulfone than onto silicon, but that it follows typical plateauing thickness characteristics over time (Fig. 1) and also that the resultant coating did not significantly influence the wettability compared to uncoated controls. More interestingly, pure water flux for polydopamine modified polyethersulfone membranes measured using a stirred cell apparatus shows an interesting pattern of changing flux with increasing deposition time shown in Fig. 1. We attribute this to the three dimensional island growth proposed for polydopamine deposition.17 As the islands grow, they begin to block pores and provide a rough surface with heterogeneous chemistry, reducing flux. Then, as the islands start to link together, the surface chemistry becomes more homogenous and smoother and better facilitates water flow through the membrane, peaking at the 8 hr coating time that has flux comparable with the shortest 20 min coating time. From this point increased reaction time simply increases coating thickness, reducing flux.

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THEME: WINE, FOOD AND DAIRY APPLICATION

Water Flux

Polydopamine thickness

200

45

180

40

Average Flux (L/m2/h )

160

35

140

30

120

25

100 20

80

15

60

10

40

5

20 0

0 Control

20 min

30 min

1 h

2 h

4 h

6 h

8 h

10 h

16 h

24 h

Coating Time

Figure 1. Water flux and coating thickness of polydopamine deposited onto ultrafiltration membranes

After coating the membranes with polydopamine we further modified them with a amine terminated polyzwitterions through Michael addition and Schiff base coupling.18 Using this coating we were able to improve the filtration performance of freshly coated membranes, marginally increasing milk flux and significantly improving both the fouling coefficient (lower is better) and recovery (higher is better) of the membrane, as shown for experiment 1 in Table 1. The fouling coefficient and recovery are measures that compare water flux before fouling to water flux after fouling and after membrane cleaning respectively, and so the results indicate that the coating both reduces the strength of binding between proteins and the membrane and makes any bound proteins more easily removed in cleaning. Despite the excellent results for freshly prepared membranes, the filtration performance in terms of fouling coefficient and recovery slowly degraded in subsequent experiments when used in conditions that mimic multiple filtrations of skim milk and subsequent cleaning. Further, sanitation using hydrogen peroxide / peroxyacetic acid applied to the membrane between experiments 5 and 6 in Table 1 significantly increased the fouling coefficient. This shows that while polydopamine based coatings can produce strong filtration results for freshly prepared membranes, the mostly supramolecular associations that bind the coating together and to the membrane surface can easily be disturbed in harsh industrial membrane cleaning procedures and sanitation processes.

Table 1. Cross flow filtration results for polyzwitterion modified polydopamine coated ultrafiltration membranes exposed to multiple preconditioning, milk filtration and clean in place procedures. Between experiment 5 and 6 the system was also sanitised with an oxidation agent. GOLD SPONSOR

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REFERENCES 1 H.-C. Yang; J. Luo; Y. Lv; P. Shen; Z.-k. Xu, J. Membr. Sci. 2015, 483, 42-59. 2 D.R. Dreyer; D.J. Miller; B.D. Freeman; D.R. Paul; C.W. Bielawski, Langmuir 2012, 28, 6428-6435. 3 L. Zhang; J. Shi; Z. Jiang; Y. Jiang; S. Qiao; J. Li; R. Wang; R. Meng; Y. Zhu; Y. Zheng, Green Chem. 2011, 13, 300-306. 4 D.R. Dreyer; D.J. Miller; B.D. Freeman; D.R. Paul; C.W. Bielawski, Chemical Science 2013, 4, 3796. 5 B. Zhu; S. Edmondson, Polymer 2011, 52, 2141-2149. 6 J. Jiang; L. Zhu; L. Zhu; B. Zhu; Y. Xu, Langmuir 2011, 27, 14180-14187. 7 B.D. McCloskey; H.B. Park; H. Ju; B.W. Rowe; D.J. Miller; B.D. Freeman, J. Membr. Sci. 2012, 413-414, 82-90. 8 K.-Y. Kim; E. Yang; M.-Y. Lee; K.-J. Chae; C.-M. Kim; I.S. Kim, Water Res. 2014, 54, 62-68. 9 S. Azari; L. Zou, J. Membr. Sci. 2012, 401-402, 68-75. 10 D. Rana; T. Matsuura, Chem. Rev. 2010, 110, 2448-2471. 11 M. Ginic-Markovic; T.G. Barclay; K.T. Constantopoulos; E. Markovic; S.R. Clarke; J.G. Matisons, DES 2015, 369, 37-45. 12 S. Azari; L. Zou; E. Cornelissen, Colloid Surface B 2014. 13 S.M. Kang; N.S. Hwang; J. Yeom; S.Y. Park; P.B. Messersmith; I.S. Choi; R. Langer; D.G. Anderson; H. Lee, Adv. Funct. Mater. 2012, 22, 2949-2955. 14 B.D. McCloskey; H.B. Park; H. Ju; B.W. Rowe; D.J. Miller; B.J. Chun; K. Kin; B.D. Freeman, Polymer 2010, 51, 3472-3485. 15 J.T. Arena; S.S. Manickam; K.K. Reimund; B.D. Freeman, Desalination 2014. 16 D.J. Miller; P.A. Araújo; P.B. Correia; M.M. Ramsey; J.C. Kruithof; M.C.M. van Loosdrecht; B.D. Freeman; D.R. Paul; M. Whiteley; J.S. Vrouwenvelder, Water Res. 2012, 46, 3737-3753. 17 L. Klosterman; J.K. Riley; C.J. Bettinger, Langmuir 2015, 31, 3451-3458. 18 H. Lee; S.M. Dellatore; W.M. Miller; P.B. Messersmith, Science 2007, 318, 426-430.

THOMAS BARCLAY Title: Dr Future Industries Institute, University of South Australia, Australia Phone: (+61 8) 8302 3632 E-mail: [email protected] 2012

Awarded PhD in Chemistry, Flinders University

2009-2012

Research Assistant/Associate; Chemical and Physical Sciences, Flinders University

Since 2013 Research Associate/Fellow; Future Industries Institute, UniSA Research interests: Self-assembly and supramolecular chemistry, Drug delivery, Anti-fouling coating using polydopamine adhesive layers

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: WINE, FOOD AND DAIRY APPLICATION

T3.7 ENDRE NAGY MASS TRANSPORT ANALYSIS AND MEMBRANE CHARACTERIZATION FOR THE PRO AND FO PROCESSES ENDRE NAGY1, JÓZSEF DUDÁS1 1 Research Institute of Chemical and Process Engineering, University of Pannonia, Egyetem u. 10, H-8200, Veszprém, Hungary The performance of forward osmosis (FO) and pressure retarded (PRO) osmosis can be significantly affected by The performance of the pressure retarded osmosis (PRO) and forward osmosis (FO) processes strongly depends on the salt- and water transport rates. Thus, the exact description of the mass transport through the osmotically driven membranes is crucially important for prediction and improvement of the process performance. Nagy’s model1 defines the salt transfer rate for every single mass transport layer, and using them several new information can be obtained regarding the process performance. This new equations made possible to get new method for .determination of the water or salt permeability coefficient and the structural parameter. The aim of this paper is to show partly some new parameters and properties in the PRO processes which can be obtained by means of the defined salt transport rates. Accordingly, every single interface salt concentration will be expressed and its values analyzed as a function of the membrane and operating parameters ; it discusses the change of the overall mass transfer coefficient, the individual internal concentrations; the potential error of the often used expressions, e.g. Cm=Cdexp (-Jw/kd) or. Cs=Cspexp(JwS/D) or Csp=Cfexp(Jw/kf) in PRO process (kd, kf are the diffusive mass transfer coefficient of the external boundary layers; Jw is the water flux; S is the structural parameter of the membrane support layer; D denotes the diffusion coefficient; Cd, Cm, Cs and Csp are the draw bulk concentration, interface concentrations on the draw and the feed side selective as well as sponge layers, respectively), will be shown; on the other hand, a new expressions will be shown for determination of the salt permeability coefficient, B, and the structural parameter, S applying the flux rates obtained by both the PRO (draw solution faces the dense layer) and the FO modes (draw solution faces the support layer). Detailed analysis will be presented to illustrate the effect of the operating and the membrane parameters on the above parameters and how the membrane performance can be improved applying the newly developed process parameters. Results should help the user in the better understanding of the salt and water transport through an asymmetric PRO membrane. The results will be illustrated and confirmed by experimental data. The National Development Agency grant, Hungarian Research Fund (OTKA 116727) greatly acknowledged for the financial support.

GOLD SPONSOR

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REFERENCES 1 E. Nagy, A general, resistance-in-series, salt- and water flux models for forward osmosis and pressure retarded osmosis for energy generation, J. Membr. Sci., 460 (2014) 71-81

ENDRE NAGY Title: Mass transport analysis and membrane characterization for the PRO and FO processes University of Pannonia, Hungary Phone: +36203518725 Fax: +3688624040 E-mail: [email protected]; [email protected] 1969

Veszprém University of Chemical Engineering Degree: M. Sc

1973

degree of dr. techn

2000

degree of habilitation

2002

full professor at University of Pannonia (previously: Veszprém Univ.)

2005-2011 director 2016

160

Emeritus professor



Research interests:



1 Pervaporation process: separation of two-component mixtures (1971-)



2 Enzyme catalyzed reactions: hydrolysis of maltodextrin, hydrolysis of triglicerid esters, enzyme membrane bioreactors (1985-)

3 Heterogeneous catalytic reaction: isomerization of n-hexane on zeolite catalyst (1979-1990)



4 Mixing in fermentation reactors, scale-up (1991-1994)



5 Mass transfer and separation by membrane processes (1971-)



6 Separation of optically active components by membrane processes (2000-2011)



7 Controlled drug release (2002-2008)



8 Biomass utilization, bioethanol, biochemicals production (2005-)



9 Investigation of enzyme nanoparticles (2005-)

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: WATER AND WASTE WATER TREATMENT

THEME: WATER AND WASTE WATER TREATMENT T4.2 ARMINEH HASSANVAND ION TRANSPORT MODELLING IN MEMBRANE CAPACITIVE DEIONISATION

ARMINEH HASSANVAND1, GEORGE Q. CHEN1, PAUL E. WEBLEY1, SANDRA E. KENTISH1 1 Chemical and Biomolecular Engineering, University of Melbourne, Parkville, VIC 3010, Australia Capacitive Deionisation (CDI) is a desalination technology in which ions are adsorbed onto oppositely charged carbon electrodes. Electrical double layers, formed in the micropores (< 2 nm) of these carbon materials, are where the charged species are temporarily stored1. At the time that the electrodes reach their saturation point, adsorption capacity declines. Then by dropping the cell voltage to zero, the CDI cell can be regenerated with the adsorbed ions released back into a brine stream. In Membrane Capacitive Deionisation (MCDI), ion-exchange membranes (IEMs) are introduced in front of the electrodes to enhance the performance (Fig.1). By placing cation and anion exchange membranes in front of the cathode and anode respectively, only counter-ions are allowed to move toward the carbon electrodes. Hence the efficiency is improved by preventing co-ion repulsion. Another advantage of employing IEMs, is the fact the MCDI cell can be regenerated at reversed voltage, which results in a thorough depletion of carbon pores. This regeneration method not only is quicker than the former, but also is more effective2. MCDI, which was first introduced in 20063, is still considered as a new technique. Therefore, while different experimental work is being conducted in this area, a comprehensive ion transport model is needed to probe into more details and predict the performance. In this work, we have developed a dynamic ion transport model to describe the ion removal process in MCDI. To describe the storage of ions in the electrical double layers of the carbon micropores, an improved modified Donnan theory4 was implemented. Other novel aspects have been introduced to build a stronger model including direct measurement of the diffusivity coefficient of counter-ions though the membrane, and consideration of the activity coefficient in the Donnan potentials at the membrane interfaces. Accurate determination of the model parameters allows some of the simplifying assumptions to be dropped, which then results in a more comprehensive mathematical model. A good agreement between the modelling results and experimental data across a range of operating conditions was obtained.

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Figure 1. Schematic diagram of a MCDI cell during adsorption and desorption of ions. REFERENCES 1 Y. Oren, Desalination. 2008, 228, 10-29 2 S. Porada, R. Zhao, A. van der Wal, V. Presser, P.M. Biesheuvel, J. Prog. Mater Sci. 2013, 58, 1388-1442 3 J.B. Lee, K.K. Park, H.M. Eum, C.W. Lee, Desalination. 2006, 196, 125-134 4 P.M. Biesheuvel, S. Porada, M. Levi, M.Z. Bazant, J. Solid State Electrochem. 2014, 18, 1365-1375

ARMINEH HASSANVAND Ms. Chemical and Biomolecular Engineering, University of Melbourne, Parkville, VIC 3010 Australia Phone: +61 3 8344 8863 E-mail: [email protected] 2014 – Present: Doctor of Philosophy in Chemical Engineering at University of Melbourne, Victoria, Australia 2010 – 2012:

Master of Science in Chemical Engineering

2006 – 2010:

Bachelor of Science in Chemical Engineering

2006 – 2013:

Bachelor of Science in Mechanical Engineering, At Amirkabir University of Technology, Tehran, Iran

Research interests: Wastewater purification including Desalination technologies, AOP methods for degradation of organic compounds, Mass and charge transfer in Eletrochemical processes, Reactor design and Heterogeneous catalysis, Oil refinery and petrochemical processes

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T4.3 KATIE CHARLOTTE KEDWELL FORWARD OSMOSIS FOR PHOSPHORUS RECOVERY FROM WASTEWATER

KATIE CHARLOTTE KEDWELL1, GEORGIOS GIANNAKAKIS1, CEJNA QUIST-JENSEN1, MADS KOUSTRUP JØRGENSEN1, MORTEN LYKKEGAARD CHRISTENSEN1 1 Department of Chemistry and Bioscience, Aalborg University, Fredrick Bajers Vej 7H, 9100, Aalborg, Denmark Phosphorus has many uses, and its application is especially prevalent in agriculture. Peak phosphorus, the term given to the point in time at which the world’s phosphorus production will be at a maximum, will be reached as soon as 2030. This raises the concern that global phosphorus reserves will be depleted within 50-100 years. Considering phosphorus plays such an important role in day-to-day life it is necessary to find ways to recover or recycle phosphorus in the event of reserve depletion. One such way of doing this is by recovery from sludge reject water and digester centrate. Currently the most common method of phosphorus recovery from wastewater is by struvite (NH4MgPO4.6H2O) or calcium phosphate precipitation. However, in order to achieve as efficient a reaction as possible it is necessary to further increase the phosphate concentration in the reactor vessel or add a greater quantity of MgCl2 to improve the stoichiometric ratio. Increasing the phosphorus concentration can be achieved by removing a fraction of the water content from sludge reject water and or digester centrate. Membrane technologies, such as reverse osmosis and electrodialysis, have been utilised for this purpose to some avail. However, in these instances the need to apply hydraulic pressure or electrical potential across the membrane has led to a high degree of membrane fouling and operational expenditure (OPEX). As such it stands to reason to investigate other methods of concentrating phosphate which do not rely on hydraulic pressure as the driving force behind the process. Forward osmosis (FO) has proved to be a viable option. FO is the movement of water molecules across a selectively permeable membrane from a solution with low osmotic pressure to a solution with high osmotic pressure. The membrane rejects most solute molecules and ions, which enables the retention of phosphate molecules on the feed side of the membrane. The process is cost effective as it utilises osmotic pressure over hydraulic pressure, thus encouraging a lesser degree of fouling than pressure driven processes, promoting a lower OPEX.

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Furthermore, reducing the volume of water in the feed solution by ~33% can lead to spontaneous struvite crystallization in a solution with similar concentrations of phosphate and magnesium, as seen at Aaby WWTW (Denmark), and a water removal of 80% has the potential to lead to a phosphorus recovery of >90%, as shown in Figure 1, provided phosphate ions remain in the feed solution. As such, economically it makes sense to use FO in these situations rather than dose high concentrations of magnesium into the reactor vessel. This study focuses on two membrane types; carbon nanotube (CNT) (Porifera Inc, Hayward, USA) and biomimetic (Aquaporin A/S, Copenhagen, Denmark), and assesses their suitability in concentrating phosphorus in sludge reject water using seawater as a draw solution. Both membranes have a thinner support layer than traditional membranes, such as CTA or TFC, resulting in lower internal concentration polarisation (ICP) and higher water flux. Experiments were conducted using a laboratory test membrane cell. Run time was 6 hours and CNT membranes were used with the active layer facing the feed solution (AL-FS). Sludge reject water was collected from Aaby WWTW (Denmark) and used as the feed solution, while the draw solution was NaCl solution. Results show NaCl rejections >99%, phosphorus rejections >90% by the membrane, and a maximum flux of 15 L/m2h resulting in a 2-fold increase in feed phosphorus concentration during the 6 hour experiment. Additionally, the same experiments were carried out at pH 5 and 9, however, this had little effect on the process with experiments at pH 5 achieving >84% phosphorus rejection, while those at pH 9 realised a >90% phosphorus rejection, at both pH 5 and 9 NaCl rejection was >99%. Flux was not affected by changes in pH. Furthermore, while the flux fell to 47% of its initial capacity due to fouling, it could be restored to 98% of its original capacity simply by using DI water as the feed solution in-between experimental runs. Flux decreased more significantly on subsequent experimental runs, however because the fouling is mostly reversible without chemical cleaning it is possible to keep the OPEX low.

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From these results, along with Figure 1, it is clear that FO has great potential to aid the recovery of phosphorus from wastewater thanks to its high rejection of solute molecules and reasonable reduction in feed solution volume. Furthermore, the CNT membranes ability to withstand a wide pH range is beneficial in this instance since optimum struvite precipitation occurs around pH 9. KATIE CHARLOTTE KEDWELL PhD Fellow Aalborg University, Department of Chemistry and Bioscience, Denmark Phone: +45 9940 8493 E-mail: [email protected] Since 2015 PhD Fellow, Aalborg University 2014-2015

MSc Water and Wastewater Engineering, Cranfield University

Research interests: Forward osmosis, electrodialysis, membrane crystallisation, phosphorus recovery.

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T4.4 RANWEN OU HYDROPHILIC MICROFIBER-POLYMER HYDROGEL MONOLITH AS FORWARD OSMOSIS DRAW AGENT

RANWEN OU1, HUACHENG ZHANG1, GEORGE P. SIMON2 AND HUANTING WANG1 * 1 New Horizons Research Centre, Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia Phone: +61-3-9905-3449. 2 New Horizons Research Centre, Department of Materials Science and Engineering, Monash University, Clayton, Victoria 3800, Australia. Water desalination and purification are critical to address the global issue of the shortage of clean water. Forward osmosis (FO) desalination is an emerging low-cost technology for clean water production from saline water. The lack of a suitable draw agent is one of hurdle for the commercialization of FO desalination technology. Recently, the thermoresponsive hydrogel has been demonstrated to be a potential draw agent for the FO process. However, the commonly used hydrogel powder shows a much lower flux than other kind of draw agent such as inorganic salts. Stimuli-responsive polymer hydrogels have shown great potential for use as draw agent in emerging forward osmosis (FO) technology. The swelling pressure of hydrogel and the effective contact area between FO membrane and hydrogel are key parameters for achieving high water flux. Herein, we have demonstrated that the forward osmosis performance of hydrogels can be significantly improved by producing composite hydrogel monoliths containing thermoplastic polyurethane (TPU) microfibers. The use of monolithic hydrogels and the addition of microfibers enhance the effective contact area between membrane and draw agent, water diffusion through the draw agent, and sustain high swelling pressure, resulting in improved FO performance compared to the pure hydrogel particles. The proposed swelling mechanisms of hydrogel particles and composite monolith are shown in Figure 1. As observed in the sigmoidal swelling curves in Figure 2a, the swelling kinetics of microfiber– hydrogel composite (TPU microfiber-poly (NIPAM-co-SA), TPU-PN5S5) is faster than that of pure hydrogel (PN5S5), and the time required for the composite to reach swelling equilibrium decreases significantly; the diffusion exponent of TPU-PN5S5 composite increases from 0.73 to 0.81 (Figure 2b), indicating that addition of microfibers increases the water diffusion rate. Further studies show that water transports more quickly through the microchannels around TPU microfibers due to their hydrophilicity and capillary forces. The composite monolith was tested as forward osmosis draw agent, and it was found that the 1st hour FO water flux and dewatering flux of TPU-PSA are 1.81 and 3.51 Lm-2 h-1, respectively, twice of those for PSA particles alone, as shown in Figure 2c-d.

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This work was published in Journal of Membrane Science (R. Ou, H. Zhang, G. P. Simon, H. Wang, J. Membr. Sci. 2016, 510, 426-436).

Figure 1. The proposed swelling mechanisms of (a) pure hydrogel particle and (b) TPU-hydrogel composite.

Figure 2. (a) Swelling behaviour and (b) swelling kinetics of pure hydrogel and composite hydrogel. SR in (a) is short for swelling ratio. Reusability of (c) PSA particles and (d) TPU-PSA. 5 cycles of forward osmosis performance were tested, 5 h water flux was measured in each cycle.

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RANWEN OU Title: Ms. Australia Phone: +61435345948 E-mail: [email protected] 2007-2011

South China University of Technology, B. Sc.

2011-2014

University of Science and Technology of China, M. Eng.

2014-now

Monash University, PhD candidate

Research interests: stimuli-responsive polymer, membrane separation, water treatment

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T4.5 STEVEN CAO MEMCOR® CPII UF MEMBRANE FOR SECONDARY EFFLUENT TREATMENT AT ULU PANDAN WATER RECLAMATION PLANT

STEVEN CAO1, THAI LAW1, PAUL GALLAGHER2 1 Evoqua Water Technologies Membrane System 15 Blackman Crescent, South Windsor, NSW, Australia 2 Evoqua Water Technologies LLC, 558 Clark Road, Tewksbury MA 01876 Singapore, a highly urbanized and developed city-state country in Southeast Asia with a population of approximately 5 million, has limited native freshwater supplies. Provision of sustainable water supply has always been a top priority for the Singapore government, placing huge emphasis on development of water reuse strategies. In recent years, with the rapid increase in population and industrialization, wastewater reuse became even more important in Singapore’s government water strategy and provision was made to increase the reuse water from 30% of the nation’s current water needs to 55% by 2060. UF membrane systems will play a key role in the expansion of treating secondary effluent for high grade reuse water in Singapore. Memcor® CPII aims to offer improved customer benefits such as a smaller footprint and easier maintenance while offering superior hydraulic performance, reliability and efficiency. This product incorporates a complete redesign of the sub-module, the housing, the unit and the process that builds on previous generations of Memcor® products. CFD simulations were used to assist the optimisation of the housing and manifold designs. Pilot testing is generally required to ensure the successful application of UF membrane systems when treating variable quality secondary effluent streams. In this research, an Evoqua Water Technologies Memcor® CPII pilot plant was set up at Singapore Public Utilities Board, Ulu Pandan WRP to evaluate ultrafiltration membrane performance in treating secondary effluent. The main components of the pilot system include a MEMCOR® CPII pressurized membrane pilot system and associated pre-filter and feed system, chemical dosing systems, and waste discharge systems. Feed subsequently passes through an AMIAD® filter for physical screening of undesirable particles before being channelled to the CPII pilot feed tank. The pH, temperature and turbidity of incoming water are measured by corresponding online sensors. The filtered water will then be discharged to the drain. The pilot setup details are illustrated in Figure 1.

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Figure 1. MEMCOR® CPII Pilot System Trial Setup at Ulu Pandan WRP

During the initial process optimization trial, key process parameters, including operating flux, backwash intervals, maintenance clean protocols and intervals, were determined via accelerated trials and comparison trials. As a result of the optimization trial, the final operation conditions for the long term validation trial was maintained at 60 LMH with 20 minute backwash intervals, a daily maintenance wash (MW) with Sodium Hypochlorite and 30-day clean-in-place (CIP) intervals. Chlorine consumption during MW and CIP were tested regularly. Both process optimization trial results and long term validation trial results are discussed. Figure 2 shows the hydraulic performance of the MEMCOR®CPII pilot systems during the initial validation trial stage. Results showed the pilot was able to operate stably at designed trial conditions during the trial period. Transmembrane pressure was generally below 80 kPa throughout the trial period. Near the end of the first CIP cycle, a feed quality issue caused significant high fouling for a few days and, as a result, TMP increased to more than 150 kPa for a short period of time. However, this did not cause any impact on membrane integrity and CIP efficiency. CIP#2 was able to recover the module permeability and consequently the hydraulic performance was stable.

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Figure 2: Hydraulic Performance of MEMCOR® CPII pilot system at Ulu Pandan WRP

Throughout the trial, TMP rise per backwash cycle was generally greater than 10 kPa/BW, suggesting the operating conditions set in the trial were challenging. However, the combination of efficient backwash, MW and CIP enabled the MEMCOR® CPII pilot system to operate stably throughout the validation phase of the trial. Membrane integrity was monitored throughout the trial and no significant integrity issue was found. Evoqua Water Technologies has successfully conducted a secondary effluent pilot trial with the new MEMCOR® CPII product at Ulu Pandan WRP. Results showed the pilot operated stably under challenging operating conditions throughout the trial period. No integrity issue was found during the trial. This pilot study also demonstrated the importance of trial planning, regular process monitoring and troubleshooting, and active pilot and site maintenance in ensuring a successful operation. With excellent results obtained from the current trial, the operating flux will be increased to 70LMH in the coming months.

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T4.6 AZIZ GHOUFI PHYSICS BEHIND WATER TRANSPORT THROUGH NANOPOROUS GRAPHENE AND BORON NITRIDE

LUDOVIC GARNIER1, ANTHONY SZYMCZYK2, PATRICE MALFREYT3 AND AZIZ GHOUFI1 1 Institut de Physique de Rennes, IPR, UMR CNRS 6251, Université de Rennes1, Rennes, France 2 Institut des Sciences Chimiques de Rennes, CNRS, UMR 6226, Université de Rennes1, Rennes, France 3 Institut de Chimie de Clermont-Ferrand, ICCF, UMR CNRS 6296, ClermontFerrand, France Surface tension of water on graphene is a key-factor in desalination process based on graphitic membranes. Its knowledge is fundamental to rationalize water/ graphene interactions in order to improve our understanding of water permeation through nanoporous graphene (NPG). Many indirect approaches such as contact angle measurement have been used to evaluate the interfacial tension between water and graphitic surfaces. In parallel, several groups have focused on the prediction of water permeation through NPG and other 2D materials1-3. Despite recent progress, no direct determination of surface tension between water and graphitic surfaces has been attempted and the relationship between surface tension and water permeation performance has not been investigated yet. Additionally, while other materials such as graphyne and MoS2 have been well explored as potential nanofilters, boron nitride (BN) has never been considered. In this work, molecular dynamics simulations were used to determine the surface tension profile of water on multilayer graphene and BN (see Fig1. a), and to predict water permeation through nanoporous graphene and BN layers. For multilayer graphene and BN a decrease in surface tension (γ) was evidenced as the number of layers increases. This lessening in γ is the result of a negative surface tension contribution due to the long range wetting of water which contributes to lower water permeation through a two-layer system with respect to permeation through a single layer. We also depicted that a decrease in surface tension of water on BN monolayer with regards to graphene was at the origin of an increase in water permeation through BN (see Fig1. b ). Our findings suggest that nanoporous BN membranes could be attractive candidates for desalination applications.

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a)

b)

Figure 1. a) Illustration of water on graphene where red, white, blue, pink and grey atoms represent the oxygen, hydrogen, nitrogen, boron and carbon atoms, respectively. B) Number of water molecules crossing NPG and Nanoporous BN membranes as a function of the transmembrane pressure difference. The inset represents an enlargement for a pressure difference of 100 MPa

GHOUFI AZIZ Lecturer Institute of Physics Rennes (IPR), France Phone: +33223236993 E-mail: [email protected] 2006

Phd in Chemical-Physics

2006-2008

Post-Doc, IFPEN & Gerhardt institute (Montpellier, France)

Since 2008

Lecturer in Physics

Research interests: Confinement at nanoscale, Molecular Simulation, Water transport Aziz Ghoufi (Institut de Physique de Rennes; IPR, France) studied at the Université Blaise Pascal, Clermont Ferrand. He carried out postdoctoral research at the Institut Français du Pétrole and the Institut Gerhardt, Montpellier, and was appointed maître de conferences at the IPR in 2008. Ghoufi’s research interests include the development and applications of advanced molecular and mesoscale simulation techniques to modeling heterogeneous systems.

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T4.7 SEUNGHO KOOK EFFECT OF INITIAL FEED AND DRAW FLOWRATES ON THE PERFORMANCE OF AN 8040 SPIRAL-WOUND FORWARD OSMOSIS MEMBRANE ELEMENT

SEUNGHO KOOK1, JUNGEUN KIM2, SUNG-JO KIM1, JINWOO LEE1, DOSEON HAN1, SHERUB PHUNTSHO2, WANG-GEUN SHIM2, MOONHYUN HWANG3, HO KYONG SHON2,*, IN S. KIM1,3,** 1 School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), 123 Cheomdangwagi-ro, Buk-gu, Gwangju 61005, South Korea 2 Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney (UTS), P.O. Box 123, 15 Broadway, NSW2007, Australia 3 Global Desalination Research Center, Gwangju Institute of Science and Technology (GIST), 123 Cheomdangwagi-ro, Buk-gu, Gwangju 61005, South Korea FO-RO hybrid process has been suggested to reduce the energy consumption in desalination plants utilizing impaired water as feed streams and seawater as draw streams [1]. Here, FO functions as a pretreatment followed by RO in this scheme by diluting the seawater with impaired water sources and transporting the diluted seawater to the following RO process to lower the energy consumption and improve the overall plant cost effectiveness. In a practical perspective, connecting the FO elements in series is of critical importance to achieve desired RO feed concentration in the FO-RO hybrid system since the energy cost reduction is primarily induced by the seawater dilution in the FO step. In element based tests, the draw stream plays a critical role in generating the osmotic pressure difference within the elements and consequently draw water from the feed streams. Thus, it can be hypothesized that the initial draw flowrates will govern membrane element performances while initial feed flowrates have negligible impacts; a higher initial draw flowrate is expected to yield a higher averaged water flux of an FO membrane element due to a faster replenishment of osmotic driving force and a lower degree of dilution of draw streams due to lower retention time of the draw water body in the membrane element. The objective of this study is to perform single element-based tests to mimic a serial configuration of up to three 8040 FO membrane elements considering initial feed and draw flowrates as major independent variables without circulating draw streams to maintain osmotic driving force with time. The resulting water flux patterns and degrees of dilution of draw solution were systematically analyzed as the element number increases in series.

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THEME: WATER AND WASTE WATER TREATMENT

FO membrane module consists of an FO membrane element and a pressure vessel that can withstand an operating pressure of up to 30 bar. The 8-inch FO membrane element employed for this study was a spiral-wound CSM RE8040-FO. The element contains 10 polyamide thin-film composite (PA-TFC) membrane leaves with total effective membrane area of 15 m2. To minimize the effect of hydraulic pressure within the element on the membrane performance, the pressure difference (ΔP) between the feed outlet and the draw inlet of the element was maintained at 0.21 ± 0.01 bar to prevent membrane leaves from rupturing. The feed stream was circulated and the feed solutions for the following elements were produced with concentrations that matched to the concentrations at the feed outlet of the previous elements. On the contrary, the draw streams were not circulated and the diluted draw streams were collected and employed as the input draw streams for the following elements (Fig. 1). Average water flux (Jw,ave, L/m2h) of the element was computed by incorporating effective membrane area and the flowrates at the inlet and outlet of the draw channel; the flowrates were automatically recorded every minute. The Jw,ave values for each test remained consistent due to the non-circulating draw streams. Initial feed flowrates were in the range of 20 – 50 L/min and 2 – 5 L/min for initial draw flowrates.

Figure 1. Illustration of the single element-based serial configuration test procedure

It was found the averaged Jw,ave values for varying feed and draw flowrates were found to be 20.93, 19.38 and 18.71 LMH at E1, E2 and E3, respectively, with averaged diluted draw concentrations of 12.55, 7.88 and 5.77 g/L (Initial conc. 35 g/L). To quantitatively compare the impacts of feed and draw flowrates more vividly, water retrieval rates (QP=QD,N+1-QD,1 (N=1,2,3)) were computed in Fig. 3 with varying initial flowrates and the element numbers. Fig. 2b and 2d clearly shows the initial assumption on the feed flowrates that, for a fixed initial draw flowrate, the initial feed flowrates indeed have negligible impact on the water transport toward the draw streams. On the other hand, QP was significantly deviated with an apparent increasing pattern as both the initial draw flowrates and the increasing element number (Fig. 2a and 2c).

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Figure 2. Illustration of the single element-based serial configuration test procedure

Figure 3. (a) Diluted draw solution concentrations exiting the membrane elements in series and (b) averaged diluted draw solution concentrations and dilution ratio (DR = diluted / initial X 100) for E1, E2 and E3

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The initial draw flowrates have a significant effect on the dilution of the draw streams while the initial feed flowrates have negligible impacts. It is important to note the diluted draw solution concentration has positive correlation with the pattern of Jw,ave. Higher diluted draw solution concentration and higher Jw,ave at higher initial draw flowrate (i.e. shorter retention time of the draw streams) confirms the hypothesis that the higher initial draw flowrate reduces the draw stream dilution. These results address an important finding that, for spiral-wound FO membrane elements, initial draw flowrates govern the element performances and higher Jw,ave does not necessarily lead to better dilution of the draw streams. Thus, controlling initial draw flowrate is of critical importance in obtaining desired membrane performances. REFERENCES 1

T.Y. Cath, N.T. Hancock, C.D. Lundin, C. Hoppe-Jones, J.E. Drewes, J. Memb. Sci. 2010, 362, 417-426

SEUNGHO KOOK Title: Mr. Gwangju Institute of Science and Technology (GIST), South Korea Phone: +82-62-715-2477 Fax: +82-62-715-2434 E-mail: [email protected] 2012-2014

M.S. Course at Gwangju Institute of Science and Technology (GIST)

2015-2016

Collaborative research at University of Technology Sydney (UTS)

Since 2014

Ph. D. Course at GIST

Research interests: membrane-based desalination, hybrid desalination processes

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T4.10 PAMELA EL JBEILY, KEVIN CLARKE TREATING CLARIFIER AND BACKWASH WASTEWATER WITH ULTRAFILTRATION MEMBRANES

PAMELA EL JBEILY1, KEVIN CLARKE2, FRED BARENDREGT3, FADI AKKAWI1 1 Ixom Operations Pty Ltd 2 DOW Chemical (Australia) Pty Ltd 3 KBR The Botany Groundwater Treatment Plant (GTP), located in Sydney NSW, forms a major component of the Groundwater Cleanup Project being undertaken by Orica and Chemicals division (now Ixom Operations)1 to clean up contaminated groundwater arising from former chemical industry operations at Botany Bay. The GTP generates wastewater from clarifier and backwash processes at 32 kL/h, all of which was formerly discharged to the sewer. In order to reduce trade waste costs, Orica and the Chemicals division investigated the use of membranes to recover some of the waste discharged to the sewer and trialled DOW outside-in polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes in 2013. The trial assessed the suitability of the DOW membrane format and configuration and enabled optimization of system design parameters. The feedwater quality to the UF system was particularly challenging as the water was highly biologically active, with the total iron being as high as 10 mg/L and suspended solids up to 45 mg/L. The objective of the trial was to recover water of sufficient quality to allow it to be returned to groundwater treatment process. From the trial results, reprocessing the wastewater with UF was expected to provide savings of more than $600K annually in reduced trade waste costs to GTP. The plant has been in operation since October 2014 with the UF system producing filtrate with total iron less than 0.5 mg/L and turbidity less than 1 NTU. This paper discusses the concept technology selection process, the pilot trial methodology and results, the project delivery, the current plant performance, operational challenges, and financial benefits.

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PAMELA EL JBEILY Senior Process Engineer Ixom Operations Pty Ltd, Australia Phone: +61 (0) 405 386 604 E-mail: [email protected]

KEVIN CLARKE ANZ Technical & Services Manager DOW Chemical (Australia) Pty Ltd, Australia Phone: +61 (0) 400 588 491 E-mail: [email protected]

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T4.11 DEVELOPMENT AND APPLICATION OF A HYDROPHILIC PVDF MEMBRANE FOR SEAWATER RO PRETREATMENT IN AUSTRALIA

GEOFFREY JOHNSTON-HALL INFORMATION TO COME

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T4.12 ELISE DES LIGNERIS DESIGN OF ELECTRO-SPUN METAL-BASED ANTI-BACTERIAL MICRO-FILTERS

ELISE DES LIGNERIS1, ANDREA MERENDA1, MIKEL DUKE2, JÜRG SHUTZ3, LUDOVIC DUMÉE1, LINGXUE KONG1 1 Institute for Frontier Materials, Deakin University, Waurn Ponds, VIC 3218, Australia 2 Institute for Sustainability and Innovation, Victoria University, Werribee, VIC 3030, Australia 3 Commonwealth Scientific and Industrial Research Organisation CSIRO, Waurn Ponds, VIC 3218, Australia The design of bactericidal micro-filters is of high interest for water and air disinfection in a world where the action and proliferation of bacteria is well more understood1,2. In this area, nanofibers membranes have been preferred over microfiber nonwovens for their small pore size (sub-micrometer) and up to a thousand times larger surface area to volume ratio1. The electro-spinning technique as a method of fabrication of nanofibers possess outstanding advantages such as the versatility and high homogeneity in reachable fiber diameter (from tens to thousands of nanometers) and membrane pore size (down to fractions of nanometer), together with an interconnected pore size structure and a relatively low density2,3. Electrospun polymer nanofibers post-functionalized with biocides - such as bronopol, thiocyanic acid or silver nanoparticles - have previously been reported and showed good potential for anti-bacterial filtration, with a removal over 4.0 log10 CFU/100 ml removal over an inoculum of 106 CFU/ml for both gram positive and gram negative bacteria using the standard AATCC Test Method 100-20054,5. However, the use of these nanofiber membranes is hindered by some limitations, including the use of toxic chemicals for the biocide agent synthesis, and more importantly the leaching of the biocide agent, which can attain 6% over the first 2 L of feed water4,6. In this study, we considered the use of silver and as a cheaper alternative copper to be used as biocide agents. To tackle the leaching issue and improve the contact surface area, metal nanofibers have been successfully fabricated and assembled onto a ceramic support to improve the compression resistance and ensure optimal separation performance. The use of metal-based nanofiber membranes further combine the high surface area associated nanofibers to the water quality stand, and semi-conducting properties of metals at the nano-scale. The synthesis of alloys have also been considered to enhance bactericidal activity against both gram negative and positive bacteria as well as to combine single metals properties such as corrosion resistance.

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The chosen fabrication route for metal nanofiber membranes consists of the electrospinning of a compatible polymer-metal salt sol-gel precursor into a high porosity and sub-micrometer pore size membrane of regular diameter (around 700 nm) hybrid nanofibers, further annealed to remove the organic content and initiate the grain nucleation and coalescence, thus forming metal oxide grain necklaces that are sizedependent of the applied temperature (Fig.1). Another thermal treatment under reductive atmosphere (15% H2 in N2) enable the control of the fiber oxidation degree. SAXS and TEM diffraction have been used to analyse the reorganisation of the microstructure to form polycrystalline nanofibers (Fig.2). Assembly of the metal-based nanofibers onto a support layer through thermal sintering has also been investigated to provide a suitable adhesion. Although this fabrication route can be found in the literature7, the application of metal nanofiber membranes for anti-bacterial microfiltration has not yet been reported, and further work was required on the synthesis of nano-alloys as well as on the characterization of the influence of the fabrication parameters on the fiber texture, porosity and oxidation degree (Fig.3), which directly impact the catalytic and bactericidal activity as well as the mechanical resistance of the membrane. Bactericidal activity against gram negative Escherichia coli and gram positive Staphylococcus aureus bacteria showed high potential for hospital or spiked water treatment (Fig.4). Air disinfection through antibacterial and air filtration testing is also being considered to be used as anti-bacterial vacuum filters (Fig.4). Furthermore, the use of a total anti-bacterial surface is believed to hinder the attachment of bio-contaminants onto the surface of the fibers, hence engendering an anti-biofouling activity which could be of interest for a wide range of waste effluents. REFERENCES 1 N. Daels, Membranes in drinking and industrial water treatment, 2010 2 R. Wang, Y. Liu, Journal of Membrane Science 2012, 392, p. 167-174 3 Z-M. Huang, S. Ramakrishna, Composites Science and Technology 2003, 63, p. 2223-2253 4 N. Daels, Desalination 2011, 275, p. 285-290 5 L. Zhang, Journal of Membrane Science 2011, 369 p. 499-505 6 K. Tan, S-K. Obendorf, Journal of Membrane Science 2007, 289, p. 199-209 7 H. Wu, W. Pan, Journal of Advanced Ceramics 2012, 1, p. 2-23

Figure 4. Transmission Electron Micrographs of an electrospun polyvinyl alcohol PVA-Copper acetate salt mixture (a) annealed respectively at 300 ⁰C, 500 ⁰C, 700 ⁰C (b,c,d) performed under air at 5 ⁰C/min heating rate.

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(a)

(b)

(c)

(d)

C

28.0

0.39

0.34

3.27

O

30.4

16.2

10.0

14.6

Cu

41.6

83.4

89.7

82.2

Figure 2. Up: Scanning Electron Micrographs of an electro-spun PVA-Copper acetate structure (a), respectively annealed under air at 500⁰C (b), under air at 500⁰C then under 15% H2 at 300⁰C (c), and under 15% H2 at 500⁰C (d). Down: Corresponding elemental composition in wt% obtained by X-ray photospectroscopy.

E-coli Membrane Membrane

E-coli

Figure 3. Left: Selected Area Diffraction patterns obtained at 40 cm camera length on an air-annealed electro-spun PVA-Copper nanofiber at 700⁰C on the whole fiber (left) and on a single grain (right). Right: Microscope images showing the inhibition zone of an electro-spun PVA-Copper membrane after 24h contact with Escherichia coli bacteria following a standard procedure. The membrane was poorly affected by moisture (PVA).

ELISE DES LIGNERIS Title: Ms Affiliation, Country: Institute for Frontier Materials, Deakin University, Australia Phone: +61(0)411131862 E-mail: [email protected] 2011

Bachelor in Applied Mathematics and Physics with honours

2011-2014

Master in Textile Engineering

Since 2015

PhD in electrospinning of metal-based nanofiber membranes

Research interests: electrospinning, nanostructures, metals, electron microscopy

GOLD SPONSOR

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THEME: WATER AND WASTE WATER TREATMENT

T4.13 RECYCLING CARWASH WASTE WATER USING CERAMIC MEMBRANE ULTRAFILTRATION

SHAMIMA MOAZZEM, SUSANTHI LIYANAARACHCHI, LINHUA FAN, FELICITY RODDICK, JEGA JEGATHEESAN School of Engineering, RMIT University, GPO Box 2476, Melbourne 3001, Australia Carwash wastewater is an environmental concern as it contains a range of pollutants such as petroleum hydrocarbon wastes (gasoline, diesel and motor oil), heavy metals (such as copper, lead and zinc), nutrients (phosphorus and nitrogen), surfactants and suspended solids, microorganisms, sand and dust. More than 35 billion liters of contaminated wastewater from carwash centers are directed into the sewerage systems across Australia each year1.Therefore appropriate treatment processes are required to treat this wastewater to enable its reuse within those carwash facilities and to effectively prevent the transfer of the pollutants to the sewerage systems. This paper focuses on a treatment method consisting of coagulation and sand filtration followed by ultrafiltration using a ceramic membrane to enable the reuse of the carwash wastewater. Carwash wastewater was collected from a heavily used carwash facility in Melbourne and stored at 4ºC. Coagulation was performed using ferric chloride without adjusting the initial pH and the optimum dose was determined to be 45 mg/L. Samples were mixed at 300 rpm for 1 min and 30 rpm for 30 min, then allowed to settle for 30 min after which the supernatant was collected for analysis and subsequent treatment. Slow sand filtration utilised a filter of 0.235 m height and the flow velocity varied from 0.302 m/s to 0.226 m/s with periodic backwash upon the increase in turbidity. The effluent from the sand filtration was collected and then treated by ultrafiltration. The membrane (0.02 µm) was comprised of α-alumina oxide as supporting material with α-alumina oxide, zirconia oxide and titanium oxide as membrane material; the trans-membrane pressure was 2.4 bar and the pure water flux was 100 L/m2h. After each treatment step, the treated water was analysed for chemical oxygen demand (COD), turbidity and total organic carbon (TOC) according to Standard Methods (APHA, 1998)2. According to the Environment Protection Authority (EPA) of Victoria, the quality of recycled water for car washing should be Class A3. The characteristics of the treated water were compared with those for EPA class A and two International Standards (Table 1). It was found that the treated water met the criteria except for COD. According to an International Carwash Association report the treated water should not contain particles greater than 10 μm as it will be used in high pressure pumps to perform the wash cycle4, so the particle size of the wastewater was determined using a Mastersizer 3000. In the carwash waste water the particle size was normally distributed around 11.4 µm (50% of particles), with lower and upper values of 2.4 and 50 µm, respectively, and a small proportion up to 144 μm. After completing the treatment sequence there was 100% removal of those particles was obtained

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THEME: WATER AND WASTE WATER TREATMENT

Table 1 Comparison of the treated water quality with EPA Class A recycled water and International Standards Parameter

Carwash Coagulation

Coagulation

waste

(45 mg/L

+ Sand

water

FeCl3)

Filtration

Coagulation+ Recycled Sand Filtration+ UF (0.02 µm)

pH COD (mg/L) Turbidity (NTU) TOC (mg/L)

6.42

4.47

6.24

6.5

295

105.5

104.5

88.5

522

2.24

1.49

0.857

70.38

64.49

39.36

32.38

water Class A

Standard

Standard

in

in China6

Flanders5

according to EPA3 6-9

6.5-9

6.5-9

<125

50

2(5)

As shown in Table 1, coagulation greatly reduced the COD (by 65%) and turbidity (by 99%) of the carwash water, and there was little further removal of these components by sand filtration. In contrast, there was markedly greater removal of TOC by sand filtration compare to coagulation. There was further removal of the COD and TOC, or “polishing” of the wastewater, by the ultrafiltration step. However, although an overall removal of 70% of the COD from the raw carwash water was achieved by the treatment sequence, which met the EPA of Victoria and Flanders criteria, further process optimisation would be required for the treated water to comply with the Chinese standard. The two waste streams arising from this process: 0.94 L sludge from 25 L sample (equivalent to 10 g dry weight) after coagulation and 4 L retentate generated from 20 L of pre-treated carwash water after ultrafiltration, will require further treatment to enable their safe disposal. These streams will be analysed to enable determination of a mass balance for the treatment process and appropriate management processes devised. It can be concluded that the use of coagulation by ferric chloride and slow sand filtration prior to ultrafiltration with the ceramic membrane was effective for removing the COD, turbidity, TOC, suspended solids and particles and so treating the carwash wastewater to enable its reuse. Moreover the E-coli bacteria of the ultra filtration effluent would be measured to satisfy the criteria of recycled water of EPA of Victoria. However, to comply with the standard in China further treatment would be required. Keywords: Carwash waste water, Coagulation, Sand Filtration, Ceramic Membrane, Ultrafiltration REFERENCES: 1

I.A.R Boluarte, M. Andersen, B.K. Pramanik,C. Chang, S. Bagshaw, L. Farago, V. Jegatheesan & L. Shu, 2016, ‘Reuse of car wash wastewater by chemical coagulation and membrane bioreactor treatment processes’, International Biodeterioration & Biodegradation, http://dx.doi.org/10.1016/j. ibiod.2016.01.017 GOLD SPONSOR

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2

APHA, 1998, Standard Methods for the Examination of Water and Wastewater, 20th edn, United Book Press Inc., Baltimore, Maryland.

3

EPA Victoria, 2003, Guidelines for Environmental Management USE OF RECLAIMED WATER, Publication 464.2, page 20.

4

C. Brown, 2000, Water Conservation in the Professional Car Wash Industry, first ed. Washington, USA: International Car Wash Association.

5

K. Boussu, K. Kindts, , C. Vandecasteele, & B. Van der Bruggen, 2007, ‘Applicability of nanofiltration in the carwash industry’, Separation and Purification Technology, vol. 54, no. 2, pages. 139-46.

6

T. Li, T. Xue-jun, C. Fu-yi, Z. Qi, Y. Jun, 2007, ‘Reuse of carwash wastewater with hollow fiber membrane aided by enhanced coagulation and activated carbon treatments’, Water Sci. Technol. 56 (12), pages. 111-118.

SHAMIMA MOAZZEM Title: Mrs Affiliation: RMIT University, Country: Australia Phone: + 61 3 9925 3195, E-mail: [email protected] Masters by Research Student in Environmental Engineering in RMIT University since 2015 Research interests: Membrane technology, Wastewater treatment

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THEME: MEMBRANE BIOREACTORS

THEME: MEMBRANE BIOREACTORS T3.10 CROSSING THE BORDER BETWEEN LABORATORY AND FIELD: BACTERIAL QUORUM QUENCHING FOR ANTI-BIOFOULING STRATEGY IN AN MBR

SANG HYUN LEE, KIBAEK LEE, CHANG HYUN NAHM, SEONKI LEE AND CHUNG-HAK LEE School of Chemical and Biological Engineering, Seoul National University, Seoul 08826, South Korea. Phone: +82-10-8770-0672, E-mail: [email protected] Quorum quenching (QQ) has recently been acknowledged to be a sustainable antifouling strategy and has been investigated widely using lab-scale membrane bioreactor (MBR) systems1-3. This study attempted to bring this QQ-MBR closer to potential practical application. Two types of Test Bed for QQ-MBRs with either flat-sheet or hollow fiber modules were installed and run at a wastewater treatment plant, feeding real municipal wastewater to test the systems’ effectiveness for membrane fouling control and thus the amount of energy savings, even under harsh environmental conditions. In QQ-MBR with quorum quenching bacteria entrapping-media (beads or hollow cylinders), the rate of transmembrane pressure (TMP) build-up was significantly mitigated compared to that in a conventional-MBR. Consequently, QQ-MBR can substantially reduce energy consumption by reducing coarse bubble aeration without compromising the effluent water quality. The addition of QQ-media to a conventional MBR substantially affected the EPS concentrations, as well as microbial floc size in the mixed liquor. Furthermore, the QQ activity and mechanical stability of QQ-media were well maintained for at least four months, indicating QQ-MBR has good potential for practical applications. The evolution of QQ media will be also addressed from microbial vessel, via spherical beads to cylinders/ hollow cylinder and sheets.

Figure 1. QQ-Bacteria entrapping QQ media. GOLD SPONSOR

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REFERENCES 1

K. M. Yeon, W. S. Cheong, H. S. Oh,; W. N. Lee, B. K. Hwang, C. H. Lee, H. Beyenal, Z. Lewandowski, Quorum sensing: a new biofouling control paradigm in a membrane bioreactor for advanced wastewater treatment. Environ Sci Technol. 2009, 43, (2), 380-5.

2

C. Fuqua, M. R. Parsek, E. P Greenberg, Regulation of gene expression by cell-to-cell communication: acyl-homoserine lactone quorum sensing. Annu Rev Genet. 2001, 35, 439-68.

3 S.K. Lee, S.K. Park, H.P. Kwon, S.H. Lee, K.B. Lee, C.H. Nam, S.J. Jo, H.S. Oh, P.K. Park, K.H. Choo, C.H. Lee, T.W. Yi, Crossing the Border between Laboratory and Field: Bacterial Quorum Quenching for Anti-Biofouling Strategy in an MBR, Environ Sci Technol. 2016, 50 (4), 1788-1795

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE BIOREACTORS

T3.11 SOJIN MIN EFFECT OF REACTOR TEMPERATURE ON A QUORUM QUENCHING MEMBRANE BIOREACTOR (QQ-MBR) FOR WASTEWATER TREATMENT

SOJIN MIN1, KIHONG KIM1, JEONGWON PARK1, HYOEUN KWAK1, JOOWAN LIM1, PYUNG-KYU PARK1,*, ISMAIL KOYUNCU2 1 Department of Environmental Engineering, Yonsei University, Republic of Korea 2 Environmental Engineering Department, Istanbul Technical University, Turkey INTRODUCTION

For over thirty years, membrane bioreactors (MBRs) have been widely applied to advanced wastewater treatment and reuse. However, the major problem of the MBR is membrane biofouling which leads to high operating costs. It was reported that one of the causes for the biofouling was bacterial quorum sensing (QS), i.e. the communication between bacteria cells through releasing small signal molecules called autoinducers, and thus the inhibition of the bacterial QS, which is known as quorum quenching (QQ), was effective to mitigate biofouling in MBR.7, 8 To inhibit bacterial QS, a bacterial QQ method was developed in a previous study: Bacteria which produce quorum quenching enzymes to degrade QS signal molecules were embedded in polymeric beads (QQ-beads) and inserted to MBR, which resulted in effective reduction of biofouling in MBR due to biological and physical washing effects of the QQ-beads.9 The effects can be affected by temperature because QS is generally inhibited at low temperature due to reduced bacterial growth and activity. For example, the production of a homoserine lactone, a QS signal molecule, by Aeromonas hydrophila 519, a foodborne bacterium, was reduced at 12oC.10 The QQ effect may change as a function of temperature because QS in MBR is likely to depend on reactor temperature. However, the temperature effect on QQ in MBR has not been investigated. Therefore, the goal of this study was to investigate the effect of temperature on the performance of QQ-MBR for designing a QQ-MBR working properly in cold climates. MATERIALS AND METHODS

QQ-beads were prepared using dripping method: The mixture of poly (vinyl alcohol), alginate and Rhodococcus sp. BH4, a QQ bacterium, was dripped into CaCl2-boric acid solution to form spherical beads. Next, the beads were immersed in sodium sulfate solution and then stored in deionized water. The average diameter of the beads was approximately 4.1 mm. The activity of QQ-beads was examined in batch tests using bioluminescence assay for measuring the concentration of N-octanoyl-DL-homoserine lactone (C8-HSL). The C8-HSL was chosen as representative signal molecule because it is one of the dominant GOLD SPONSOR

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THEME: MEMBRANE BIOREACTORS

homoserine lactones in MBRs for wastewater treatment.3 A. tumefaciens A136 was used as a reporter strain for the C8-HSL. A laboratory-scale submerged hollow-fiber MBR with a working volume of 2.5 L was operated with synthetic wastewater (Fig.1). The temperature of reactors was maintained at certain constant value, which was changed in each experiment from 25oC to 10oC to investigate the temperature effect. Other operating parameters are listed in Table 1. The dosage of QQ-bead was 0.5%v/v of the reactor volume. The rise-up pattern of transmembrane pressure (TMP) was measured and compared for conventional MBR (without any beads), vacant-bead MBR and QQ-bead MBR during continuous operation. Extracellular polymeric substances (EPS) concentrations were analysed to figure out the temperature effect on biofouling mitigation.

Figure 1. Schematic diagram of MBR operation. Table 1. MBR operating conditions

Parameter pH HRT SRT MLSS Flux Air flow rate

190

7.30~7.45 6h 30 d 5000 ~ 5500 mg/L 20 L/(m2∙h) 1.25 L/min

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE BIOREACTORS

RESULTS AND DISCUSSION

In the QQ-bead activity test, the C8-HSL concentrations were reduced to 44% and 87% at 8 and 23oC, respectively, by the QQ-beads in 120 min. Especially, the initial degradation of the C8-HSL in 1 min was quite inhibited at low temperature even though the degradation rates (the slope of the curves) after 1 min were similar to each other. This difference in QQ effect as a function of water temperature was further investigated in continuous MBRs. At 25oC, the TMP rise-up in the course of biofouling was slower for the QQ-bead MBR than the vacant-bead MBR as well as the conventional MBR, indicating that QQ effect worked well at normal temperature. When the reactor temperature was reduced to 16.5oC, it was also confirmed that the biofouling in QQ-bead MBR was relatively decreased by the QQ effects even though the TMP rise-up for all three MBRs were quicken due to the temperature decrease. The QQ effect has been further investigated at around 10oC, and TMP, EPS and other parameters will be compared. ACKNOWLEDGEMENTS

This research was supported by the International Research and Development Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning of Korea (2014K2A1B8048425). SOJIN MIN Department of Environmental Engineering, Yonsei University, Republic of Korea Phone: +82-10-7711-8334 Fax: +82-33-760-2889 E-mail: [email protected] 2015 Bachelor of engineering at Yonsei University, Republic of Korea Research interests: MBR, Biofouling, Quorum Quenching

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THEME: MEMBRANE BIOREACTORS

T3.12 MS SOFIE T. MORTHENSEN AN INTEGRATED MEMBRANE SYSTEM FOR ENZYMATIC COFACTOR REGENERATION AND DOWNSTREAM PURIFICATION OF PRODUCTS Department Of Chemical And Biochemical Engineering, Center For Bioprocess Engineering, Technical University Of Denmark Lignocellulosic biomass is an abundant and renewable feedstock with the potential to supplement fossil resources for production of valuable chemicals and fuels. In order to exploit the full potential of lignocellulose, effective utilization of all biomass constituents must be accomplished at all stages of biorefining1. As an example, xylose and glucose released during biomass pretreatment could be separated in order to obtain pure sugar streams for production of specific building block chemicals. It was previously shown2 that separation of xylose from glucose can be greatly enhanced through enzyme-assisted nanofiltration (NF), in which glucose is converted to another value-added chemical (gluconic acid) with charge properties significantly different from xylose. In the present work, an integrated membrane process is investigated for the conversion of glucose by an enzymatic cofactor regeneration system and the subsequent purification of products (Fig. 1). L-lactic dehydrogenase (LDH) was selected as the cofactor regenerating enzyme since it operates at the same optimal conditions (37°C, pH 7.5-8) as glucose dehydrogenase (GDH) and at the same time produces another value-added product, lactic acid (from pyruvate).

Figure 1. Separation of xylose from xylose-glucose mixtures using an integrated membrane process for (1) enzymatic cofactor regeneration and (2) downstream purification of products performed in two different sequences (2a and 2b). Xyl = xylose; Glc = glucose; Pyr = pyruvate; GA = gluconic acid; LA = lactic acid; GDH = glucose dehydrogenase; LDH = l-lactic dehydrogenase; NF=nanofiltration.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE BIOREACTORS

The results obtained showed that the initial cofactor (NADH) concentration could be decreased to 10 % of the stoichiometric value without compromising process time and substrate conversion due to i) efficient cofactor regeneration in the membrane bioreactor and ii) high retention of cofactor (R=0.98) after each reaction cycle. The retention of NADH was mainly governed by electrostatic repulsion between the negatively charged NTR 7450 membrane and the negatively charged cofactor. Despite the relatively high MW of NAD+ (664 Da) compared to the MWCO of the membrane (600-800 Da), the retention of the oxidized cofactor was only 0.76 which indicated that the solute permeation in the absence of charge effects was mainly governed by the shape of the solute which comprised several smaller subunits (≤270 Da). Separation of the cofactor from xylose (R<0.1), lactic acid (R=0.38) and gluconic acid (R=0.63) was achieved; however the membrane had lost >70 % of its initial water permeability after three consecutive cycles indicating that significant fouling occurred probably due to pore blocking and adsorption by the enzymes. Xylose, lactic acid and gluconic acid could be separated based on charge repulsion and size exclusion in a sequence of NF steps. The separation mechanism was controlled through pH adjustment in order to induce or eliminate electrostatic repulsion. It was concluded that sequence 2a provided the highest yields and purities of the different streams. Xylose (R=0.30) was first separated from the acids (R>0.83) at pH 9.5 with the NF270 membrane, and subsequently lactic acid (0.17) was separated from gluconic acid (0.77) with the BW30 membrane at pH 2.5. Since pH 2.5 was below the pKa of the acids and the isoelectric point of the membrane, charge effects were eliminated so the separation mechanism was merely governed by size exclusion. The broad substrate specificity of GDH, which led to conversion of xylose to xylonic acid, was indeed a negative side effect. However, this problem could potentially be overcome by application of a GDH from another origin. Generally, our study showed that if one can design a system where yields and purities are maximized, the strategy of facilitating the purification of one molecule by value-adding the other(s) is a novel and promising approach for enhancing the separation performance in other similar applications. SOFIE THAGE MORTHENSEN Title: Ms Technical University of Denmark (DTU), Denmark Phone: +45 45 25 26 12 E-mail: [email protected] Since 2014

PhD student (DTU)

2011-2014

M.Sc. in Chemical and Biochemical Engineering (DTU)

2008-2011

B.Sc. in Chemistry and Technology (DTU)

Research interests: Integration between enzyme technology and membrane separation in biorefinery processes

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193

THEME: MEMBRANE BIOREACTORS

T3.13 LISA LECKIE CRITICAL SUCCESS PARAMETERS FOR MBR MODULE IMPROVEMENTS

LISA LECKIE1, STEVEN CAO1, JESSICA TOLA1, CHAN TUN1, GERIN JAMES1, PAUL GALLAGHER2 1 Evoqua Water Technologies Membrane Systems Pty. Ltd 2 Evoqua Water Technologies LLC Changes to designs of hollow fibre membrane modules, albeit improvements, require robust testing and validation protocols in order to justify product improvements and process improvements both thoroughly and efficiently. MBR modules, in particular, encounter some of the most aggressive environments, due to the combination of high mixed liquor suspended solids concentrations, tough cleaning processes and, at times, exposure to unusual foulants. All components of an MBR module must be proven to withstand both the environment in which they are applied as well the cleaning protocols necessary for continued performance. This includes both the membranes themselves and the potting compounds used to hold the membranes and separate the feed and filtrate sides of the system. Described in this paper are the results of accelerated testing to ensure lifetime reliability of all the components of MBR modules when higher fibre packing densities are introduced. Early generations of MBR modules were designed with very low packing density of fibres (the ratio of fibre cross-section area to overall pot cross-section area). As MBR technology has advanced, the trends have been towards improved aeration for module cleaning, towards somewhat lower mixed liquor suspended solids concentration. These changes have enabled and encouraged incremental increases in module packing density. Success criteria for packing density changes includes demonstration of sustained hydraulic capabilities, both through reliable treatment capability at the membrane surface and resistance to solids build-up in the bulk module, and without detriment to pot or membrane integrity under concurrent exposure to a lifetime’s worth of pressure cycling and cleaning chemicals. Membrane aeration can be aggressive to MBR modules, particularly at the fibre pot interface at the time of flow change, so this, too, must be validated with respect to membrane integrity. This paper describes both the accelerated testing used during the product development of an increased packing density version of Evoqua’s B40N module, the criteria considered important to the success of the testing and the subsequent field validation testing at a customer site.

194

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE BIOREACTORS

LISA LECKIE R&D Program Manager Evoqua Water Technologies Membrane Systems Pty. Ltd, Australia Phone: +61 2 4577 0822 Fax: +61 2 4577 0919 E-mail: [email protected] 1998 - Present Evoqua Water Technologies Membrane Systems Pty Ltd (inc. roles in project management, membrane manufacturing, water and wastewater operating processes for membranes, systems and applications engineering, and sales and marketing. 1994-1997

Bachelor of Chemical Eng. (Hons 1), UNSW

2008

Cert IV Project Management - ACPM

Research interests: Hollow fibre membrane processes and manufacturing, accelerated product commercialisation

GOLD SPONSOR

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THEME: MEMBRANE BIOREACTORS

T3.15 G.BLANDIN OPPORTUNITIES AND CHALLENGES TO RETROFIT EXISTING MEMBRANE BIOREACTOR (MBR) IN OSMOTIC MEMBRANE BIOREACTOR (OMBR) FOR (POTABLE) WATER REUSE

G.BLANDIN1, CLÉMENT GAUTIER1, JOAQUIM COMAS1,2, IGNASI RODRIGUEZ-RODA1,2 1 LEQUIA, Institute of the environment, University of Girona, Spain 2 ICRA, Catalan Institute for Water Research, Girona, Spain Recently, forward osmosis (FO) has been applied to the context of membrane bioreactor (MBR) and is called osmotic MBR (OMBR). Instead of using a porous ultrafiltration (UF) or microfiltration (MF) membrane, a dense FO membrane is submerged in a bioreactor. Interestingly, higher rejections of contaminants and lower fouling propensity than for MBR were observed 1 As such, OMBR combined with reverse osmosis (RO) for draw recovery is a promising alternative to MBR (and MBR-RO) to produce improved quality water which is crucial in the context of (potable) water reuse2 (Figure 5).

Figure 5: Example of integration of OMBR in potable water reuse treatment train

However, first tests demonstrated that salinity build-up occurred in the submerged OMBR tank affecting the biodegradation efficiency3and therefore additional UF 4 or MF 5 system were implemented to allow for stable operation. As an alternative, it is proposed here to evaluate the opportunity to (partially) retrofit existing MBR into OMBR. Such configuration has the advantages of (1) using existing MBR installation, (2) flexibility/reversibility of operation in MBR/OMBR modes to fit with (seasonal) water quality needs, (3) limiting the number of membrane stacks to operate and their associated piloting systems. However, apart from the experimental validation, such implementations requires the development of OMBR/FO module similar to MBR/UF ones and similar permeation OMBR/MBR permeation flux to avoid increased filtration surface area.

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THEME: MEMBRANE BIOREACTORS

Thus, OMBR plate design were first developed based on Kubota cartridge 203 design and using new generation of thin film composite FO membrane. Initial extended validation of optimized design and operation for OMBR plates were realized. The impact of draw channel spacers, cross flow velocity, pumping in pulsion or suction and draw solution concentration on water and salt fluxes and module robustness were evaluated. Then, pilot tests were conducted using a 50L MBR/OMBR pilot for two months. The system was seeded with sludge from a wastewater treatment plant and fed with synthetic wastewater (hydraulic retention time of 1 day and sludge retention time of 30 days). Concentration of the mixed liquor was maintained at 8g.L-1. The pilot consists in two 25L tanks (anoxic/ aerobic) with a recirculation loop. Aeration was provided in the aerobic tank below the membranes stack to act also as air scouring. The system was operated with 3 membrane plates, either MF plate or combination of MF and FO plates. Overall, those tests allowed for (1) comparison of MBR and OMBR in terms of water flux, membrane fouling, (2) evaluation of OMBR/MBR process stability with regards to salinity build up, membrane degradation, depuration performance. The optimized plate design consisted in a U-shape draw circulation channel similar to those observed in spiral wound FO module with mesh spacer to allow for water circulation in the draw channel. First tests demonstrated that it is preferable to operate the draw circulation by placing the pump in suction and with a minimum cross flow velocity of 100rpm. Despite some significant lower flux than in cross flow cell configuration, it has been possible to obtain water flux up to 17 L.m-2.h-1 (Figure 6a) using Porifera membrane, confirming the potential of commercial TFC membrane to overcome former FO flux limitations. Initial validation tests were performed within the MBR/OMBR pilot reactor during 3 days and using 35 g.L-1 of sea salts as draw solution (a new draw solution was prepared every day). Despite combined MBR/OMBR operation allowing for salt bleeding via the MF membrane, salinity increase was observed in the reactor; however, it did not impact the depurative capacity of the biomass. Flux decrease by nearly 20% over the three days of OMBR operation (Figure 6b, when comparing initial flux for each day of operation) demonstrated significant fouling. However the fouling layer was completely removed after 1 hour of osmotic backwashing allowing for sustainable operation with limited cleaning. Following these initial observations, long term pilot scale operation using two different types of commercial TFC membranes (Porifera and Toray) were performed; those results will also be presented.

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Figure 6: (a) Impact of draw solution cross flow velocity and concentration on permeation flux and (b) water flux evolution during 3 days of operation within OMBR reactor with draw solution at 35g.L-1 sea salts, new draw solution prepare every day (Porifera membrane, draw circulation operated in suction) REFERENCES 1

Holloway, R. W.; Achilli, A.; Cath, T. Y. Environmental Science: Water Research & Technology 2015, 1, 581.

2

Lutchmiah, K.; Verliefde, A. R. D.; Roest, K.; Rietveld, L. C.; Cornelissen, E. R. Water Research 2014, 58, 179.

3

Yap, W. J.; Zhang, J.; Lay, W. C. L.; Cao, B.; Fane, A. G.; Liu, Y. Bioresource Technology 2012, 122, 217.

4

Holloway, R. W.; Wait, A. S.; Fernandes da Silva, A.; Herron, J.; Schutter, M. D.; Lampi, K.; Cath, T. Y. Desalination 2015, 363, 64.

5

Luo, W.; Hai, F. I.; Kang, J.; Price, W. E.; Nghiem, L. D.; Elimelech, M. Chemosphere 2015, 136, 125.

BLANDIN GAETAN Title: Marie Curie and TECNIOspring Postdoctoral fellow LEQUIA, Institute of the environment, University of Girona, Spain Phone: +34 618 804 214 E-mail: [email protected]

198

2007-2012

R&D engineer for water and sludge treatment applications at Lhoist R&D (Belgium)

2012-2015

Joint PhD at UNSW, Australia and Ghent university, Belgium (Assisted forward osmosis for energy savings in seawater desalination)

Oct 2015

Marie Curie and TECNIOspring Postdoctoral fellow (OMBReuse: Osmotic membrane bioreactor for water reuse



Research interests: forward osmosis, membrane separation, water reuse, desalination

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE BIOREACTORS

T3.16 WENHAI LUO CONTROLLING SALINITY BUILD-UP IN OSMOTIC MEMBRANE BIOREACTORS

WENHAI LUO1, LONG NGHIEM1, WILLIAM PRICE2, FAISAL HAI1 1 Strategic Water Infrastructure Laboratory, School of Civil, Mining and Environmental Engineering, University of Wollongong, Wollongong, NSW 2522, Australia 2 Strategic Water Infrastructure Laboratory, School of Chemistry, University of Wollongong, Wollongong, NSW By integrating forward osmosis (FO), an osmotically pressure-driven membrane process, with conventional activated sludge treatment, osmotic membrane bioreactor (OMBR) can potentially be a low fouling alternative to traditional membrane bioreactor (MBR) systems.1 Moreover, due to the high separation capacity of FO in comparison with microfiltration (MF) or ultrafiltration used in conventional MBR, OMBR can effectively remove a broad range of contaminants, including emerging chemicals of significant concern, such as pharmaceutically active and endocrine disrupting compounds.2, 3 Nevertheless, several technical challenges, particularly salinity build-up in the bioreactor, need to be addressed for further development of OMBR. Salinity build-up in the bioreactor due to the reverse draw solute flux and the high rejection of salts by the FO membrane can result in several negative effects, mainly including flux decline, aggravated membrane fouling, and inhibition of biomass activity.4 We have successfully developed two techniques to mitigate salinity build-up during OMBR operation. They involve the use of ionic organic draw solutes and periodic salinity extraction by an MF membrane. Subsequently, we demonstrate the application of OMBR for phosphorus recovery from wastewater. Our results show that at the same osmotic pressure, ionic organic draw solutions, such as sodium acetate (NaOAc) and ethylene-diamine-tetra acetic acid disodium salt (EDTA-2Na), significantly reduced salinity build- up in the bioreactor in comparison with sodium chloride (NaCl) during OMBR operation (Figure 1). This observation is attributed to the lower reverse salt fluxes of these two ionic organic draw solutes due to their larger molecular weights and thus smaller diffusion coefficients compared to NaCl. In addition, the reverse diffusion of these draw solutes considerably affected the membrane fouling behaviour as well as the biological performance by altering biomass characteristics.

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Figure 1: Mixed liquor conductivity during OMBR operation with each draw solute at a solution osmotic pressure of 23 bar. Experimental conditions: draw solution cross-flow velocity = 2.8 cm/s; DO = 5 mg/L; initial MLSS = 5 g/L; initial HRT = 33 – 43 h; temperature = 22 ± 1 ºC.

Salinity build-up during OMBR operation could also be effectively controlled by periodic salt extraction through the MF membrane (Figure 2). As a result, sustainable and stable OMBR operation could be achieved with excellent wastewater treatment performance. More importantly, phosphorus retained in the bioreactor by the FO membrane could be recovered from the MF permeate via precipitation. Our results indicate that precipitates obtained by simply adjusting the MF permeate pH to 10 contained 15 – 20% (wt/wt) of phosphorus (Figure 3).

Figure 2: Mixed liquor conductivity during OMBR operation with periodic MF extraction. OMBR was run in a cycle of 8 d on and 2 d off. MF was operated for 1 d to extract 3 L water from the bioreactor for phosphorus recovery during OMBR off time. The bioreactor was then replenished with 3 L sewage and aerated for 1 d before a new OMBR operational cycle.

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Figure 3: Major elements in the precipitates obtained from the MF permeate, extracted periodically from the OMBR mixed liquor, at pH 10. Error bars represent standard deviation from duplicate measurements. REFERENCES 1 A. Achilli, T. Y. Cath, E. A. Marchand, A. E. Childress, Desalination 2009, 239 (1), 10-21. 2 R. W. Holloway, J. Regnery, L. D. Nghiem, T. Y. Cath, Environ. Sci. Technol. 2014, 48 (18), 10859-10868. 3 A. A. Alturki, J. McDonald, S. J. Khan, F. I. Hai, W. E. Price, L. D. Nghiem, Bioresour. Technol. 2012, 113, 201-206. 4 W. Luo, F. I. Hai, W. E. Price, W. Guo, H. H. Ngo, K. Yamamoto, L. D. Nghiem, Bioresour. Technol. 2014, 167,

WENHAI LUO PhD candidate University of Wollongong, Australia Phone: 61 451 882 050 E-mail: [email protected] Since 2013

University of Wollongong, NSW, Australia

2011 – 2013

China Agricultural University, Beijing, China M.Eng.

PhD candidate

2007 – 2011

Changchun Normal University, Jilin, China B.Sc.

Research interests: Wastewater treatment and reuse by osmotic membrane bioreactors

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T3.17 DR. LI-HUA CHENG FORWARD OSMOSIS PROCESS FOR MICROALGAE SEPARATION FROM WATER

DR. LI-HUA CHENG1, ZHI-YI NI1, YU-PENG GONG1, WEN-ZHE FANG1, DR. XIN-HUA XU1 1 College of Environmental and Resource Science, Zhejiang University, Hangzhou, 310058, China 2 Engineering Research Center of Membrane & Water Treatment Technology, Ministry of Education, Hangzhou, 310027, China. The process of forward osmosis, characterized in low-energy consumption and low membrane fouling, has been increasingly penetrated into the field of microalgae separation from water [1]. In this work, the permeate flux of microalgae is found not decreased with the increase of biomass density (Fig. 1(a)). To understand the effect of microalgae growth on separation of biomass from water, the chemical composition, Zeta potential, and secretion of extracellular polymeric substances (EPS) of Chlorella vulgaris cultured in the secondary water, are fully characterized during the whole period of cell growth. The results show that the polysaccharide content in the soluble EPS (SEPS) are the highest for those in adaptation growth phase, enabling that the water flux decline is the highest (Fig. 1(b)). The consistent increase of negative zeta potential of cell increases the stability of microalgae-water system, and the possible reduced reverse diffusion due to the initial inner membrane fouling allows that the water flux of biomass at exponential growth is higher even than the baseline with only the culture medium [2]. The increase of cell density together with the variation of cell composition then allows the slightly lower permeate flux for microalgae growth at plateau phase than that during exponential growth phase, but still higher than the baseline. This work is endeavored to propel the integration of forward osmosis with traditional field of microalgae separation from water.

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Figure 1. Effect of microalgal growth phase on (a) the water flux of forward osmosis and (b) their EPS content 1

P. Praveen, K.-C. Loh, Bioresour. Technol. 2016, 206, 180–187

2

M. Xie, E. Bar-Zeev, S. M. Hashmi, L. D. Nghiem, M. Elimelech, Environ. Sci. Technol.2015, 49, 13222-13229

LI-HUA CHENG Associate Professor Zhejiang University, P.R. China Phone: +86-571-88982025 Fax: +86-571-88982025 E-mail: [email protected] 2001-2006

PhD student, Biochemical Engineering, Zhejiang University, China

2006-2009

PostDoc, Chung-Yuan Christian University, Taiwan

Since 2009

Associate Professor, Zhejiang University, China

Research interests: Microalgal Bioenergy; Water treatment by membrane processes;CO2 capture and utilization; Novel membrane and membrane bioreactors for environmental and energy problems.

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T3.18 EXTERNAL OSMOTIC MEMBRANE BIOREACTOR OPERATED WITH A NOVEL MEMBRANE

MURAT EYVAZ1, TAHA ASLAN2,4, SERKAN ARSLAN1, AYŞE YÜKSEKDAĞ3,4, MURAT DÜNDAR2, DERYA IMER3,4, EBUBEKIR YÜKSEL1, İSMAIL KOYUNCU3,4 1 Department of Environmental Engineering, Gebze Technical University, 41400, Cayirova, Kocaeli, Turkey. 2 Department of Environmental Engineering, Bartın University, 74100, Bartın, Turkey. 3 Department of Environmental Engineering, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey. 4 National Research Center on Membrane Technologies, Istanbul Technical University, 34469, Maslak, Istanbul, Turkey This study reports the short term operation of an osmotic membrane bioreactor (OMBR) integrated with a reverse osmosis (RO) system for municipal wastewater treatment. For this purpose, a novel forward osmosis (FO) tubular nanofiber membrane [1] was fabricated by interfacial polymerization method and operated in external OMBR. The membrane exhibited high water flux (average 55 LMH) and low reverse salt flux (0.36 GMH). Sodium chloride solution (0,5 Molar) was employed as draw solution at the beginning of the system. Afterwards, concentrate of the RO was recirculated as draw solution to osmotic membrane. OMBR combined with RO was operated with the concept of zero liquid discharge (ZLD) during the operation period of 90 days. Removal efficiencies for chemical oxygen demand (COD), total phosphorus (TP) and total nitrogen (TN) were obtained as about 99.5%, 99.2% and 96.3 % respectively. EXPERIMENTAL

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The support layer of novel tubular osmotic membrane used in this study was fabricated from polyacrylonitrile by electrospinning method coated on hollow braided rope. Polyamide thin film was coated on support layer with interfacial polymerization method. FO membrane was operated in external system as given in Figure 1. The FO membrane was operated in active layer facing feed solution (AL-FS) mode. The permeate of UF membrane submerged into the bioreactor was sent to FO membrane as feed solution. After startup of system with NaCI solution, the concentrate of RO was used as draw solution by recirculating at the rest of the operation. TN, TP, nitrate and nitrite nitrogen were regularly measured by using Hach-Lange DR5000 UV-spectrophotometer. Mixed liquor suspended solids (MLSS) and mixed liquor volatile suspended solids (MLVSS), COD, specific oxygen uptake rate (SOUR) were analyzed in accordance with standard methods [2]. Conductivity, dissolved oxygen, temperature and pH were also measured and recorded (Hach-Lange HQ40d). 9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE BIOREACTORS

Fig. 1. Schematic illustration of the external OMBR RESULTS AND DISCUSSION

During 90 days operation time, MLVSS and MLSS were maintained as about 6500 and 10000, respectively. High COD removal efficiencies at different sludge retention times (SRT 15, SRT 30, SRT 45) were achieved. The nutrient removals were measured as 96,3% and 99,2% for TN and TP, respectively (see Table 1). Nitrate concentrations in UF permeate ranging between 40-50 mg/L means that the complete nitrification in bioreactor was maintained during the study. Water fluxes of FO membrane varied between 50 and 100 LMH. The high FO water fluxes were resulted from the hydrodynamic conditions and superior properties of the tubular nanofiber membrane structure.2 Table 1. Performance of the OMBR+RO system

Parameters

Feed Water

UF Permeate

RO Permeate

Total N (mg/ L)

55±5

49±3

2,2±0,5

Total Phosphorus (mg/ L)

14±0,5

7,5±0,5

<0,1

COD (mg/L)

1100±80

35±10

5±2

CONCLUSION

As a conclusion, forward osmosis membrane in external configuration showed a lower membrane fouling propensity due to the fact that OMBR operates at virtually zero or very low hydraulic pressure. Moreover, concentrate management of the reverse osmosis in this study was carried out successfully and zero liquid discharge was achieved for whole system. Reverse osmosis membrane life was extended with external OMBR compared to conventional MBR combined with RO system.

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ACKNOWLEDGEMENT

This work was supported by the Scientific and Technological Research Council of Turkey (TÜBİTAK), Grant No: ÇAYDAG-113Y340 REFERENCES 1

Arslan, S., Aslan, T., Eyvaz M., Güçlü S., Yüksekdağ A., Yuksel, E., Koyuncu, İ., A Novel High Performance Tubular Nanofiber Supported Forward Osmosis (TuNFO) Membrane, unpublished.

2

APHA (1995) Standard methods for the examination of water and wastewater. 19th edn. American Public Health Association, Baltimore, MD

RES. ASST. MURAT EYVAZ Title: PhD Affiliation, Country: Gebze Technical University, TURKEY Phone: +90 (262) 605-3223 Fax: +90 (262) 605-3145 E-mail: [email protected] 2004

Bachelor Degree (Kocaeli University- Environmental Eng.)

2006

Master’s Degree (Gebze Institute of TechnologyEnvironmental Eng.)

2013

Doctor of Philosophy (Gebze Institute of TechnologyEnvironmental Eng.)

Research interests: Wastewater treatment, Forward osmosis membrane, Nanofiber membranes, Osmotic MBRs

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T3.19 RECEP KAYA VIBRATORY SHEAR ENHANCED SYSTEMS IN LAB-SCALE MBR

RECEP KAYA1, NILÜFER TIROL2, HALE ÖZGÜN1, MUSTAFA EVREN ERŞAHIN1, OSMAN ATILLA ARIKAN1, NEVZAT ÖZGÜ YIĞIT3, MEHMET KITIŞ3, İSMAIL KOYUNCU1 1 Istanbul Technical University, Faculty of Civil Engineering, Environmental Engineering Department, Istanbul 2 Istanbul Technical University, Graduate School of Science Engineering and Technology, Environmental Sciences And Engineering Graduate Program, Istanbul 3 Suleyman Demirel University, Faculty of Engineering, Environmental Engineering Department, Isparta Submerged membrane bioreactor (MBR) systems are widely used in wastewater treatment systems and water reuse applications. However, membrane fouling remains a critical issue that limits the performance of MBRs. Increasing the shear stress at the membrane surface using air sparging and crossflow and membrane cleaning with permeate backwash are frequently used in order to reduce membrane fouling. However, the application of these fouling mitigation approaches in the field is often limited due to high costs1. Mostly, air sparging is used in MBR systems in order to reduce membrane fouling. However, air sparging provides only limited flux improvement and may correspond to 70% of the total energy cost of MBR operation2. Thus, there is a clear need for a fouling control strategy that is both efficient and cost-effective. Vibratory shear enhancement (VSE) technology can show promising results in this field. A salient example of the application of vibratory motion to membrane surface is the vibratory shear enhanced processing (VSEP) technology introduced by Armando et al.2 The magnetically induced membrane vibration (MMV) system, first introduced by Bilad et al.3, is another type of VSE. The MMV system includes a magnetically induced vibration engine, which is controlled by a driver device with an audio software. The objective of this study is to investigate the performance of different vibration types. Two different vibratory MBR modules were designed to compare the effect of vibration type on TMP profiles. One is mechanically vibrated and the other is magnetically vibrated module. Non-vibrated module is also included in the system as a control module. The vibratory systems are operated by using mechanical vibratory motors and magnetically induced vibration drivers. Each system consisted two drivers and motors. It is observed that filtration performances as TMP profiles changed dramatically for each MBR modules on the lab-scale experiments based on the vibration system used. Treatment GOLD SPONSOR

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performances for all three membrane modules has not been changed during the long term study. ACKNOWLEDGEMENT

The authors would like to express their gratitude to the financial support granted by The Scientific and Technological Research Council of Turkey (TÜBİTAK) Project No: 113Y341. REFERENCES 1

Judd S.J., The MBR Book: Principles and Applications of Membrane Bioreactors in Water and Wastewater Treatment. 2006 Elsevier, Oxford, UK.

2 A.D. Armando, B. Culkin, D.B. Purchas, New separation system extends the use of membranes, in: Proceedings of Euromembrane 1992, vol. 6, p. 459. 3 Bilad Muhammed R., Gergo Mezohegyi , Priscilla Declerck, Ivo F.J. Vankelecom, Novel magnetically induced membrane vibration (MMV) for fouling control in membrane bioreactors, Water Research, 2012, 46, 6372.

RECEP KAYA Title: PhD Candidate, Research Assistant Istanbul Technical University, Turkey: Phone: +905064116191 Fax: +2122853473 E-mail: [email protected] 2006-2010

Sakarya Uni. Bachelor

2010-2012

Istanbul Technical Uni. MSc.

Since 2012

Istanbul Technical Uni. PhD

Research interests: membrane, module, membrane bioreactor, desalination, CFD : Waste water management using membrane and catalysis

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THEME: MEMBRANE BIOREACTORS

TH3.2 DAVID C. STUCKEY EFFECT OF SALINITY ON THE CHARACTERISTICS OF SOLUBLE MICROBIAL PRODUCTS (SMP) AND MEMBRANE FOULING

LIN CHEN1, HUI CHIN TAN 1, DAVID C. STUCKEY1, 2 1 Advanced Environmental Biotechnology Centre, Nanyang Technological University, Singapore, [email protected], [email protected] 2 Corresponding author, Department of Chemical Engineering, Imperial College London, UK, [email protected] Abstract: Soluble microbial products from an anaerobic membrane bioreactor under different salinities was characterized and examined with respect to its role in membrane fouling. The carbohydrate content seemed to be little affected by salinity, and was present in the range of 4.0 - 5.7 mg/L as the salinity increased from 0.5 g/L to 15.0 g/L. In contrast, the presence of higher salinity caused a greater accumulation of proteins, from 17.8 mg/L at a salinity of 0.5 g/L to 42.3 mg/L at a salinity of 15.0 g/L. Results from excitation-emission matrix (EEM) spectra analysis revealed that the fluorophores associated with humic-like material were dominant in the spectra of all samples, and an increase in the salinity enhanced the accumulation of tryptophan and tryptophan-like proteins. Additionally, elevated salinity aggravated SMP fouling by increasing solution ionic strength, which might have led to a higher supersaturation index, and double layer compression. Keywords: Anaerobic membrane bioreactor; characterization; fouling; salinity; Soluble microbial products. INTRODUCTION

Anaerobic membrane bioreactors (AnMBRs) have recently received considerable attention, due to their low sludge production and long-term sustainability with regards to net energy gains1. To alleviate freshwater shortages, seawater has been used increasingly as a substitute for freshwater for sewage2, leading to high salinity wastewaters and increasing treatment difficulties; essentially, the change in salinity disturbs or alters microbial metabolism. Soluble microbial products (SMPs) have been found to constitute the majority of the effluent, and the key component responsible for long-term membrane fouling3. However, very few studies have investigated the characteristics of SMPs in AnMBRs under conditions of increasing salinity. Therefore, the aim of this research was to further explore the effect of salinity on SMP characteristics, focusing mainly on its chemical constituents. Fouling was further described by interaction energy in order to obtain a deeper understanding of the fouling mechanism. MATERIALS AND METHODS

A laboratory-scale AnMBR fed with synthetic municipal wastewater was operated at 35 oC, and NaCl stock solution was added to yield different levels of salinity ranging from 0.5 GOLD SPONSOR

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to 15 g/L. Analysis of SMPs in the biomass was carried out after 0.45 μm membrane filtration, and included the carbonate/protein concentrations, UV254, UV spectral slope (S), and a three-dimensional excitation-emission matrix (EEM) spectra. Membrane filtration tests were conducted using a stirred filtration cell with constant pressure and declining flux. RESULTS AND CONCLUSIONS

Concentration changes of SMPs with salinity. The variations in carbohydrate and protein composition with salinity are shown in Figure 1(a). Proteins appeared to be more sensitive to salinity change, while carbohydrates only fluctuated slightly throughout this study. The protein content increased from 17.8 to 42.3 mg/L as salinity increased from 0.5 to 15.0 g/L, while the carbohydrate kept relatively stable, and the standard deviation was 0.5 mg/L with an average of 4.7 mg/L. The humic substances characterized by UV254 also increased from 0.087 to 0.352 cm-1, (Figure 2(b)). The S values were in the range of 0.136 - 0.169 (Figure 1(c)), and the slight increase in S indicated that the ratio of fulvic to humic acids might decrease with salinity. Noticeably, when the salinity of the bulk phase decreased to around 0.5 g/L, the protein, carbohydrates and humic acids also returned to their original levels. Fluorescent characteristics of SMP. The EEM spectra of SMP under different salinities are shown in Figure 2(a-d). EEM fingerprints showed that the fluorophores associated with humic-like material were dominant in the spectra of all the samples. Additionally, less distinct peaks were assigned to protein-like and fulvic components. In order to further demonstrate the compositional changes of SMPs with salinity, the fluorescence regional integration method was used to analyze the six excitation–emission regions. The majority of proteins in the SMPs existed in the form of tryptophan and tryptophan-like proteins which accounted for more than 49.2%, whereas the combination of tyrosine and tyrosine-like proteins only accounted for less than 9.3%. Fulvic acid-like substances reduced from 25.0% to 21.7% with increasing salinity, while the humic acid-like substances increased from 14.6% to 21.7%, which was in agreement with the calculation of spectral slop.

Figure 1 (a) Variations of carbohydrate and protein content; (b) changes of UV254 against operation time, and (c) UV spectral slope (S) against salinity.

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Figure 2. EEM spectra of SMP (a) salinity = 3.2 g/L; (b) 8.0 g/L; (c) 12.0 g/L and (d) 15.2 g/L;

(e) Variation of flux during filtration of SMPs at different salinity. J stands for flux and J0 for the initial flux. Flux performance of SMPs with salinity. The flux variations of SMPs at different salinities are illustrated in Figure 2(e). The SMPs with higher salinity exhibited higher flux decreases, which can be understood from the DLVO theory. With increasing salt concentration, the Debye length is reduced, which is known as double layer compression, thus particles can come closer resulting in agglomeration as they became destabilized, and this effect was more pronounced at higher salt levels. REFERENCES 1

Stuckey, D.C. (2012), Recent developments in anaerobic membrane reactors. Bioresource Technol. 122, 137-148.

2

Li, Y., Li, A.-M., Xu, J., Li, W.-W. and Yu, H.-Q. (2013), Formation of soluble microbial products (SMP) by activated sludge at various salinities. Biodegradation 24(1), 69-78.

3

Jarusutthirak, C. and Amy, G. (2006), Role of soluble microbial products (SMP) in membrane fouling and flux decline. Environ. Sci. Technol. 40(3), 969-974.

DAVID STUCKEY Title: Professor Affiliation, Country: NEWRI, NTU Singapore, and Imperial College London, UK E-mail: [email protected]

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TH3.3 SHENG LI BIO-METHANE PRODUCTION VARIATION UNDER DIFFERENT DRAW SOLUTE REVERSE DIFFUSIONS IN AN ANAEROBIC DIGESTER SIMULATED FOR FOANMBR

SHENG LI 1, YOUNGJIN KIM2,3, SHERUB PHUNTSHO2, HO KYONG SHON2, TOROVE LEIKNES1, NOREDDINE GHAFFOUR1 1 King Abdullah University of Science and Technology (KAUST), Water Desalination and Reuse Center (WDRC), Biological and Environmental Sciences & Engineering Division (BESE), Thuwal, 23955-6900, Saudi Arabia 2 School of Civil and Environmental Engineering, University of Technology, Sydney (UTS), Post Box 129, Broadway, NSW 2007, Australia 3 School of Civil, Environmental and Architectural Engineering, Korea University, 1-5 Ga, Anam-Dong, Seongbuk-Gu, Seoul, 136-713, Republic of Korea Lately, fertilizer-drawn forward osmosis (FDFO) has received increased interest since the diluted draw solution can be used directly for irrigation purposes and therefore no recovery process is required 1, 2. In FDFO, the FO process was driven by fertilizers (draw solution) and thus the treated water drawn from the wastewater (FO feed) is used to dilute the fertilizer solution which can then be directly used for fertigation. By combining FDFO and anaerobic membrane bioreactor (AnMBR), users can have multiple benefits, namely bio-methane production, higher effluent quality than ultrafiltration based AnMBR systems and direct fertigation. Different fertilizers have been compared in terms of water flux, bio-methane production rate and reverse diffusion 3. However, it is still not clear why different fertilizers exhibited different bio-methane production rates. It could be related to the bacteria community variation caused by different reverse diffusion rates of different fertilizers, but there is no substantial proof to support this hypothesis. This study was conducted to investigate the relationship among the reverse diffusion of fertilizer draw solute, bacteria community and bio-methane production rate in the FDFO-AnMBR system. Three fertilizers were evaluated in this study, namely KCl, KNO3 and KH2PO4. The fertilizer reverse diffusion was determined in a FO setup for all three fertilizers first. Secondly, the corresponding amount of fertilizer was spiked in bottles with 700 ml anaerobic sludge each collected from an anaerobic digester in Sydney. Anaerobic sludge with different fertilizer addition was incubated at 35℃ for 20 days. The bio-methane production was continuously monitored during the whole experiment. After the 20 days incubation, the sludge with different fertilizers was sampled for DNA extraction and 454 pyrosequencing. Results showed that all three fertilizers exhibited different reverse diffusion. KH2PO4 showed the lowest reverse diffusion of 0.8 mMol, while KCl and KNO3 were 4.9 and 19.6 mMol,

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respectively. Interestingly, bio-methane production displayed an opposite order. KH2PO4 showed the highest bio-methane production which was comparable with the blank control (anaerobic sludge without fertilizer added), followed by KCl and KNO3. The pyrosequencing results revealed that bacteria communities of different fertilizers were clearly different from each other. The bacteria community of sludge with KH2PO4 added was very similar to the blank control. The sludge with KCl exhibited a higher similarity to the sludge with KH2PO4 than KNO3. Within the sludge of blank control and KH2PO4, the percentage of five methane production bacteria species was higher than the sludge of KCl and KNO3. These five species are Bacteroidetes: proteiniphilum, Bacteroidetes:f_009E01-B-SD-P15, Firmicutes: Trichococcus, Proteobacteria: Syntrophorhabdus, and Spirochaetae: f_spirochaetaceae. On the other hand, the nitrogen gas production species (Proteobacteria: Comamonas) was found to have a higher percentage (1.2) than the sludge with other fertilizers (0). REFERENCES 1. Phuntsho, S.; Shon, H. K.; Hong, S.; Lee, S.; Vigneswaran, S., A novel low energy fertilizer driven forward osmosis desalination for direct fertigation: Evaluating the performance of fertilizer draw solutions. Journal of Membrane Science 2011, 375, (1-2), 172-181. 2. Phuntsho, S.; Shon, H. K.; Majeed, T.; El Saliby, I.; Vigneswaran, S.; Kandasamy, J.; Hong, S.; Lee, S., Blended fertilizers as draw solutions for fertilizer-drawn forward osmosis desalination. Environmental Science and Technology 2012, 46, (8), 4567-4575. 3. Kim, Y.; Chekli, L.; Shim, W.-G.; Phuntsho, S.; Li, S.; Ghaffour, N.; Leiknes, T.; Shon, H. K., Selection of suitable fertilizer draw solute for a novel fertilizer-drawn forward osmosis–anaerobic membrane bioreactor hybrid system. Bioresour. Technol.

NAME SHENG LI Title: Dr King Abdullah University of Science and Technology (KAUST) Phone: +966 12 8084919 Fax: +xxx E-mail: [email protected] 1999-2003

Anhui University of Technology, China

2006-2011

Delft University of Technology, Netherlands

Since 2012

King Abdullah University of Science and Technology, Saudi Arabia

Research interests: membrane fouling, desalination, wastewater reuse. Forward osmosis and membrane distillation.

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TH3.4 CHUN HENG LOH THIN FILM COMPOSITE HOLLOW FIBER MEMBRANES FOR EXTRACTIVE MEMBRANE BIORACTOR

CHUN HENG LOH1, RONG WANG1,2 1 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Ceantech Loop, Singapore 637141, Singapore 2 School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore Extractive membrane bioreactor (EMBR) is a novel wastewater treatment process combining aqueous-aqueous extractive membrane process and bio-augmentation1. In EMBR, target organic pollutants transport through a non-porous membrane from the feed solution to the receiving solution by solution-diffusion mechanism, driven by the concentration gradient across the membrane; the organic pollutants are then biodegraded by specific microorganisms at the receiving side. Since the bioreactor and the wastewater are separated by the membrane, the harsh conditions in the wastewater have little impact on the microorganisms in the bioreactor. This enables treatment of bio-inhibitory wastewater without the need for pretreatment. The membranes used in EMBR process should have high organic flux while effectively impermeable to inorganics and water. In most of the previously reported studies on EMBR, commercial silicon rubber tubes were used as the membranes for phenol extraction1,2. They suffered from low organic flux due to their large thickness (> 0.2 mm), and thus limited the feasibility of removing phenol via EMBR. In this work, composite membranes prepared by coating polydimethylsiloxane (PDMS) on the lumen surface of polyetherimide (PEI) and polyvinylidene fluoride (PVDF) hollow fiber substrates were developed for EMBR process. The prepared membranes were characterized using aqueous-aqueous extractive process to determine its extraction efficiency for phenol, followed by operation in EMBR. To study the effects of PDMS intrusion on phenol transfer, coating conditions were varied to achieve different levels of PDMS intrusion. Based on silicon distribution measured by EDX as shown in Fig.1, PDMS has fully penetrated into the substrate for PEI-1. For PEI-2, silicon was found only near the membrane coating surface, demonstrating a partial PDMS intrusion. The overall mass transfer coefficient, ko, of the developed membranes and commercial silicon tubing is listed in Table 1. Due to the much thicker PDMS coating, ko is significantly lower when PDMS is completely penetrated into the substrate. Therefore, PDMS intrusion should be minimized to enhance ko. As shown in Table 1, all of the composite membranes developed in this work showed ko of at least an magnitude higher than the commercial silicon tubing, demonstrating the low mass transfer resistance imposed by the thin film composite membranes.

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Figure 1. Cross-sectional images and Si distribution of composite membranes PEI-1 & PEI-2 Table 1. ko of developed membranes & commercial silicon tubing

Membrane

PDMS intrusion

ko (x 10-7 m/s)a

PEI-1

Complete

15.3

PEI-2

Partial

34.2

PVDF

Partial

23.3

Silex (Commercial silicon tubing)

N.A.

1.0

a ko was tested using a cross-flow configuration (feed solution: 1000 mg/L phenol, 50 g/L NaCl, pH = 0 or 2) (Receiving solution: deionised water)

Stability test under harsh conditions (pH 0 or 2) for over 7 days indicates that high acid content at low pH=0 may have resulted in some defects in the PEI composite membrane while PVDF composite membranes showed good integrity even at pH=0. In terms of mechanical properties, PEI exhibited higher tensile strength but lower elongation at break compared with PVDF. The good ductility, as well as the better chemical resistance of PVDF, might be beneficial for long term operation in submerged EMBR where vigorous air bubbling and occasional cleaning will be applied to control biofilm attachment on the membrane surface. To study the effects of substrate materials on EMBR performance, both PEI and PVDF composite hollow fiber membranes were tested in cross-flow EMBR for about 2 weeks. A feed solution containing 1000 mg/L of phenol and 5 g/L of NaCl was circulated through the lumen side of hollow fibers. The bioreactor contained sludge, which had been acclimated to 750 ppm phenol, and essential inorganic nutrients. As shown in Fig.2 (a), PEI membranes showed a more significant drop in ko despite its higher initial value. Autopsy results in Fig.2 (b) indicate that there was more biomass covered on the PEI membrane GOLD SPONSOR

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surface compared with PVDF, thus resulting in the higher ko drop. Study on the mechanism for biofilm attachment on the surface of different membrane materials is ongoing. Different aspects such as hydrophobicity, partition coefficient, surface roughness, and zeta potential of the membranes are considered.

(b)

(a)

Figure 2. Overall mass transfer coefficient (a) and biomass coverage on membrane surface (b) for PEI and PVDF composite membranes

In conclusion, the developed thin film composite membranes have significantly higher ko compared with commercial silicon tubing due to their much thinner selective layer. The choice of substrate materials demonstrated significant influence on the EMBR performance, which requires further study. REFERENCES 1 A.G. Livingston, Biotechnol. Bioeng. 1993, 41, 915-926 2 E.A.C. Emanuelsson, J.P. Arcangeli, A.G. Livingston, Water Res. 2003, 37, 1231-1238

LOH CHUN HENG Title: Research Fellow Nanyang Technological University, Singapore Phone: +65 98309445 Fax: +65 6791-0756 E-mail: [email protected] 2013-present

Research Fellow, Singapore Membrane Technology Centre, NTU

2009-2013

Ph.D. in Environmental Engineering, NTU

2005-2009

Bachelor of Engineering (Environmental Engineering), NTU

Research interests: Polymeric membrane fabrication, hollow fiber membranes, extractive membrane bioreactor

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TH3.5 CHINAGARN KUNACHEVA EFFECT OF OPERATING PARAMETERS ON SOLUBLE MICROBIAL PRODUCTS (SMPS) IN A SUBMERGED ANAEROBIC MEMBRANE BIOREACTOR

CHINAGARN KUNACHEVA1, YAN NI ANNIE SOH1, DAVID C. STUCKEY1 1 Advanced Environmental Biotechnology Center, Nanyang Environment & Water Research Institute, Nanyang Technological University, 1 Cleantech Loop, CleanTech One, Singapore 637141, Singapore Soluble microbial products (SMPs) are defined as the soluble organic products created from biological metabolism in wastewater treatment systems that are not known intermediates such as volatile fatty acids (VFAs) or incoming feed1. Their presence affects the performance of most biological treatment systems in terms of COD removal, and causes the fouling of membranes2. It has been noted over the years in both aerobic and anaerobic biological processes, that around 2% of the incoming feed COD is present in the effluent as SMPs3. However, under transient conditions including nutrient limitations, the presence of toxicants, or when the feed flow or composition is changed radically, the effluent SMPs can be as high as 17% of the influent COD4. This research aimed to understand the effect of different operating parameters (temperature and pH of the feed) on the production of SMPs and colloids in submerged anaerobic membrane bioreactors (SAMBR). MATERIALS AND METHOD

Two submerged anaerobic membrane bioreactors (SAMBR) had a working volume of 3 L. A microfiltration flatsheet membrane from Kubota was used. The surface area of the membrane was 0.116sq.m. with a nominal pore size of 0.2μm. The other reactor was an ultrafiltration hollow fibre membrane module (ZeeWeed, PVDF) from GE. The surface area of the membrane was 0.047sq.m. with a nominal pore size of 0.04μm. The fluxes of both membranes were maintained at 15 LMH. Recycle biogas was pumped through a stainless steel tube diffuser to generate coarse bubbles in order to mix the biomass in the reactor and clean the surface of the membrane, and the SAMBRs were operated at an HRT of 6 h. The reactor was continuously fed with a synthetic feed comprised of glucose, peptone, meat extract, and essential nutrients (COD = 466±35 mg/L). The SAMBR was fed at pH5 and pH11, and the temperature was set at 15, 25, and 35°C. The amount of SMPs is typically estimated by subtracting the COD due to intermediate VFAs and residual substrate, from the soluble effluent COD (Barker and Stuckey 1999). VFAs were measured using a Shimadzu high-performance liquid chromatography (HPLC, SPD-20AD) with a UV diode array detector (DAD, SPD-M20A) at 210 nm using an Aminex® HPX-87H (300×7.8mm) column. Size exclusion chromatography (SEC) was carried out using two columns (PolySep GFC-P1000 and 4000, Phenomenex) connected in series, and GOLD SPONSOR

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detection was performed using UV-DAD and refractive index (RI) detectors (Shimadzu). The composition of biogas (methane, oxygen, nitrogen, and carbon dioxide) from the SAMBR was determined using a Shimadzu GC-2010plus gas chromatograph with a thermal conductivity detector (TCD). MF and UF membranes were used to separate the colloid fractions and SMPs (>5μm, 1 – 5μm, 0.2 - 1μm, 100kDa - 1μm and <100kDa). The fouling potential for each fraction was estimated using a small flow cell (70 ml) to imitate a SAMBR. Organic compounds were extracted from samples using solid phase extraction (SPE) followed by liquid-liquid extraction (LLE): a Waters Oasis®HLB SPE cartridge was used for the initial extraction. The compounds were eluted with 2 mL of selected solvents (methanol, acetone, dichloromethane, n-hexane) in sequence into individual glass sample vials. The eluent from each SPE cartridge was collected and analysed separately. Samples which passed through the cartridge were collected and extracted using LLE. Mixtures of n-hexane, chloroform and dichloromethane were used for extraction. Eluted samples were then analysed using a GC-MS system (Shimadzu) with RTX®-5MS column. Mass spectra were acquired from m/z 30 to 580. The chromatographic peaks were identified using the NIST11 library (National Institute of Standards and Technology, Gaithersburg, MD, USA), and the compound was considered identified if the match percentage was higher than 80%. RESULTS AND DISCUSSION

The performance of the SAMBR decreased when fed with a pH 5 feed for 4 h. COD in the effluent increased from 7 to 17 mg/L. VFAs were not detected in the effluent sample, hence SMPs increased from 3% to 4% of the incoming feed COD. However, VFAs (acetate and butyrate) started to accumulate in the supernatant inside the SAMBR. The size distributions of the colloids and SMPs inside the reactor also changed dramatically; large MW compounds (MW<134,000 Da) increased significantly, while lower MW compounds (MW<194) decreased after the feed pH was decreased to 5 (Figure 1). The performance of the SAMBR was stable for 6h with the pH 11 feed, but then, the COD in the effluent rapidly increased to 420mg/L in 24h. Temperature (35°C to 25°C) did not affect the performance much of the SAMBRs, with their COD removals remaining stable at 97%. However, the COD in the effluent increased to 92±21mg/L (79%COD removal) when the SAMBR was operated at 15°C.

pH7

MW 134,300

pH 5 (RID)

pH5

MW 1,522,000

MW 194

Figure 1. Size exclusion chromatography of supernatant samples under pH 5 and 7.

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Figure 2. Fouling test of supernatant fractions (<100k, 100k – 0.2μm, 0.2μm – 1μm, 1μm – 5μm, and >5μm) under pH 5, 7, and 11 feed.

Figure 2 shows the fouling test of the supernatant fractions with the pH 5, 7 and 11 feeds. The results shows significant differences in the fouling behaviour of the fractions when we fed the SAMBR at different pHs. 53 low MW compounds (GC-MS) were identified after the pH change, and N-butyl benzenesulfonamide and cyclosulfer concentrations increased significantly. However, the membrane with the fouling layer inside the SAMBR could reject 86±7% of low MW compounds. ACKNOWLEDGMENT

This research grant was supported by the Singapore National Research Foundation under its Environmental & Water Technologies Strategic Research Programme and administered by the Environment & Water Industry Programme Office (EWI) of the PUB. REFERENCES 1 D.J. Barker, D.C. Stuckey, Water Research 1999, 33(14), 3063-3082. 2 S. Liang, C. Liu, L. Song, Water Research 2007, 41(1), 95-101. 3 S.F. Aquino, Imperial College of Science Technology and Medicine 2004. 4 P. Schiener, S. Nachaiyasit, D.C. Stuckey, Environmental Technology 1998, 19(4), 391-399.

CHINAGARN KUNACHEVA Title: Dr (Research fellow) Advanced Environmental Biotechnology Centre, Nanyang Environment & Water Research Institute, Nanyang Technological University Phone: +65-9863-2360 E-mail: [email protected] 2013-present: Research fellow (NTU) 2011-2012:

Assistant Professor (Kyoto University)

2009-2011:

Postdoctural researcher (Kyoto University)

Research interests: Anaerobic digestion, micropulltants, membrane, adsorption GOLD SPONSOR

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TH3.6 SYNERGY OF MICROBIAL QUORUM QUENCHING AND CHEMICALLY ENHANCED BACKWASHING FOR BIOFOULING CONTROL IN MEMBRANE BIOREACTORS

NUWAN A. WEERASEKARA1,2, KWANG-HO CHOO1, CHUNG-HAK LEE3 1 Department of Environmental Engineering, Kyungpook National University, 80 Daehak-ro, Buk-gu, 41566, Republic of Korea 2 Department of Engineering Technology, Faculty of Technology, University of Sri Jayewardenepura, Gangodawila, Nugegoda, 10250, Sri Lanka 3 School of Chemical and Biological Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, 08826, Republic of Korea Although membrane biofouling can be mitigated with various physicochemical approaches, it has been accepted as an unavoidable problem because biofilm formation can occur naturally in membrane bioreactors (MBRs) where substantive amounts of microbes are present. Recently, it was found that microbial quorum sensing resulting in biofouling can be well inhibited by enzymatic and bacterial destruction of signal molecules (quorum quenching (QQ))1,2. Signalling autoinducers (e.g., N-octanolyl-Lhomoserine lactone) were degraded via injection of lactonase and QQ bacteria (e.g., Rhodococcus sp. BH4) in various bio-carriers, which interrupted biofilm growth on submerged membranes substantially.3 QQ based biofouling control became much clearer when the aeration to scour the membrane or cyclic operation was less intensive. This was because biofouling became severer under mild hydrodynamic reactor operating conditions and thereby, QQ can eliminate such impacts more effectively.2 Normally, MBRs employ harsh maintenance cleaning strategies in real membrane plant operations, such as periodic chemical injection (e.g., NaOCl) for membrane cleaning. Chemically enhanced backwashing (CEB) with a high chlorine dose (e.g., >100 mg/L as Cl2) is one of the most common approaches in hollow fiber MBRs for real wastewater treatment plant designs and operations. Therefore, the focus of this research was to investigate whether the combination of QQ and CEB can create a synergistic effect on biofouling control in MBRs. The CEB with 100 mg/L as Cl2 was conducted once every day in addition to periodic permeate backwashing every 20 min for QQMBR. Membrane biofouling was substantially delayed with efficient disturbance of biofilms at the membrane when the two physicochemical (CEB) and biological (QQ) strategies were simultaneously applied (Fig. 1). The fouling fraction that cannot be controlled by CEB was controlled by QQ and vice versa. In summary, QQ had the synergy for biofouling control with CEB in hollow fiber MBRs.

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Fig. 1. Comparisons of transmembrane pressure build-up between CEB alone and QQ with CEB for membrane bioreactors. REFERENCES 1. Yeon, K.-M., Cheong, W.-S., Oh, H.-S., Lee, W.-N., Hwang, B.-K., Lee, C.-H., Beyenal, H., Lewandowski, Z., 2009. Quorum sensing: A new biofouling control paradigm in a membrane bioreactor for advanced wastewater treatment. Environ. Sci. Technol. 43(2), 380-385. 2. Weerasekara, N.A., Choo, K.-H., Lee, C.-H., 2014. Hybridization of physical cleaning and quorum quenching to minimize membrane biofouling and energy consumption in a membrane bioreactor. Water Res. 67, 1-10. 3. Lee, S.H., Lee, S., Lee, K., Nahm, C.H., Kwon, H., Oh, H.-S., Won, Y.-J., Choo, K.-H., Lee, C.-H., Park, P.-K., 2016. A More Efficient Media Design for Enhanced Biofouling Control in a Membrane Bioreactor: Quorum Quenching Bacteria Entrapping Hollow Cylinder. Environ. Sci. Technol.

KWANG-HO CHOO Title: Professor Department of Environmental Engineering, Kyungpook National University 80 Daehak-ro, Buk-gu, 41566, Republic of Korea Phone: +82-53-950-7585 Fax: +82-53-950-6579 E-mail: [email protected] 1996

Ph.D., Seoul National University, Korea

1997-1998

Post-Doc, University of Washington, Seattle

Since 2004

Professor at Kyungpook National University, Korea

Research interests: Membrane bioreactor, biofouling control, membrane catalysis, membrane adsorber

GOLD SPONSOR

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TH3.7 LAURA CHEKLI PERFORMANCE OF VARIOUS FERTILIZER DRAW SOLUTIONS IN A NOVEL HYBRID MICRO-FILTRATION FERTILIZER-DRAWN FORWARD OSMOSIS AEROBIC BIOREACTOR (MF-FDFO-MBR)

JIN WANG1,2, NIREN PATHAK1, LAURA CHEKLI1, SHERUB PHUNTSHO1, YOUNGJIN KIM1,3, SHENG LI4, NOREDDINE GHAFFOUR4, TOROVE LEIKNES4, HO KYONG SHON1 1 Centre for Technology in Water and Wastewater (CTWW), School of Civil and Environmental Engineering, University of Technology, Sydney (UTS), P.O. Box 123, 15 Broadway, NSW 2007, Australia 2 College of Environmental Science and Engineering, State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, Donghua University, Shanghai 201620, China 3 School of Civil, Environmental and Architectural Engineering, Korea University, 1-5 Ga, Anam-Dong, Seongbuk-Gu, Seoul, 136-713, Republic of Korea 4 King Abdullah University of Science and Technology (KAUST), Water Desalination and Reuse Center (WDRC), Division of Biological & Environmental Science & Engineering (BESE), Thuwal 23955-6900, Saudi Arabia INTRODUCTION

Diminishing freshwater resources due to the impacts of global warming, rapid industrialization and urbanization has prompted increased interest in indirect and direct potable reuse of impaired water1. Recently, the osmotic membrane bioreactor (OMBR) combining forward osmosis (FO) with activated sludge process has attracted growing interests in the field of wastewater treatment and reclamation2. OMBR can provide high rejection of contaminants and retain a significant portion of suspended solids but also has limitations such as salinity build-up (i.e. accumulation of dissolved salts), internal concentration polarization and recovery of diluted draw solution3. Therefore, fertilizerdrawn forward osmosis (FDFO) has attracted increased attention since the diluted draw solution can be used directly for irrigation purpose avoiding an energy-demanding recovery process. The main objective of this study was to compare different fertilizers as draw solution for the novel MF-FDFO-MBR hybrid system in terms of water flux and reverse salt flux. Also, the effect of various operating parameters (such as draw solution concentration, FO flow rate and MF flow rate) on the process performance was also studied.

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METHODS AND SET-UP

Fig. 1 shows the lab-scale submerged OMBR system with a side-stream MF membrane used in this study. The active volume of the bioreactor was 10 L. The FO membrane used in the experiments was provided by Hydration Technology Innovation (Albany, OR, USA) and was made of cellulose-based polymers with an embedded polyester mesh for mechanical strength with an effective membrane area of 0.024 m2. The in-house fabricated side stream PVDF MF membrane, having an effective area of 0.0754 m2, was employed for salinity control inside the reactor. All chemical fertilizers (ammonium sulphate (SOA), mono-ammonium phosphate (MAP) and potassium phosphate monobasic) used in this study were reagent grade (Sigma Aldrich, Australia) and were prepared at an initial concentration of 1M.

Figure 1. Flow diagram of the MF-FDFO-MBR hybrid system used in this study RESULTS AND DISCUSSION

Results presented in Fig. 2 show that the water flux for all of the draw solutions significantly declined in the initial stage (up to 48 hours), then remained fairly stable at 2-3 LMH for the next 2 days. NaCl exhibited the highest initial water flux (i.e. 7.7LMH) followed by SOA, KH2PO4 and MAP. However, the theoretical osmotic pressure of the different fertilizers showed a different trend compared to water flux. In fact, MAP has a higher osmotic pressure than KH2PO4.This difference in water flux between fertilizers could be explained from the variations of extent of internal concentration polarization (ICP) which will affect the effective osmotic pressure difference across the membrane4. Results in Fig. 2 also show that NaCl exhibited the highest specific reverse salt flux (SRSF) (i.e. 1.91 g/L) followed by MAP, SOA, KH2PO4, resulting in higher salinity build-up inside the bioreactor. This is because RSF is theoretically a function of the salt rejecting properties of the membrane characterized by the salt permeability coefficient (B value) which varies with different fertilizers5. For instance, the low SRSF values of SOA, KH2PO4 and MAP are most likely related to their low B parameters (i.e. 0.022, 0.029 and 0.024 kg.m2.h-1, GOLD SPONSOR

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respectively). A draw solution exhibiting a lower SRSF would be the preferred option for this hybrid MF-FDFO-MBR system since the accumulation of inorganic salt ions in the bioreactor could potentially inhibit the aerobic microbial activity3.

Figure 2. Water flux and reverse salt diffusion of different fertilizer draw solutions in the MF-FDFO-MBR hybrid system (DS concentration: 1M; Flow rate: 200mL/min, Temperature: 25oC) REFERENCES 1

F.R. Rijsberman, F.R, J. Agric. Water Manage. 2006, 80, 5-22

2 X.H. Wang, B. Yuan, Y. Chen, X. Li, Y. Ren, Bioresour. Technol. 2014, 167, 116-123 3 X. Wang, V.W.C. Chang, C.Y. Tang, J. Membr. Sci. 2016, 504, 113-132 4 J.R. McCutcheon, M. Elimelech, J. Membr. Sci. 2006, 284, 237-247 5 Y. Kim, S. Lee, H.K. Shon, S. Hong, Desalination. 2015, 355, 169-177

LAURA CHEKLI Title: Postdoctoral Research Associate University of Technology Sydney (UTS), Australia Phone: +61 405140445 E-mail: [email protected] 2010:

Master degree in Process Engineering (University of Technology Compiegne, France)

2010:

MSc in Environmental Water Management (Cranfield University, UK)

2015:

PhD in Environmental Engineering (University of Technology Sydney, Australia)

March 2015 till now: Postdoctoral Research Associate (UTS, Sydney, Australia) Research interests: Nanotechnologies and Membrane technologies for water treatment

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TH3.8 TIAN LI FOULING CONTROL OF SUBMERGED ANAEROBIC MEMBRANE BIOREACTORS WITH SANDWICH VIBRATORY-STIRRING (SVS) MEMBRANE MODULES

TIAN LI1, ADRIAN WING-KEUNG LAW1,2, ANTHONY G. FANE2,3 1 Environmental Process Modelling Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore 2 School of Civil and Environmental Engineering, Nanyang Technological University, Singapore 3 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore A submerged anaerobic membrane bioreactor (SAnMBR) combines a submerged membrane filtration unit and the anaerobic digestion process in one reactor to operate as a compact system. It has drawn considerable attention due to the advantages of high volumetric loading rate, small amount of sludge production, and high quality effluent. In addition, with the anaerobic digestion, methane gas can be produced which can serve as a renewable energy source to generate electricity or heat1. However, despite the advantages, problems associated with cake formation and membrane fouling are still hindering the development of SAnMBRs for wastewater treatment. For membrane fouling control, innovative systems using transverse vibration have been proposed in recent years to be viable alternatives that could effectively reduce membrane fouling. The transverse vibration not only produces shear stresses on the membrane surface that removes the foulant deposits, but also secondary flows and vortices that further enhance the shear rate in the vicinity of the membrane surface2. However, the sole use of transverse vibration cannot induce sufficient mixing of the bulk biosolids in an SAnMBR, which then leads to a progressive buildup of a dense sludge layer in the reactor that fouls the membrane over a long operating period. Therefore, additional mixing and stirring jointly with the membrane vibration is desirable to suspend the feed solution inside the reactor for fouling control. In this study, we introduced a novel design concept of a sandwich vibratory-stirring (SVS) membrane module, which incorporated a structural feature sandwiched amid a bundle of hollow fibre membranes. The rationale of the SVS configuration was to enable mixing and stirring of the reactor fluid by the structural feature, while simultaneously generating additional turbulence that can further scour the membrane surface to reduce membrane fouling on top of the effects of the imposed vibratory shear. The effectiveness of the SVS membrane module in terms of membrane fouling control, was examined in a laboratory unit SAnMBR for an extended operating period of 300 days. GOLD SPONSOR

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During this test period, the membrane filtration was operated in 5 stages, with the first 3stages having a permeate flux of 5 Lm-2h-1 and the last 2 stages with 10 and 15 Lm-2h-1, respectively. Fig. 1 shows the trans-membrane pressure (TMP) profiles of the SAnMBR for the 300-day operation. It can be seen that in the first 3 stages of 200-day filtration, the TMP only increased slightly from 12 to 15 kPa which demonstrated that the fouling control was very effective. Such superior membrane fouling control with the SAnMBR had not been reported in the literature so far. Overall, the present study demonstrated that the SVS membrane module was able to operate with a significant filtration flux (up to 10 Lm-2h-1) for a long period of 300 days without significant TMP rise, and also without any permeate backwash or chemical cleaning. Eventual fouling occurred when the flux was increased to a threshold limit of 15 Lm-2h-1. Fig. 1 also shows that when vibration was accidentally stopped there was a serious TMP jump3 ; the low TMP was restored when vibrations restarted. The results from this study demonstrate that the operation of the SVS membrane module can be effective for fouling control of SAnMBRs.

Figure 1. TMP profiles of the membrane filtration in the SAnMBR. The three curves I, II and III show the membrane performance when vibration accidentally stopped. REFERENCES 1

C.M. Ji, P.P. Eong, T.B. Ti, C.E. Seng, C.K. Ling, Renew. Sustainable Energy Rev. 2013, 26, 717-726.

2 T. Li, A.W.K. Law, A.G. Fane, J. Membr. Sci. 2014, 455, 83-91. 3 B.D. Cho, A.G. Fane, J. Membr. Sci. 2002, 209, 391-403.

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TIAN LI Title: Dr Nanyang Technological University, Singapore Phone: +65-67905296 Fax: +65-67906620 E-mail: [email protected] Personal History: 2010-2015

Research Associate, Nanyang Technological University, Singapore

Since 2016

Research Fellow, Nanyang Technological University, Singapore

Research interests: MF/UF/RO, MBR, membrane fouling, hydrodynamics

GOLD SPONSOR

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TH3.9 BAHAR YAVUZTÜRK GÜL1 EVALUATION OF N-ACYL-HOMOSERINE LACTONE DEGRADATION BY BACTERIA ISOLATED FROM MARINE, POND, SALTERN, LEACHATE AND BIOFOULING CONTROL WITH BACILLUS SP. T5 IN MBR

BAHAR YAVUZTÜRK GÜL1,2 AND İSMAIL KOYUNCU1,2 1 Istanbul Technical University, Environmental Engineering Depertment, Istanbul, Turkey 2 Prof. Dr. Dincer Topacık National Research Center on Membrane Technologies (MEM-TEK), Istanbul, Turkey ABSTRACT

Current study evaluated Quorum Quenching (QQ) exists among cultivable bacteria that are isolated from different environments and the link between bacterial diversity in the saltern, pond, marine habitats and leachate sample and the occurrence of N-AcylHomoserine Lactone (AHL) degradation. Using C8-HSL as the sole carbon source, 25 AHL-utilizing bacteria belonging to 13 genera from environmental samples were identified, including the genera Shewanella, Acinetobacter, Klebsiella, Bacillus, Deftia, Vibrio, Comamonas, Microbacterium, and Pseudomonas, Brevundimonas, Bosea, Stenotrofomonas and Tistrella. The biological degradation of quorum sensing signal molecules, and presence of the lactonases were investigated by bioassay. The overall results indicate that Tistrella exhibited QQ activities for the first time, and strains T21, T22, T4, G2, G4 G5, G6, H1, H3, H7, H8, H10 presented lactonase activity which have not been recorded in the previous research. Strain T5 and T6 from saltern and strain S5 and S10 from leachate degraded more than 90% of the AHL, thus demonstrating the highest capability to degrade AHL of the strains tested. Especially Bacillus sp. T5, degraded the majority of the AHL within just 30 min. Sodium alginate beads entrapped with Bacillus sp. T5 was applied to a lab scale MBR to test its potential to inhibit biofouling. Quorum quenching activity of T5 in MBR was determined by using TMP profiles obtained from two parallel MBRs. After the MBR operation, the TMP values of QQ MBR were as much as half of the TMP values of control MBR. Total anti-biofouling effect was found out as approximately 85%. Up to date two different QQ bacteria (Rhodococcus sp. BH4 and Pseudomonas sp. 1A1) are used for biofouling control in MBR applications. In this study, new and highly active QQ strains were isolated from different environmental source. Bacillus sp. T5, was used as antibiofouling agent in MBR and biofilm formation was successfully inhibited.

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ACKNOWLEDGMENTS

This work supported by The Scientific and Technological Research Council of Turkey (TUBITAK) (Project No: 114Y706). Keywords: N-Acyl-Homoserine Lactone, AHL Degradation, Quorum Sensing, Lactonase, Bacillus sp. T5

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THEME: APPLICATION IN MINING INDUSTRY AND AGRICULTURE T2.15 QI ZHENG THE INFLUENCE OF CO2 LOADED SOLVENTS ON MICROALGAE GROWTH THROUGH A PDMS MEMBRANE SYSTEM

QI ZHENG1, 2, GREGORY J. O. MARTIN2, SANDRA E. KENTISH1 1 Peter Cook Centre for CCS Research, Department of Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria 3010, Australia. 2 Algal Processing Group, Department of Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria 3010, Australia As a method to capture carbon dioxide and reduce greenhouse gas emissions, microalgae technologies have attracted much attention. However, efficient delivery of carbon dioxide to microalgae is a barrier to practical application, as carbon dioxide may be lost to the atmosphere as gas bubbles and the energy demand associated with carbon dioxide capture, compression and transportation is high. This article demonstrates a novel membrane system to utilize CO2 loaded solvents to enhance microalgae growth. CO2 loaded solvents can be obtained by absorbing CO2 from flue gas streams. These solvents can then be pumped through polydimethylsiloxane (PDMS) hollow fibre membranes which are submerged in microalgae ponds. The CO2 is released from the solvent through the membrane, providing a carbon source to the microalgae. In this article, three solvents of different CO2 loadings (20 wt% K2CO3, 30 wt% monoethanolamine and 2 mol/L potassium glycinate) were evaluated and compared as carbon sources for this membrane delivery system. Enhanced growth and lipid production of Chlorella sp. was observed with potassium carbonate, potassium glycinate of different CO2 loadings and monoethanolamine of 0.5 CO2 loading. However, monoethanolamine of 0.2 CO2 loading inhibited Chlorella sp. culture growth. This was probably the result of free MEA passing through the PDMS membrane. As an alternative way to regenerate solvents, this membrane delivery system can avoid the high energy penalty for solvent regeneration in a reboiler and solvent degradation during the regeneration. On the other hand, as a novel way to deliver carbon dioxide in CO2 loaded solvent to microalgae, this system can reduce the energy associated with gas compression and transportation.

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Fig. 1 A schematic of the proposed process. Carbon dioxide is absorbed from a combustion flue gas into a potassium carbonate solvent which is then pumped through a microalgal raceway pond or photobioreactor. The carbon dioxide desorbs into the microalgal culture medium and the depleted solvent is returned to the absorber. There is no need for a receiving solution, or a capture stripping operation. Reprinted from paper ‘ Zheng Qi, Gregory JO Martin, and Sandra E. Kentish. Energy efficient transfer of carbon dioxide from flue gases to microalgal systems. Energy & Environmental Science (2016).’

QI ZHENG PhD candidate Department of Chemical and Biomolecular Engineering, The University of Melbourne, Parkville, Victoria 3010, Australia +61452262603 [email protected] 2013-2016

PhD candidate, the University of Melbourne

2010-2013

Master, Tsinghua University

2006-2010

Bachelor, Tsinghua University

Research interests: Carbon Dioxide Capture, Algae, Membrane

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T2.16 H.K. SHON PILOT-SCALE FORWARD OSMOSIS DESALINATION OF MINE IMPAIRED WATER FOR FERTIGATION

S. PHUNTSHO, J.E. KIM, H.K. SHON * Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology, Sydney (UTS), Broadway, NSW 2007, Australia INTRODUCTION

Despite significant progress in desalination technologies, desalination still remains a capital and energy intensive process (high carbon footprint) (Beltrán & Koo-Oshima, 2006). Irrigation constitutes up to 70% of world’s total water consumption (Shaffer et al., 2012) and hence more cost-effective desalination technologies are needed to make irrigation affordable for irrigation to meet the increasing food demand. Forward osmosis (FO) process has emerged as one of the most promising and innovative new technologies for low-pressure desalination by mimicking the osmosis present in the natural living cells (Zhao et al., 2012). In the concept of fertiliser driven FO (FDFO) desalination process, saltwater is converted into nutrient rich water for irrigation using a fertiliser solution as draw solution (DS) (Phuntsho et al., 2011, Phuntsho et al., 2012). The FDFO process has so far mostly studied, mostly through lab-scale experiments except for a recent process optimisation study using 8040 FO membrane module (Kim & Park, 2011). This paper reports a six-month field study of the FDFO-NF process at a pilot-scale level for the desalination of saline water produced during coal mining activities. MATERIALS & METHODS

The pilot-scale FDFO-NF hybrid system (Figure 1) was operated in the filed for about six months for the desalination of saline groundwater water produced during the coal mining activities suing (NH4)2SO4 (SOA) as DS. NF was used as a post-treatment to reduce the SOA fertiliser concentration before fertigation. Test-fertigation was conducted on the turf grass (nearby turf farm) and potted tomato plants. The total dissolved solids of the coalmine water varied 3,500–4,500 mg/L and turbidity 1-3 NTU. The pilot-scale unit consisted of two 8040 cellulose triacetate (CTA) FO modules (HTI, USA) and one 4040 NF module (NE90 from Toray Chemicals Korea).

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Figure 1: Schematic layout of the pilot-scale FDFO-NF desalination system used for field testing RESULTS AND DISCUSSION

The long-term pilot-scale operation of the FDFO-NF desalination system (six batch cycles with each cycle lasting for more than a week and results) shows that the feed water quality could affect membrane fouling and the membrane flux performance of the FO process, however, this study observed that simple hydraulic cleaning was adequate to almost fully recover the water flux under the conditions tested without the need of chemical cleaning. Although the NF process could still consume energy however, NF process works efficiently without being significantly affected by membrane fouling or scaling issues as it receives an excellent feed water quality treated by the FDFO process. Reverse diffusion of fertiliser nutrients towards the feed brine will be a significant challenge using CTA FO membranes. The NH4+ and SO42- concentrations in the feed brine failed to meet the standard for feed brine discharge. The low feed rejection of the CTA FO membrane also could result in the build-up of feed salts such as Na+ and Cl- in the DS during repetitive recycling and reuse, eventually affecting the final water quality unless adequate bleeding from the closed FDFO-NF system occurs through NF permeate and also through re-reverse diffusion from the recycled and reused DS. This study therefore demonstrates the significance of FO membranes with higher membrane reverse flux selectivity for the FDFO-NF desalination technology to become a commercial reality. Test fertigation conducted on the turf grass and potted tomato plants indicate that, the FDFO-NF desalination system can produce water quality suitable for the fertigation of crops. Blending the NF permeate either with the diluted fertiliser DS or with the saline water in a specified proportion was also found suitable for fertigation. Such blending option could help lower the FDFO-NF plant capacity while still achieving water quality for fertigation. Using NF membrane with lower rejection and higher permeability could potentially save NF energy consumption while still meeting the water quality for fertigation. Although this study demonstrated that the integrated FDFO-NF desalination system is technically feasible for fertigation purpose, a detailed economic analysis is important to fully understand its comparative advantages with existing desalination technologies such as the RO process. GOLD SPONSOR

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REFERENCES 1

Beltrán, J. M. et al. (2006). Proceedings of the FAO Expert Consultation on Water Desalination for Agricultural Applications. FAO, Rome, Italy.

2

Kim, Y. C et al. (2011). Environmental Science & Technology 45, 7737–7745.

3

Phuntsho, S., et al. (2011). Journal of Membrane Science 375, 172-181.

4

Phuntsho, S., et al. (2012). Environmental science & technology 46, 4567-4575.

5

Shaffer, D. L., et al., (2012). Journal of Membrane Science 415–416, 1-8.

6

Zhao, S., et al. (2012). Journal of Membrane Science 396, 1-21.

HO KYONG SHON Title: Associate Professor University of Technology Sydney (UTS), Australia Phone: +61 432 239 507 E-mail: [email protected] 2015-present

ARC Future Fellow

2015-present

Associate Professor at UTS

Research interests: Forward Osmosis, Electrospinning, Membrane fabrication, Membrane modification, Membrane Technology

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T2.17 VALERIA ALMEIDA LIMA MEMBRANE SCREENING FOR IN-SITU SUB-SURFACE DESALINATION IRRIGATION SYSTEMS

VALERIA ALMEIDA LIMA1, PIERRE LE-CLECH1, GREGORY LESLIE1, BRUCE G. SUTTON1,2 1 UNESCO Centre for Membrane Science and Technology, University of New South Wales, Sydney, NSW, Australia 2 University of Sydney, Sydney, NSW, Australia Irrigation with brackish water can damage soil structure and reduce crop yield. Consequently, it is necessary to remove salts prior to irrigation; however, the use of conventional desalination such as reverse osmosis (RO) to treat brackish water is economically prohibitive in all but very high value agricultural applications. An alternative strategy that eliminates the mechanical complexity and energy consumption of RO, takes form on a new subsurface irrigation method where subsurface irrigation pipes are fashioned from polymeric membrane material1-4. The system allows brackish water to be treated and delivered directly to the soil-plant interface due to a negative potential generated by both soil matric potential and plant demand, which is expected to deliver water at rates that matches crop demand during various stages of growth. Additionally, delivery of the water through a sub-surface irrigation system would retain water in the soil and eliminate surface evaporative losses. A study was conducted to evaluate the effect of two semi-permeable membranes, BW30 reverse osmosis (RO) and CTA-ES forward osmosis (FO), on the performance of the proposed membrane-based irrigation system for conditions of high evaporative demand during summer. Membranes were tested during germination and seedling establishment of common bean (Phaseolus vulgaris cv. Jade) in a silty clay loam soil on saline solutions of 0.3 (Sydney tap water) and 3.6 dS/m (2,500 mg/L). The system performance was evaluated in terms of water flux, here expressed as evapotranspiration in mm/day. The highest values of evapotranspiration were observed for days 9 and 12, which corresponded to the highest temperatures averaged for the period between 10am and 2pm, equal to 33.8 and 31.7oC respectively. Temperature coupled relative humidity, among other factors, of 41.3 and 43.9% resulted in water demands of 3.6 and 3.8 mm/day for the respective days. For those conditions, a better performance was observed for the RO membrane in comparison to the FO, considering that the water flux observed for the RO fed with tap water was observed to be close to that measured for the control, starting from day 8 (Fig. 1). After the seven day germination period5, seedlings start to unfold their leaves and evapotranspiration is highly affected by the evaporative demand of the environment. Although the FO membrane is thinner (thickness 90 μm6) than the RO membrane (160.2 GOLD SPONSOR

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μm7), the water permeability of the RO (4 l/m2.h/bar)8 was almost six time higher that the FO (0.7 l/m2.h/bar)6 under the same conditions over the 14 day growing cycle (Figure 1). Permeability has also been referred to as the most relevant membrane characteristic affecting the model prediction of water temporal variation for a membrane pervaporation irrigation system9.

Figure 1. Overview of water flux by means of evapotranspiration for the control, ro and fo membrane for using tap water for 14 days

For the development of leaf area per plant (cm2), although the RO presented the best result for the lowest salinity level, no statistical difference was observed among treatments. Salinity was found to slightly hinder leaf development for the control and the RO system (Fig. 2), although no large difference was observed for the FO system. Notwithstanding this, the mechanism affecting leaf development for the control and membrane systems differs as a function of how water is provided to the root system. For the membrane-based irrigation, the soil matric potential draws water across the membrane prior to germination. As the osmotic pressure of the feed water increases, the water flux and consequently leaf area declines. For the control treatment, the salt content in the water is the limiting factor to leaf growth as the plants were grown under conditions of no water stress. The study emphasizes the importance of membrane selection and also demonstrates the ability of the proposed irrigation system to meet crop water demand according to variations of environmental evaporative demand. However, extended growth periods are required for additional evaluation of the effect of salinity on plant growth and salt accumulation in the soils in the control experiments compared to the membrane-based irrigation system.

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Figure 2. Leaf area per plant (cm2) after 15 days for conditions of conventional irrigation (control) and membrane-based irrigation for ro and fo membranes. *Means followed by same letter are not significantly different by the Tukey test at 5% probability REFERENCES 1 Leslie, G. L.; Sutton, B. G. Reverse Osmosis Irrigation. AU pat. WO 2009105808 A1, 3 set. 2009. 2 Leslie, G. L.; Sutton, B. G; Antony, A. A Plant Watering Device. AU pat. WO2012103590 A1, 9 ago. 2012 3 V. Lima, A. Antony, P. Le-Clech, G. Leslie, B. G. Sutton Lima, V. I. A. New method for subsurface irrigation to improve use of brackish water. In III Inovagri International Meeting 2015 (pp. 1–9). Fortaleza, Brazil: Institute for Research and Innovation in Irrigated Agriculture. 4 V. Lima, P. Le-Clech, G. Leslie, B. G. Sutton, In-situ desalination for climate-resilient irrigation, Water e-Journal 2016, 1 (3), 4p. 5

FAO. (2013). Crop Water Information: Bean. Retrieved Jun 20, 2016, from http://www.fao.org/nr/ water/cropinfo_bean.html

6

Yeo, S. Y.; Wang, Y; Chilcott, T.; Antony, A.; Coster, H.; Leslie, Greg. Characterising nanostructure functionality of a cellulose triacetate forward osmosis membrane using electrical impedance spectroscopy, Journal of Membrane Science 2014, 467, p.292-302.

7

N. M. Al-Bastaki and H.I. Al-Qahtani, Assessment of thermal effects on the reverse osmosis of salt/ water solutions by using a spiral wound polyamide membrane. Desalination 1994, 99 (1), p. 159-168.

8 Liu, M.; Lü, Z.; Chen, Z.; Yu, S.; Gao, C. Comparison of reverse osmosis and nanofiltration membranes in the treatment of biologically treated textile effluent for water reuse. Desalination 2011, 281, p.372-378. 9

Quiñones-Bolaños, E. And Zhou, H. Modelling water movement and flux from a membrane pervaporation system for wastewater microirrigation. Journal of Environmental Engineering 2006, 132 (9), p.1011-1018.

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VALERIA ALMEIDA LIMA Title: PhD candidate The University of New South Wales, Australia Phone: +61293856915, E-mail: [email protected] 2009

Bachelor in Agricultural and Environmental Engineering

2012-2013

Intern at Fillmore Greenhouses Inc., USA

Research interests: water treatment, wastewater reuse in agriculture, irrigation.

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T2.18 K. MESCHKE INFLUENCE OF PH ON THE RETENTION OF STRATEGIC ELEMENTS FROM SYNTHETIC LEACHING SOLUTIONS BY NANOFILTRATION

K. MESCHKE1, K. BOHLKE1, B. DAUS2, R. HASENEDER1, J.-U. REPKE1,3 1 Institute of Thermal, Environmental and Natural Products Process Engineering, TU Bergakademie Freiberg, 09599 Freiberg, Germany 2 Department Analytical Chemistry, UFZ – Helmholtz Center for Environmental Research, 04318 Leipzig, Germany 3 Chair for Process Dynamics and Operations, TU Berlin, 10623 Berlin, Germany Strategic elements are essential for industrialized countries to develop emerging technologies. The high economic importance and the growing demand of several strategic elements increase the risk of supply. Moreover, the quasi-monopoly on mining and processing of China strengthened the desire of supply reliability1,2. In 2014, the European Commission published a list of 20 critical raw materials (e.g. Ge, Co, Sb, In), which are fundamental for the European Union’s economy1. Secondary recourses, like mineral mining dumps, represent an unexploited resource potential for strategic elements and could ensure long-term economic growth as supply dependence can be avoided. In the presented study, a dumped flue dust from German copper shale smelting represents the feedstock for a proposed hybrid process. The metalliferous shale was mined and smelted in a blast furnace in the Mansfeld region (Central Germany) until 1990. Since 1904, accrued flue dust was suspended in water, dewatered, and resulting slurry was stored for further smelting to extract lead and zinc. For economical reasons, the secondary metal production was closed 1978, but the copper shale smelting continued. Therefore, approximately 220,000 tons of the remained sludge, the so-called Theisen sludge, were deposited between 1978 and 19903. Next to raw materials (e.g., Cu, Pb, Fe, Zn), the mining residual maintain strategic elements (e.g., Ag, Co, Ge, Mo, Re, Sb). By bioleaching, the metals can be dissolved from the mineral phase. Klink et al. (2016) evaluated the bioleaching potential of Theisen sludge and showed that a metal solubilization is possible4. The targeted strategic elements shall be separated and concentrated from the obtained multicomponent leaching solution by downstream processing like nanofiltration (NF). At the Institute of Thermal, Environmental and Natural Products Process Engineering (TU Freiberg/Germany), the pH-dependent separation performance of two commercial polymeric nanofiltration membranes consisting of poly(piperazine-amide) and polyamide (see Fig. 1) is investigated. The molecular weight cut-off (MWCO) is below 300 Da for both membranes. The experiments are conducted in dead-end set-up (25 °C, 15 bar, 500 rpm) with synthetic leaching solutions (each 300 mL), which contain next to the trace elements Co, Ge, Mo, and Re, the major components Cu and Zn. In advance, the pH-dependent GOLD SPONSOR

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retention of the single elements was determined to investigate the dominating retention mechanisms without mutual inferences.

80

Retention [%]

100

A

60 40 20 0 -20

0

2

4 pH

6

8

Mo Ge Re Co Cu Zn

B

80

Retention [%]

100

60 40 20 0 -20

0

2

4 pH

6

8

Mo Ge Re Co Cu Zn

Figure 1. The pH-dependent separation of synthetic leaching solutions (0.5 mg/L Mo, 10 mg/L Ge, 10 mg/L Re, 4 mg/L Co, 100 mg/L Cu, 300 mg/L Zn) for (A) poly(piperazine-amide); (B) polyamide.

As can be seen in Figure 1, the separation is strongly affected by the pH of the feed solution. For example, germanium and molybdenum are present as neutral species at pH 25,6. In combination with an ionic radius smaller than the MWCO, the ions can permeate nearly unimpeded through the membrane. At pH 7, the separation selectivity is increased because the ionic species and membrane charge have changed. The membranes carry a negative zeta potential and e.g. molybdenum is present as MoO42- 5. Evoked by repulsion, thus, the retention increases. A convective exclusion of the formed hydroxides like copper(II)hydroxide7 is also responsible for the enhanced retention compared to pH 2. Moreover, the MWCO and the location of the isoelectric point (IEP) of the membrane have a significant influence on the separation performance. Due to the lower MWCO and IEP of the poly(piperazine-amide) membrane, the separation selectivity is already enhanced at pH 4 in comparison to the polyamide membrane. Currently, rhenium can be separated from the multicomponent leaching solution at best at pH 7 with the poly(piperazine-amide) membrane. Further investigations are aimed to reproduce the retention mechanisms in cross-flow set-up. Furthermore, the separation selectivity shall be increased at pH 2 by adding chelating agents. REFERENCES

240

1

European Commission, Report on Critical Raw Materials for the EU, 2014, 41p.

2

U.S. Department of Energy, Critical Materials Strategy, 2011, 196p.

3

H. Weiss, M. Morency, K. Freyer, J. Bourne, D. Fontaine, B. Ghaleb, R. Mineau, M. Möder, P. Morgenstern, P. Popp, M. Preda, H.-C. Treutler, R. Wennrich, Science of The Total Environment, 1997, 203, 65-78.

4

C. Klink, S. Eisen, B. Daus, J. Heim, M. Schlömann, S. Schopf, Journal of applied microbiology, 2016, 6, 1520-1530.

5

T. Ozeki, H. Kihara, S. Ikeda, Analytical Chemistry, 1988, 60, 2055-2059.

6

G. S. Pokrovski, J. Schott, Geochimica et Cosmochimica Act,a 1998, 62, 1631-1642.

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7

H. Liu, S. Feng, N. Zhang, X. Du, Y. Liu, Frontiers of Environmental Science & Engineering, 2014, 8, 329-336.

KATJA MESCHKE Title:Dipl.-Nat.; Dipl.-Ing. Affiliation, Country: Institute of Thermal, Environmental and Natural Products Process Engineering, TU Bergakademie Freiberg, 09599 Freiberg, Germany Phone: +49 3731 39 3920 Fax: +49 3731 39 3652 E-mail: [email protected] Personal History: 2004-2010

Studies of Applied Natural Science,TU Bergakademie Freiberg, Germany

2010-2012

Technical Assistant for Water and Soil Analysis Eurofins GmbH, Freiberg/Germany

2012-2015

Studies of Environmental Engineering,TU Bergakademie Freiberg, Germany

Since 2015 Research Associate, Phd Student, TU Bergakademie Freiberg, Germany Research interests: Membrane Technology, Nanofiltration, Secondary Mining

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T2.19 XING YANG ACID RECOVERY FROM MINING PROCESSING WATER USING MEMBRANE DISTILLATION AND SOLVENT EXTRACTION (MD-SX)

LINING DING1, HAL ARAL2, NICHOLAS MILNE3, MIKEL DUKE1, XING YANG1 1 Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, P.O.BOX 14428, Melbourne, Victoria 8001, Australia; 2 Jervois Mining Limited, 10 Jamieson Street, Cheltenham, VIC 3192, Australia 3 School of engineering, Deakin University, Waurn Ponds, Victoria 3216, Australia Mining processing water contains a large amount of acid and valuable metals. The conventional neutralisation results in the formation of precipitates, high cost of chemical consumption and sludge disposal, as well as the loss of valuable metals and acids leading to an unsustainable situation. The mining industry is giving serious considerations towards acid recovery given enormous economic and environmental benefits1,2. In this study, a sustainable solution is proposed to recover both sulphuric acid and minerals from the real spent solution of ores, namely pregnant leach solution (PLS), via a combined membrane distillation and solvent extraction process, namely MD-SX3,4. It was demonstrated that sustainable performance could be achieved using a commercial hydrophobic membrane. Firstly, direct contact membrane distillation (DCMD) was employed to concentrate sulphuric acid in the leach solutions and meanwhile recover fresh water as permeate product. The membrane capacity to operate under a range of industry conditions was also explored in terms of membrane wetting, scaling and cleaning. Secondly, solvent extraction was optimized to extract free acid from the MD concentrate in high efficiency. Two PLS solutions, one containing AA (ascorbic acid) and the other without AA were chosen and compared based on their acid extraction efficiencies under optimised conditions. Ascorbic acid was used to reduce ferric iron to ferrous iron. Results showed that both sulphuric acid and iron salts were successfully concentrated approximately by 2-fold in the feed solution. For example, for the non AA sample, the acid concentration increased from 21.6 g/L to 48.2 g/L, and the total iron concentration increased from 27 g/ kg to 51 g/kg. A mineral rejection of 99.9% based on the minimal presence of metals in the permeate was observed. In addition, no wetting or membrane leakage was observed during a continuous run. Only minor membrane scaling was observed but did not affect the flux and was easily removed by simple tap water rinsing. Overall, there was no formation of iron sulphate crystallisation during or after MD run. Free acid was successfully extracted from the MD concentrates, using organic solvent consisting of 50%TEHA (tris-2ethylhexylamine) and 10% Shellsol A150 in decanol. The total acid recovery of MD concentrates and original PLS is shown in Table 1. The recovery efficiency of free acid up

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to 92.8% was achieved under unoptimized extraction conditions. This is more approximately 2-fold higher than the extraction efficiency of the original PLS solution (pre-MD). Thus, the advantages of the combined MD-SX process were compared against a single SX process in terms of overall acid recovery efficiency. Table 1. Solvent extraction of free acid from PLS and concentrated PLS samples with TDA*

TDA, A/O=1:1 Sample EX (%)

ST 1 (%)

ST 2 (%)

Rec. (%)

Original Non-AA PLS (21.6 g/L of Free Acid) Non-AA concentrate (48.2 g/L FA)

44.7 94.7

87.2 64.5

14.0 31.2

39.3 90.6

Original AA PLS (17.5 g/L of Free Acid) AA concentrate (34.5 g/L FA)

84.3 91.5

58.5 69.7

10.3 31.6

49.4 92.8

*Note: TDA represents the organic system with 50 vol% TEHA (tri-ethylhexyl amine), 40 vol% Decanol and 10 vol% ShellSol A150

It was found that: 1) pre-concentration the PLS solution by MD could greatly reduce the treating volume and increase extraction efficiency for free acid recovery; 2) the high acid recovery from the MD concentrates indicated that extraction solvent could be reduced by half; 3) high quality water could be obtained from MD and returned to the metallurgical processes; (4) over 90% of the sulphuric acid could be extracted from acidic spent process waters containing ferrous or ferric iron as dominant ionic species; and (5) iron sulphate from the SX raffinate can be crystallised with little effort (Figure. 1) which could be sold or disposed of as solid material.

Figure 1. Crystal precipitated from AA concentrate at room temperature REFERENCE 1 L. F. Dumee, K. Sears, J. Schutz, N. Finn, C. Huynh, S. Hawkins, M. Duke and S. Gray, Characterization and evaluation of carbon nanotube Bucky-Paper membranes for direct contact membrane distillation, Journal of Membrane Science, 351 (1-2) (2010) 36-43. 2 J. H. Zhang, N. Dow, M. Duke, E. Ostarcevic, J. D. Li and S. Gray, Identification of material and physical features of membrane distillation membranes for high performance desalination, Journal of Membrane Science, 349 (1-2) (2010) 295-303. 3 U. K. Kesieme, H. Aral, M. Duke, N. Milne and C. Y. Cheng, Recovery of sulphuric acid from waste and process solutions using solvent extraction, Hydrometallurgy, 138 (2013) 14-20. GOLD SPONSOR

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[4] U. K. Kesieme, N. Milne, C. Y. Cheng, H. Aral and M. Duke, Recovery of water and acid from leach solutions using direct contact membrane distillation, Water Science and Technology, 69 (4) (2014) 868-875.

NAME: XING YANG Title: Dr Victoria University, Australia Phone: +61 3 99197690 Fax: +61 3 9919 7696 E-mail: [email protected] 2012-2013

Nanyang Technological University, Singapore

Since 2013

Institute for Sustainability and Innovation, Victoria University

Research interests: Membrane technology for water treatment and reclamation, Membrane distillation and low-energy resource recovery from wastewaters Zero liquid discharge and mineral extraction; Process simulations and modeling

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THEME: MIXED SESSION ON MEMBRANES T4.15 FYNN ASCHMONEIT COMPUTATIONAL FLUID DYNAMIC ANALYSIS OF CONCENTRATION POLARIZATION AND WATER FLUX OPTIMIZATION IN SPIRAL WOUND MODULES

FYNN ASCHMONEIT1, PROF CLAUS HÉLIX-NIELSEN1 1 Technical University of Denmark, Department of Environmental Engineering, Bygningstorvet, Building 115, 2800 Kgs. Lyngby, Denmark INTRODUCTION:

In membrane separation spiral wound modules (SWMs) are a common design due to their high membrane area to volume ratio. In addition SWMs offer a good balance between ease of operation, fouling control, permeation rate and packing density and SWMs are widely used for commercial applications ranging from reverse osmosis (RO) to ultrafiltration. A common application is RO-based desalination. Systems of SWMs scale with the number of modules, thus making them popular for large treatment plant designs. The typical module sizes, referring to the module diameter, are 2.5”, 4” and 8”. There is a considerable interest in making even bigger modules, as water treatment cost could be cut considerably, but experiments with 16” prototypes showed very poor performance1: The long membrane envelopes and the resulting large pressure drop lead to higher concentration polarization (CP), reducing the modules performance. Through the application of more membrane envelopes and turbulence promoting spacers, a module could be optimized, but due to the tight packing, local measurements of the flow field and the solute concentration distribution are very difficult to conduct2. SWMs have also recently attracted interest in the design of forward osmosis (FO) membrane modules, and recent progress in FO membrane development has led to a growing interest in using FO membranes in hybrid FO-RO systems. Here low salinity waste water is used as a feed solution, which dilutes sea water through FO. The subsequent RO desalination is less energy consuming and shows a smaller fouling tendency, compared to a stand-alone RO desalination. But economic assessments of the FO-RO systems show a need for more effective FO modules3. As FO is an osmotic driven process, the pressure drop along the module is crucial for the modules performance. The implementation of turbulence promoting spacers in the feed channel reduces the CP but also increases the module’s pressure drop.

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Thus for both RO and FO SWM design a complete 3D computational fluid dynamic (CFD) model would be very beneficial for the design of modules and plants2. However, so far no CFD models of SWM modules capable of resolving the pressure drop dependency on the choice of spacer has yet been developed3. In the following, we present our design of a CFD model capable of resolving the flow field and solute concentration- and pressure distribution for an entire SWM. Once fully developed, it will be applicable for optimizing performance in both RO and FO applications. METHOD:

The underlying method was presented in Gruber et al. 4. It is the implementation of a fluid solver and a boundary condition, that acts as a membrane. With the parameters waterand solute permeability and the solute resistivity of the porous layer, the model resolves the flow field, the solution concentration- and pressure distribution in the flow domain, and the boundary effects of external- and internal CP, but only for flat membrane sheets. The first step in the development of a complete SWM is the further development of the above mentioned CFD model to also work with wound membrane boundary conditions. The major challenge in developing a complete spiral wound CFD model is the simplification of the module geometry, such that modern high performance computers can simulate the flow in reasonable time. This is met by making use of the symmetry of the model: It is sufficient to only simulate one membrane envelope and the adjacent feed channel on either side. In fact, by defining a periodic boundary in the middle of the feed channel, only half of the feed channel is simulated on either side (Fig.1). These periodic boundaries are crucial to model development. They copy the flow field at the boundary to their respective partner boundary, as if another membrane envelope was adjacent to it. Thus, only a small part of the whole module is simulated, without cutbacks in the resolution of the results. The RO SWM is based on pressure driven transport in the envelope but for FO, a flow channel needs to be created. This is achieved by pressurizing the feed inlet and implementing a baffle across ~3/4 of the length of the draw channel, forcing the draw solution stream over the membrane surface (Fig.2). With this model both FO and RO SWMs will be investigated and optimized with respect to spacer geometries, amount of envelops and baffle geometries.

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Figure 1. Sketch of the geometry of the spiral wound membrane module, with the actual computational domain highlighted in blue and a detailed sketch of the computational domain. The green surfaces are the respective membranes of the envelope. Between them, the flow field of the permeate (RO) or draw solution (FO) is indicated by the red arrows. Outside the envelope half of the feed channel is added to either side of the envelope. The grey cylinders represent the feed spacers and the black arrows indicate the feed solution flow field. The red-transparent surfaces are the crucial part of the model: They represent a pair of periodic boundaries in the middle of the feed channel. If the permeate (RO) or draw solution (FO) is indicated by the red arrows. Outside the envelope half of the feed channel is added to either side of the envelope. The grey cylinders represent the feed spacers and the black arrows indicate the feed solution flow field. The red-transparent surfaces are the crucial part of the model: They represent a pair of periodic boundaries in the middle of the feed channel.

Figure 2. Flow field in the draw channel of one unrolled envelope in FO operation: Through implementing a baffle across ~3/4 of the length of the envelope and pressurizing the feed tube inlet, a channel is created and the spiral wound membrane module can be operated in FO.

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REFERENCES 1 T. I. Yun, C. J. Gabelich, M. R. Cox, A. A. Mofidi, R. Lesan, Desalination 2005, 189, 141-154 2 A. J. Karabelas, M. Kostoglou, C. P. Koutsou, Desalination 2014, 356, 165-186 3 G. Blandin, A.R.D. Verliefde, J. Comas, I. Rodriguez-Roda, P. Le-Clech, Membranes 2016, 6, 37 4 M.F. Gruber, C.J. Johnson, C.Y. Tang, M.H. Jensen, L. Yde, C. Hélix-Nielsen, J. Memb. Sci. 2011, 379, 488-495

FYNN JEROME ASCHMONEIT Title: M.Sc. Technical University of Denmark, Department of Environmental Engineering, Denmark Phone: +45 50240586 E-mail: [email protected] 2014

physics B.Sc., Ludwig-Maximilians University Munich

2016

physics M.Sc., University of Copenhagen

Since 2016

PhD student, Technical University of Denmark

Research interests: development of computational schemes for particle transport in fluids and the application of these for the design of membrane modules

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T4.16 DR. IR. MARJOLEIN VANOPPEN RO EFFICIENCY INCREASE WITHOUT ANTI-SCALANTS: A PILOT-STUDY

DR. IR. MARJOLEIN VANOPPEN1, MSC. GRIET STOFFELS1, JOHN BUFFEL1, PROF. DR. IR. BART DE GUSSEME2,3, PROF. DR. IR. ARNE VERLIEFDE1 1

Particle and Interfacial Technology Group (PaInT), Ghent University, Coupure Links 653, Ghent, Belgium

2

Center for Microbial Ecology and Technology (CMET), Faculty of Bioscience Engineering, Ghent University, 9000 Ghent, Belgium

3

Induss nv, Mechelsesteenweg 66, 2018 Antwerp, Belgium

Reverse osmosis (RO) is a popular technique to satisfy the ever higher demand for high quality water. The water recovery of this pressure driven membrane process is often hampered by the presence of multivalent cations and anions, causing scaling on the membrane. One possibility to increase the RO recovery is to remove the multivalent cations by ion-exchange (IEX) prior to RO. Although this does prevent scaling on the membrane and thus the RO recovery can be increased, this technique requires additional water and chemicals for the regeneration of the resin, which is usually carried out with a 10wt% NaCl solution. However, the RO concentrate consists of high concentrations of monovalent cations (mainly Na + and K+) when the multivalent cations are removed from the feed stream. This concentrate could potentially be used for the regeneration of the IEX, as shown in Figure 1.

Figure 1. Schematic overview of the envisioned hybrid IEX-RO process with recirculation of the RO brine for the regeneration of the IEX (IEX = ion-exchange, RO = reverse osmosis)

Recent research1 has shown that the efficiency of the regeneration of IEX with RO concentrate depends mainly on the mono-to-multivalent cation ratio in the feed stream. For high ratios, the regeneration is similar to a classical regeneration with NaCl, while for lower ratios, the amount of monovalent cations in the concentrate is insufficient to fully GOLD SPONSOR

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recover the IEX capacity. In the latter case, the addition of NaCl to the concentrate can increase the regeneration efficiency sufficiently. This hybrid process was now demonstrated on a pilot scale at the harbor of Ghent. MATERIALS AND METHODS

A resin column containing 35L of cation exchange resin (Lewatit) was coupled to a 4 inch RO module (LE-440, Filmtec). The RO concentrate was collected in a 1 m³ tank and used to regenerate the IEX resin after saturation. A feed flow rate of 200 l/h was maintained. Four mayor experimental cycles were carried out: (1) IEX-RO operation at 75%, (2) IEX-RO operation at 85%, (3) IEX-RO operation at 75% and (4) IEX-RO operation at 75% with addition of NaCl to the concentrate. Because of the variable influent concentrations encountered in the harbor (Figure 2), experiment 1 was repeated in experiment 3, to test the influence of the changing composition.

Figure 2. Influent cation concentrations during the pilot testing RESULTS

An increase in RO recovery from 75% to 85% could easily be achieved during the tests, without any operational problems in the RO system. However, this increase in RO recovery did not influence the regeneration efficiency of the IEX when regenerated with the RO brine. At a higher RO recovery, the brine’s concentration is higher, but its volume is lower. It thus appears that it is the total amount of monovalent cations present determines the IEX regeneration capacity in these circumstances, rather than the concentration or volume. Overall, the regeneration efficiency with the brine was low, dropping below 20% after 3 regeneration cycles. In experiment 3, the Na+ concentration was about 10 times higher than during experiment 1, while the concentrations of the other cations remained stable. This resulted

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in a stable IEX regeneration efficiency of 46%. To increase the IEX efficiency back to full capacity, a small amount of NaCl was added to the RO concentrate. This indeed resulted in the full restoration of the IEX capacity. In this research, the technological feasibility of IEX-RO was demonstrated. Furthermore, an economic analysis shows its economic viability as well. Based on the results, a tool was developed to predict IEX-RO efficiencies based on feed stream composition and IEX capacity. It is believed that IEX-RO can prove economically, technologically and ecologically interesting for a wide variety of feed streams. REFERENCES 1 M. Vanoppen, G. Stoffels, C. Demuytere, W. Bleyaert, A.R.D. Verliefde, Water Res. 2015, 80, 59-70

MARJOLEIN VANOPPEN Title: Senior researcher Ghent University, Belgium Phone: +32 (0)9 264 99 11 Fax: +32 (0)9 264 62 42 E-mail: [email protected] ugent.be 2012

Graduation as a bioscience engineer in environmental technology

2012-2016

Received degree of PhD in applied biological sciences: environmental technology

Since 2016

Senior researcher at the Particle and Interfacial Technology Group (PaInT) at Ghent University

Research interests: Electrochemical membrane processes, industrial water treatment, sustainable membrane processes

GOLD SPONSOR

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T4.17 MARIAN TUREK INTEGRATED SYSTEM FOR FLOWBACK TREATMENT

MARIAN TUREK1, KRZYSZTOF LABUS2, PIOTR DYDO1, KRZYSZTOF MITKO1, EWA LASKOWSKA1, AGATA JAKÓBIK-KOLON1 1 Silesian University of Technology, Faculty of Chemistry, ul. B. Krzywoustego 6, 44-100 Gliwice, Poland 2 Silesian University of Technology, Faculty of Mining and Geology, Akademicka 2, 44-100 Gliwice, Poland Drilling of the vertical and horizontal components of a well may require 400–4000 m3 of water for drilling fluids to maintain downhole hydrostatic pressure, cool the drillhead, and remove drill cuttings. Then, 7000–18,000 m3 of water are needed for hydraulic fracturing of each well. Unfortunately, most of shale gas areas in Poland have relatively low reserves of fresh groundwater. The water scarcity means shale gas industry should reuse as much water as possible. Approximately 10 to 40% of the fracturing fluid returns to the surface during the flowback period. Flowbacks typically contain chemicals naturally present in the rocks, along with some components of the fracturing fluid. They have complicated composition, high organic content, hardness and salinity, and as such are problematic for desalination and reuse. Magnesium and sodium ions content are the limiting factor, preventing direct flowback reuse and creating the need for desalination; higher Mg2+, Ca2+, Na+, and K+ concentrations significantly affect the fluid viscosity. The Petroleum Technology Alliance Canada has laid a set of general guidelines for flowback reuse: pH between 6 and 8, iron content <25 mg/dm3, total hardness <15 000 mg/dm3 as CaCO3, carbonate content <600 mg/dm3 as CaCO3, bicarbonate content <600 mg/dm3 as CaCO3, silica content <35 mg/dm3, total dissolved salts (TDS) <50 000 mg/dm3, total suspended solids (TSS) <50 mg/dm3, no bacteria, oxidizing or reducing agents. To simulate geochemical reactions of hydraulic fracturing fluid with formation rocks, fluid-gas-rock reaction was performed in an autoclave. Energized fracturing fluid, containing 50% vol. of CO2 gas, was applied. Resulting flowback was analyzed and concept of the treatment was proposed based on the chemical composition. It was assumed that the treatment technology should allow to reuse most of the flowback volume. Various thermal and membrane methods can be applied for flowback treatment. In this work, the possibility of producing desalinated water from hydraulic fracturing flowback by electrodialysis reversal (EDR) was investigated. Electrodialysis reversal was chosen over conventional electrodialysis because of the scaling risk: the treated flowbacks had high concentrations of: calcium, sulphate and bicarbonate ions. Two cases were investigated: 1) regular operation, when the flowback is desalinated down to the level allowing its reuse in hydraulic fracturing fluid preparation; 2) final treatment, when the fracturing process

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stops and the remaining flowback is deeply desalinated by EDR. The deeply desalinated EDR diluate could then be passed to the organics removal unit operation. The composition of flowback was used in the subsequent EDR simulation. Although the obtained flowback is not highly salinized, and the sodium, potassium, magnesium concentrations, and pH criteria are met, it does not meet the HCO3- and Ca2+ concentration criteria, so it should be treated prior to its reuse. Acidification could remove the excessive CaCO3, but the flowback would then require addition of base to meet the pH criterion. The bicarbonate and calcium increase can be explained as a result of dissolving mainly the carbonate minerals present in the gas-bearing formation while the HCO3- derives from dissociation of carbonic acid formed due to CO2 dissolution in water used to produce the fluid as well as in the formation water.. The obtained flowback was supersaturated with respect to calcium carbonate (LSI +0.74), but it does not showed any signs of crystallization. We were not able to prepare a model solution of flowback having the same composition, which suggests the liquid obtained after rock-fluid-gas reaction in the autoclave was stabilized by organic substances present in the energized fracturing fluid. Next, an electrodialysis reversal of hydraulic fracturing flowback was simulated and the composition of diluate and concentrate was calculated. During the regular treatment, the flowback could be desalinated down to TDS of 1352 mg/dm3, compared with initial flowback TDS of 8279 mg/dm3, which means it should be recycled in hydraulic fracturing liquid production, especially given that the majority of non-ionic, organic components of the flowback would be kept in the produced diluate. The obtained diluate meets the water quality guidelines for the flowback reuse in terms of bicarbonate content and salinity. The obtained concentrate had LSI of +2.1 and gypsum saturation level of 390%. When the fracturing operation is stopped, the final flowback could be desalinated down to TDS of 336 mg/dm3 and passed for further treatment in order to remove organic substances. The obtained concentrate had LSI of +2.1 and gypsum saturation level of 420%. The results show that the initial ratio of diluate to concentrate volumes should be 91:9, which we assumed is the maximum ratio from a practical point of view. Water flux across the ion-exchange membranes, would increase the concentrate flow rate by ca. 15% during the course of the electrodialysis. Simulation showed that the hydraulic fracturing flowback can be desalinated down to total dissolved salts (TDS) of 1352 ppm at water recovery of 89.8%, and reused during regular operation of EDR plant. When the hydraulic fracturing stops, the remaining flowback can be deeply desalinated (down to TDS of 336 mg/dm3) and passed forward for organics removal. The results were obtained based on the assumption that without antiscalants the maximum LSI is +2.3 and maximum gypsum saturation is 520%, as in our previous work. However, since the flowback already contains a lot of antiscalants (typically up to 0.043% v/v of ethylene glycol), we believe that even higher LSI and gypsum saturation could be possible to achieve, resulting in higher water recovery. The flowback obtained in the autoclave reaction had low salinity. The actual flowbacks collected from the drilling sites can reach very high salinity. To assess the treatment of high GOLD SPONSOR

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salinity flowbacks, water from “Łebień LE-2H” drill hole in the Baltic Basin, Poland, was investigated. The flowback composition was as follows: 48 000 mg/dm3 as Cl-, 7 568 mg/ dm3 as Ca2+, 759 mg/dm3 as Mg2+, 857 mg/dm3 as Sr2+, 218 mg/dm3 as Ba2+, 5 mg/ dm3 as SO42-, 170 mg/dm3 as of HCO3-. In our work an integrated system has been proposed: flowback is decarbonized, subjected to micro- and ultrafiltration, optionally softened by caustic soda and soda ash method, and desalinated by the electrodialysis and reverse osmosis. The proposed system could produce concentrated sodium chloride solution (300 000 mg/dm3), which could be used as a raw material for salt recovery, and product water of concentration in the range 70-230 mg/dm3 as NaCl. The projected energy consumption of an ED-RO system was 25-36 kWh/m3. Finally, an integrated system for flowback treatment was proposed. The system was designed to work in two stages: 1) regular fracking operation, when the flowback water is being collected into a tank. After the flowback is collected, it is subjected to a nanofiltration (NF) with micro- or ultrafiltration pretreatment. The NF permeate can be used for preparation of fresh fracturing fluid, which decrease the water consumption in fracturing operation. The NF retentate is recycled back to the storage tank. When the fracturing operation ends and the drilling site is to be abandoned, the NF permeate is directed to an integrated RO-ED system, producing saturated brine and RO permeate, which is recycled back to the storage tank, diluting the flowback down to the levels which allow safe discharge to the environment, or treatment by biological sewage treatment plant. To test the proposed flowback treatment system, treatment of flowback, acidified with hydrochloric acid, was tested using NFX and NFG (Synder) commercial nanofiltration membranes. The compositions of permeates were as follows: in case of NFX membrane - 1 377 mg/dm3 as Cl-, 46 mg/dm3 as SO42-, 635 mg/dm3 as Na+, 136 mg/dm3 as K+, 9 mg/ dm3 as Mg2+, 82 mg/dm3 as Ca2+; in case of NFG membrane - 2 891 mg/dm3 as Cl-, 312 mg/dm3 as SO42-, 1 358 mg/dm3 as Na+, 220 mg/dm3 as K+, 80 mg/dm3 as Mg2+, 516 mg/dm3 as Ca2+. The experiments show that NF permeate can be used for preparation of a new portion of hydraulic fracturing fluid in a proposed integrated flowback treatment system. MARIAN TUREK Title: Professor Silesian University of Technology, Faculty of Chemistry, ul. B. Krzywoustego 6, 44-100 Gliwice, Poland Phone: +48 32 2371021 Fax: +48 32 2372277 E-mail: [email protected] MSc

1978

Silesian University of Technology

PhD

1991

Silesian University of Technology

Professor

2004

Silesian University of Technology

Research interests: membrane processes, desalination in integrated systems, boron removal

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T4.18 RYAN LEFERS MEMBRANE SYSTEMS FOR RECOVERY AND REUSE OF PLANT TRANSPIRATION WATER IN GREENHOUSES

RYAN LEFERS1, NARASIMHA MURTHY SRIVATSA BETTAHALLI2, NINA FEDOROFF3, SUZANA P NUNES2 AND TOROVE LEIKNES1 1 Water Desalination and Reuse Center (WDRC), Biological and Environmental Science and Engineering Division (BESE), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia 2 Biological and Environmental Science and Engineering Division (BESE), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia 3 Evan Pugh Professor Emerita, Penn State University, University Park, PA 16802, USA Estimates are that agriculture consumes about 70% of all global fresh water for irrigation of food and fodder crops. Water applied for irrigation in traditional open field production is lost to evaporation, transpiration, runoff, and deep percolation. The growth of crops in greenhouses allows greater control of water losses, with the exception of transpiration losses, which are essential for plant growth. A closed greenhouse with an integrated liquid desiccant absorption system allows transpired humidity to be recovered and condensed to liquid form in the desiccant. If fresh water is extracted (desorbed) from the desiccant, it can be reused for irrigation of greenhouse plants. The fundamental challenges undertaken in this work are humidity collection into desiccants and recovering fresh water from the desiccant. This study investigates the use of hollow fiber membrane contactors for dehumidification and membrane distillation systems to recover fresh water from the desiccant. Experimental results using PVDF hollow fiber have been positive for both membrane contactor dehumidification and vacuum membrane distillation. RYAN LEFERS Title: PhD Candidate Affiliation, Country: King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia Phone: +966 12 808 2273 E-mail: [email protected] Personal History: 2006-2013

Wenck Associates, Inc. (Consulting Engineer)

Since 2013 KAUST (PhD Candidate) Research interests: the water/food/energy nexus, sustainable agriculture, water purification and desalination GOLD SPONSOR

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T4.19 ILYA V. VOROTYNTSEV TOWARDS A NEW PARADIGM OF PROCESS INTENSIFICATION IN MEMBRANE GAS SEPARATION BY NOVEL PULSED RETENTATE FLOW APPROACH

ILYA V. VOROTYNTSEV, MAXIM M. TRUBYANOV, STANISLAV V. BATTALOV, EGOR PUZANOV, PAVEL N. DROZDOV, VLADIMIR M. VOROTYNTSEV Nanotechnology and Biotechnology Department, Nizhny Novgorod State Technical University n.a. R.E. Alekseev, 24 Minina Str., Nizhny Novgorod, 603950, Russian Federation A novel unsteady-state cyclic membrane process with a pulsed retentate flow proposed for high purification of gases has been investigated through a simulation and experimental study. Systematic theoretical modeling carried out for gas pairs having various permselectivities shows that pulsed retentate flow operation offers an extended range of performances from the selectivity-productivity point of view. A dedicated experimental verification based on a radial membrane module which can cyclically operate in a so-called closed mode (or dead end) has been done for several systems considering the case of high-penetrating impurity removal from a low-penetrating matrix. Fig.1 represents a comparison of the separation efficiency of a steady-state mode and a pulsed retentate mode depending on the productivity of the process (product recovery) for the example of 1%vol. of nitrous oxide impurity removal from nitrogen as main component on poly(arylate-siloxane) membrane. The effective selectivity α* for the N2O/ N2 system was 8±1.5 (calculated from the experimental data). The N2O concentrations in the retentate flow were measured by GС/mTCD analysis. It has been experimentally confirmed that novel and simple approach may offer substantially higher separation performances in the area of small productivities (common to high purification applications) as compared to a steady-state operation at the same given value of the product recovery (same productivity). This result differs largely from a variety of previous studies considering pulsed feed conditions where the gain in separation efficiency can be obtained mostly for diffusion-controlled separation and at the expense of unavoidable loss of productivity. Improved separation ability of the membrane module in pulsed retentate mode is observed due to the higher driving force of unsteady-state cyclic process when the module periodically works at a distance from a stationary state condition attempting to achieve it. Moreover the separation efficiency of a steady-state operation is limited in the small-productivity area due to the effect of axial mixing in case of very small retentate flow. The dependence of the separation ability of a single membrane module on the

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operating parameters of a pulsed retentate mode (valve closing and opening time, total cycle time, amount of retentate sample, etc.) has been systematically investigated. The novel approach offers a series of promising perspectives for various membrane gas purification applications. Nevertheless more rigorous parametric optimization strategy has to be developed for pulsed retentate flow operation in order to quickly and efficiently identify the best set of operating parameters for a given system and target performance. F

14000

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2000 0

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0.1

0.2

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Figure 1. Separation efficiency vs. productivity for removal of 1%vol. N2O impurity from N2 matrix on poly(arylate-siloxane) in the radial membrane module: 1 – pulsed retentate mode; 2 – steady-state mode.

This work was financially supported by Grant of the President of the Russian Federation (MD-5415.2016.8) and by the Russian Foundation of Basic research (project 16-38-60174 mol_а_dk). ILYA V. VOROTYNTSEV Title: Professor. Nizhny Novgorod State Technical University n.a. R.E. Alekseev (NNSTU), Nizhny Novgorod, Russian Federation Phone: +7 920 0609030 Fax: +78314360361 E-mail: [email protected] 2006

PhD in Physical Chemistry from Lobachevsky University

2004-2006

R&D and production manager of LH GermanLabs RUS, JV

2005-2006

Deputy Director on Science of Firm HORST, Ltd

2011-2013

Deputy Dean of Engineering Chemical Faculty of NNSTU

2014-present

Professor of Nanotechnology and Biotechnology Department of NNSTU

Research interests: gas separation, process intensification, ionic liquids, polymers, membrane module, and membranes

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TH1.2 ROLE OF PROTEIN ADSORPTION ON THEIR DETECTION BY SINGLE NANOPORE MEMBRANE

PHD SÉBASTIEN BALME1, PIERRE EUGÈNE COULON2, MATHILDE LEPOITEVIN1, BENOÎT CHARLOT3, LUDOVIC DUMEE4, MIKHAEL BECHELANY1, JEAN-MARC JANOT1 1 Institut Européen des Membranes, UMR5635, Université de Montpellier CNRS ENSCM, Place Eugène Bataillon, 34095 Montpellier cedex 5, France 2 Laboratoire des Solides Irradiés, École polytechnique, Université Paris-Saclay, Route de Saclay, 91128 Palaiseau Cedex, France 3 Institut d’Electronique et des Systèmes, Université de Montpellier, 34095 Montpellier Cedex 5, France 4 Deakin University, Institute for Frontier Materials, Waurn Ponds, 3216 Victoria, Australia Over the past two decades the emerging single nanopore technologies have opened the route to multiple sensing applications. Beside DNA1 or nanoparticles2, the identification of proteins by nano-fluidics across single nanopore membranes is a promising tool for early diagnosis. The enthusiasm around this technology comes from the apparent simplicity of resistive pulse experiment. Basically, the latter is based on electrical current measurements under a fixed applied voltage. The passage of a unique object through the nanopore induces a perturbation of the electrical current which will depend on the moieties size, shape charge etc. The protein detection can be done using SiNx nanopore, however several fundamentals questions are not totally elucidated. The first one concerns the protein dwell time inside the nanopore. Indeed, the experimental dwell time is typically several orders of magnitude larger than the expected one assuming that a protein is subject to electrophoretic mobility or diffusion only.3 The second one is related to the capture rate of the molecule by the nanopore. Indeed, the latter is lower than the calculated one assuming that the protein entrance inside nanopore is only due to a diffusion process.4 The low capture rate has been interpreted as a direct consequence of the protein adsorption and/or to the missing events due to the fast translocation of protein . In order to investigate the origin of the missing events, the influence of the interactions between the nanopore surface and the proteins should be taken into account. In this talk, we will focus on determining the influence of unspecific protein adsorption on their detection by a single nanopore membrane. Firstly, we will show the translocation dynamic of objet which translocate through a nanopore without interaction with the surface. This will be illustrated by the nanoparticle coated with ssDNA as model system. In this case, the capture rate can be predicted by a simple diffusion model. Secondly, we

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have studied the translocation of 3 proteins (avidin, lysozyme and IgG) because they exhibit different affinity with SiNx surface (Figure 1). In this case, the capture rates were lower than expected and the dwell times are several order of magnitude longer than the expected one. We evidence that they are correlated with the affinity of proteins to the surface. From our result, we propose an assumption based on two different behaviors of the proteins (Figure 1). A first population of protein does not interact with the surface and their dwell time inside the nanopore is too short to be detected. A second one interacts with the nanopore inner surface, their dwell time increases and they could be detected. We will also show the influence of protein geometry the current blockade signal. Finally an example of application to characterize the lysozyme aggregation will be discussed as application in early diagnosis. REFERENCES 1 Branton, D.; Deamer, D. W.; Marziali, A.; Bayley, H.; Benner, S. A.; Butler, T.; Di Ventra, M.; Garaj, S.; Hibbs, A.; Huang, X. H.; Jovanovich, S. B.; Krstic, P. S.; Lindsay, S.; Ling, X. S. S.; Mastrangelo, C. H.; Meller, A.; Oliver, J. S.; Pershin, Y. V.; Ramsey, J. M.; Riehn, R.; Soni, G. V.; Tabard-Cossa, V.; Wanunu, M.; Wiggin, M.; Schloss, J. A.. Nat Biotechnol 2008, 26, 1146-1153 2 Cabello-Aguillar, S.; Abou-Chaaya, A.; Bechelany, M.; Pochat-Bohatier, C.; Balanzat, E.; Janot, J. M.; Miele, P.; Balme, S. Soft Matter 2014, 10, 8413-8419 3 Talaga, D. S.; Li, J. L. Single-Molecule Protein Unfolding in Solid State Nanopores. J Am Chem Soc 2009, 131, 9287-9297 4 Oukhaled, A.; Cressiot, B.; Bacri, L.; Pastoriza-Gallego, M.; Betton, J. M.; Bourhis, E.; Jede, R.; Gierak, J.; Auvray, L.; Pelta, J. Acs Nano 2011, 5, 3628-3638 ; Plesa, C.; Ruitenberg, J. W.; Witteveen, M. J.; Dekker, C.Nano Lett 2015, 15, 3153-3158

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SEBASTIEN BALME Title: PhD, Assistent profressor Institut Européen des Membranes, UMR5635, Université de Montpellier, France Phone: + 3346714911 7 E-mail: [email protected] 2005

PhD physical chemistry European Institute of Membranes, Université de Montpellier (France)

2006-2007

Post-doc department of physical chemistry, Geneva University (Swizerland)

Since 2007

Assistant professor, European Institute of Membrane Université de Montpellier, France

Research interests: Conception, functionalization and characterization of solid-state nanopore membrane (Track-etched and SiN) to mimic biological ionic channel. Studies of transport mechanism of electrolytes, biomacromolecules (DNA, Protein), and nanoparticle through nanopore. Studies of the relationship structure/biological properties of proteins and biological channel (ionic channel, a-hemolysin) under confinement to design hybrid artificial/biological nanopores, membrane and materials.

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TH1.3 MR MATHIEU LARRONDE-LARRETCHE TOWARD A BETTER UNDERSTANDING OF THE FOULING MECHANISMS DURING MICROALGAE DEWATERING BY FORWARD OSMOSIS

MR MATHIEU LARRONDE-LARRETCHE1, DR XUE JIN1 1 School of Engineering, University of Glasgow, Scotland G12 8LT,United Kingdom INTRODUCTION

Microalgae applications have recently gained increasing attention for the production of sustainable biofuel, however harvesting and dewatering techniques still requires improvements. In the meantime, forward osmosis (FO) has shown promising results as a cost-effective filtration method, and its potential for microalgal biomass harvesting has just been realised. Using brines from seawater desalination plants for the concentration of microalgal biomass could efficiently reduce the overall cost of biofuel production. As many aspects of FO for algae harvesting remains unknown, the objectives of this study were to (i) systematically investigate the effect of draw solution (DS) chemistry on flux behaviour and algal harvesting efficiency; (ii) assess the harvesting efficiency with different microalgae species; and (iii) gain in-depth understanding of the mechanisms governing FO fouling during algal harvesting process. METHODS/MATERIALS

Three different microalgae suspensions (Scenedesmus obliquus; Chlamydomonas reinhardtii; Chlorella vulgaris) with an initial biomass concentration of 0.2 g/L, were dewatered with a custom fabricated crossflow cell, using a commercial cellulose triacetate FO membrane with an effective area of 200 cm2. Commercial sea salts, MgCl2, and CaCl2 were investigated as potential DS. Each experiment was terminated when the feed volume was reduced to 25% of its initial value. Permeating water flux, reverse solute diffusion and biomass concentration were measured during each set of experiment. Extracellular carbohydrates, known to exacerbate membrane fouling, were analysed from samples taken during each experiment. Scanning Electron Microscopy coupled with Energy-Dispersive X-ray spectroscopy (SEM-EDX) was also used to analyse the membranes. RESULTS AND DISCUSSION

Our results suggest that the chemistry of the DS used has paramount impact on the severity of fouling and harvesting efficiency during dewatering of microalgae biomass by FO. Indeed, divalent cations diffusing through the membrane such as Mg2+ and Ca2+ interact with the membrane surface, the microalgae cells, and extracellular polymeric substances (EPS), mostly carbohydrates excreted by the microalgae under stress conditions (salinity and hydraulic stress). These generate reductions in (i) permeate flux through the development of a cake layer on the membrane surface, and (ii) harvesting performances through the entrapment of biomass into the feed spacer. Our findings GOLD SPONSOR

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reveal that Ca2+-containing DS (sea salts; CaCl2) had a severe impact on the aforementioned factors with S.obliquus (Fig.1). Similar impact is also found with C. reinhardtii and C. vulgaris. For Ca2+-containing DS, the overall extent of water flux loss followed the order of S.obliquus > C.reinhardtii > C.vulgaris, with respectively 70.9 %, 13.1 %, and 5.3 % with CaCl2 as DS, and 16.3 %, 10.8 % and 8.1 % with sea salts (containing 0.82 g/L Ca2+) as DS. Severe loss of biomass loss was also observed with S.obliquus and C.reinhardtii, mostly when the DS contained high concentration of Mg2+ and Ca2+.

Figure 1. (a) Water flux loss, and (b) microalgae biomass concentration during FO experiments with S. obliquus.

The effect of Ca2+ ions on the flocculation of S.obliquus and subsequent binding of microalgae cells and extracellular polymeric substances with the membrane is highlighted by the microscope images and energy dispersive x-ray analysis (Fig.2). Ca2+ ions assisted the generation of large flocs (over 100 μm in diameter) which entrap into the feed spacer, or bind along with extracellular carbohydrates onto the membrane surface.

Figure 2. (a) Microscope image of a microalgae floc in feed solution, and (b) EDX spectroscopy of the membrane surface after the dewatering of Scenedesmus obliquus with CaCl2 as draw solution.

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Differences in the composition of the microalgae cell wall provide further insight for these results. The influence of Ca2+ ions on S.obliquus was largely due to the fact that the large amount of glucose and mannose1, probably found as glucomannans which carboxylate groups binds with Ca2+, forms bridges between adjacent algae cells and their EPS, forming a highly interconnected gel network. In addition, only S.obliquus cell wall contains fructose, in which the non-vicinal hydroxyl groups binds specifically with calcium to form a strong extensive hydrogen-bond network2. As a result, severe losses in both water flux and biomass were witnessed during the FO dewatering of S.obliquus with Ca2+containing DS. The cell wall of C.reinhardtii contains large amount of galactose3 which was reported to form strong bonds with divalent cations, the binding affinity of Ca2+ found to be greater than that of Mg2+ 4. In addition, galactose was discovered to form acidic polysaccharides with great propensity to form calcium-stabilized gels5. Thus the abundant amount of galactose in C.reinhardtii’s cell wall is very likely to cause a great algae biomass loss with MgCl2 and CaCl2 DS as well as a moderate flux decline with Ca2+containing DS. The lack of fructose, insufficient glucose, mannose and galactose may attribute to the low fouling propensity of C.vulgaris. Clear evidences were found in this study that the FO dewatering performance is highly dependent on both microalgae species and DS chemistry. Our results suggest that among the three microalgae species assessed in this work, C.vulgaris was the most suitable microalgae to be dewatered by FO process due to its unique cell wall carbohydrate composition. Further, the reduction of divalent cations in the DS and the optimization of FO membranes solute permeability would greatly improve the performances of FO for dewatering of microalgae biomass. REFERENCES 1. S. L. Guo, X. Q. Zhao, C. Wan, Z. Y. Huang, Y. L. Yang, M. A. Alam, S. H. Ho, F. W. Bai and J. S. Chang, Bioresource technology, 2013, 145, 285-289. 2. J. Guo, Y. Lu and R. Whiting, Bulletin of the Korean Chemical Society, 2012, 33,

2028-2030.

3. J. Voigt, P. Münzner and H.-P. Vogeler, Plant Science, 1991, 75, 129-142. 4. G. Cioci, E. P. Mitchell, C. Gautier, M. Wimmerová, D. Sudakevitz, S. Pérez, N. Gilboa-Garber and A.Imberty, FEBS Letters, 2003, 555, 297-301. 5. K.-s. Jiang and G. A. Barber, Phytochemistry, 1975, 14, 2459-2461.

MATHIEU LARRONDE-LARRETCHE Title: Mr University of Glasgow, UK Phone: +447724014287 E-mail: [email protected] 2012

Master Degree in Process Engineering, University of Nantes (France)

2013-2016

PhD student in Environmental Engineering, University of Glasgow (UK)

Since 2017

Research assistant in Environmental Engineering, University of Glasgow (UK) Research interests: Membrane Technology, Forward Osmosis, Microalgae, Wastewater Treatment

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TH1.4 JUNHEE RYU ORGANIC MATTER CHRACTERISTICS AND TREATABILITY OF FO CONCENTRATES PRODUCED FROM RAW WASTEWATER, PRIMARY, AND SECONDARY EFFLUENTS

JUNHEE RYU1, JAEHYUN JUNG1,JIHYEON SONG2, JIHYANG KWEON1* 1 Department of Environmental Engineering Konkuk University, 120 Neungdongro Gwangjin-gu, Seoul, Korea Phone: +82-2-450-4053) 2 Department of Civil and Environmental Engineering Sejong University, 209 Neungdong-ro Gwangjin-gu, Seoul, Korea Recently, several novel technologies using forward osmosis (FO) membranes were introduced including recovery of high salinity water from oil/gas industry, resource recovery from wastewater and zero liquid discharge systems in addition to desalination of seawater. FO is an osmotic-driven process and has strength for low energy consumption as compared with pressure-driven process such as RO and nanofiltration (NF). The integrated FO-RO process to desalinate seawater and reuse wastewater have been investigated. FO process is placed as pre-treatment of a RO process and which can reduce energy consumption by increasing the efficiency of RO process. In the FO-RO process, pure water from feed solution moves to the draw solution across the FO membrane by the osmotic pressure difference between the two solutions. Therefore, the draw solution is diluted and the feed solution is concentrated. The membrane process generates waste streams such as brine and concentrate that require disposal with particular methods to minimizing their environmental impacts. Generally, the feed solution of desalination or water reclamation process was used raw wastewater (RW), 1st wastewater effluent (FWE), and 2nd wastewater effluent (SWE). In either case, the integrated FO-RO process generated waste streams consisting of high organic matters, high nutrients, and pollutants. The concentrates from the FO process in the integrated FO-RO system therefore need treatment prior to discharge to meet water quality standards for river discharge of local or national governments. Treatment processes for FO concentrates would be determined mainly based on characteristics of organic contents since the concentrates are originated from RW, FEW, and SWE. In this study, water quality characteristics of FO concentrate using RW, FWE, and SWE, mainly for organic matter, were found out understanding which fractions of organic were remained in concentrates. Also treatment on FO concentrate using membrane bioreactor (MBR) was tried to analyze efficiency of biological treatment.

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Figure 1. Schematic diagram of lab-scale FO process for concentrate ACKNOWLEDGEMENT

This research was supported by a grant (code 16IFIP-B088091-03) from Industrial Facilities & Infrastructure Research Program funded by Ministry of Land, Infrastructure and Transport of Korean government. NAME JUNHEE RYU Department of Environmental Engineering Konkuk University, 120 Neungdongro Gwangjin-gu, Seoul, Korea Phone: +82-2-454-4056 E-mail: [email protected] Mr. Ryu is a ph. D candidate at department of environmental engineering of the Konkuk University. His research interests include membrane processes for water purification, desalination, and treatment of brine.

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TH1.5 CHEMICAL CLEANING STUDY IN COAL SEAM GAS (CSG) RO BRINE TREATMENT BY FERTILIZER-DRAWN FORWARD OSMOSIS

YOUNGJIN KIM1, 2, YUNCHUL WOO2, JIN WANG2, HOKYONG SHON2, SEUNGKWAN HONG1* 1 School of Civil, Environmental and Architectural Engineering, Korea University, Seongbuk-gu, Seoul, Republic of Korea 2 School of Civil and Environmental Engineering, University of Technology, Sydney (UTS), City Campus, Broadway, NSW 2007, Australia INTRODUCTION

Coal seam gas, well known as coal bed methane or coal seam methane, has been developed for a few decades in Australia.11 CSG produced water is extracted with not only coal seam methane gas but also high salinity, organics, and heavy metals. RO has been widely utilized for treating CSG produced water, but its maximum recovery rate is only 70-80% recovery.2 In order to further increase recovery rate for zero liquid discharge and reuse CSG produced water for the beneficial purpose such as irrigation, fertilizerdrawn forward osmosis can be applied for CSG RO brine treatment. However, since fertilizer draw solutes can be reversely diffused to feed solution through FO membrane, they may be able to significantly affect the FDFO performance during CSG RO brine treatment. Therefore, research objectives in this study are to investigate fouling behaviours in FDFO and to evaluate a variety of chemical cleaning agents for controlling membrane fouling. MATERIALS AND METHODS

A laboratory-scale cross-flow FO membrane test unit was operated in a closed-loop mode with diluted DS and concentrated feed solution (FS). The FO cell had two symmetric channels on both sides of the membrane each for the feed and draw solutions. Variable speed gear pumps (Cole-Parmer, USA) were used to provide cross-flows under co-current directions at a cross-flow rate of 8.5 cm/s and solution temperature of 25°C and the solutions were re-circulated in a loop resulting in a batch mode of process operation. The draw solution tank was placed on a digital scale and the weight changes were recorded by a computer in real time to determine the water flux. Conductivity and pH meters (HACH, Germany) were connected to a computer to monitor RSF of draw solutes in the feed tank. Experiments were conducted with TORAY thin-film composite (TFC) polyamide FO membranes with three different fertilizers (i.e. calcium nitrate, CAN (Ca(NO3)2), ammonium phosphate dibasic, DAP ((NH4)2HPO4) and potassium nitrate (KNO3)) as DS and CSG RO brine3 as FS.

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RESULTS AND DISCUSSION

Flux decline in FDFO during CSG RO brine desalination was first investigated. Fig. 1a shows that KNO3 exhibited the severest flux decline due to the significant increase in TDS concentration (i.e., 75.7% for KNO3, 33.9% for CAN, and 35.5% for DAP) caused by the highest reverse salt flux (RSF). Due to both severe flux decline and high RSF, it can be said that KNO3 is not appropriate fertilizer draw solution for CSG RO brine treatment by FDFO. CAN showed severer flux decline than DAP due to its higher initial flux. In order to find out the cause of flux decline, the SEM analysis was carried out. When comparing virgin membrane with membrane with KNO3, organic foulants are observed on the membrane surface. However, membrane surfaces with DAP and CAN are fully covered by foulants which look like scales. To further investigate foulants in detail, the EDX analysis was conducted (Fig. 1c). In case of KNO3, C element was more than 80% of total elements, indicating that most of foulants are organics. In case of CAN, the fouling layer is consisted of only Ca, C and O elements, suggesting that the major foulant is calcite (CaCO3) scale. In case of DAP, EDX results show that P and O elements exist in the fouling layer. Thus, it can be estimated that the major foulant is PO4 related scale. To confirm our estimation, the XRD analysis was carried out (Fig. 1d). XRD results show that KNO3 and CAN have similar peaks with virgin membrane, which indicates that no scaling was formed. However, DAP has similar peaks with reference peaks of struvite, indicating that struvite was dominantly formed on the membrane surface. To investigate reversibility of the membrane fouling layer, physical cleaning was applied (Fig. 1b). KNO3 showed the severest flux decline, but water flux was fully recovered by physical cleaning since the major cause of flux decline was a significant increase in feed concentration by RSF. In case of CAN, after physical cleaning, water flux was easily recovered more than 95%. In case of DAP, only 80% of water flux was recovered by physical cleaning. Therefore, chemical cleaning is required for controlling membrane fouling when using fertilizer draw solution (e.g., DAP and MAP) containing NH4+ and PO43- nutrients. To investigate the effect of DAP concentration on membrane fouling, FDFO experiments were carried out with varying DS concentration. Results showed that flux decline was getting severer and flux recovery was getting lower as DS concentration increases. To investigate the effect of various chemical cleaning agents on membrane cleaning efficiency, 3 different chemicals (EDTA, Citric acid, and NaOH) were employed and citric acid showed the highest cleaning efficiency. To evaluate the effect of the consecutive chemical cleaning on fouling mitigation, long-term experiments were carried out for 5 days. This consecutive chemical cleaning slightly affected flux recovery rate and fertilizer draw solution quality (i.e., final concentration and organic rejection)

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Figure 1 (a) Flux decline in fertilizer-drawn forward osmosis during CSG RO brine treatment, (b) the influence of physical cleaning on flux recovery, (c) EDX measurement results, and (d) XRD analysis results CONCLUSION

CSG RO brine treatment by FDFO was investigated to minimize CSG RO brine and reuse treated water for an agricultural purpose. KNO3 having high RSF accelerated flux decline by increasing TDS concentration in feed solution. CAN and DAP having Ca2+ and PO42nutrients caused membrane scaling fouling but PO43- related scaling showed less reversibility than CaCO3 scaling. As DAP DS concentration increased further, both flux decline and physical cleaning efficiency became severer. When testing a variety of chemical agents, it was found that citric acid has the highest cleaning efficiency since major foulants were inorganic scales. During the consecutive chemical cleaning, recovery rate and DS quality became lower. ACKNOWLEDGEMENTS

This research was supported by a grant (code 16IFIP-B088091-03) from Industrial Facilities & Infrastructure Research Program funded by Ministry of Land, Infrastructure and Transport of Korean government.

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YOUNGJIN KIM Title: Mr. Korea University, South Korea Phone: +82-10-5425-8644 Fax: +82-2-928-7656 E-mail: [email protected] 2010-2011

M.S at Korea University, Republic of Korea

Since 2012 Ph.D student at Korea University, Republic of Korea Research interests: Desalination (i.e., RO, FO and MD) and Wastewater treatment Organic micro-pollutants (OMP) rejection in closed-loop FO/RO: a pilot plant study dr.ir. Juan Carlos Ortega-Bravo1, Ing. Danny Harmsen2, prof. dr.ir. Arne Verliefde3, Ir. Arnout D’Haese3, prof.dr.ir. David Jeison1, Dr.ir Emile Cornelissen2,4 1Universidad de La Frontera (Chemical Engineering Department), 2KWR Watercycle Research Institute, 3Ghent University (Particle and Interfacial Technology Group), 4Singapore Membrane Technology Centre 1992 - He obtained his Chemical Engineering MSc degree at the University of Twente (the Netherlands). 1997 - He obtained his Chemical Engineering PhD degree at the University of Twente (the Netherlands). 1997-2002 - He worked as a Process Engineer at Seghers better technology for Water in Belgium and worked on membrane filtration in waste water treatment. Since 2003 - He is a Senior Scientific Researcher at KWR Watercycle Research Institute and his research topics include membrane fouling and cleaning, rejection of emerging contaminants by pressure driven membranes and developing innovative processes Since 2014 - He is a Visiting Scientist at the Singapore Membrane Technology Centre (SMTC) at the NTU in Singapore. He published more than 81 papers in well-respected scientific journals (h-factor of 22), co-filed 3 patents and written three book chapters. He received several innovation awards in the field water treatment and membrane filtration.

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TH1.6 ELHAM RADAEI NUMERICAL MODELLING OF HYDRODYNAMIC CHARACTERISTICS OF SPHERICAL CAP BUBBLE FLOW IN AN IMMERSED HOLLOW FIBRE MEMBRANE SYSTEM

ELHAM RADAEI1, YUAN WANG1, GREG LESLIE1, FRANCISCO TRUJILLO1, 2 1 UNESCO Centre for Membrane Science & Technology, School of Chemical Engineering, University of New South Wales, Sydney 2052, Australia 2 Food Science & Technology, School of Chemical Engineering, University of New South Wales, Sydney 2052, Australia Fouling in submerged membrane systems can be controlled by air sparging which generates shear stress at the membrane surface and increases the rate of particle back-transport1. The efficiency of gas sparging for fouling control depends mainly on the effective distribution of bubbles and the bubble-induced flow across membranes. Both the time-averaged and the amplitude of wall shear stress (the difference between the maximum and minimum shear stress) influence flux enhancement2. Gaucher et al. showed that the fluctuating component of wall shear rate is the most important factor that controls fouling3. Recently, large spherical cap bubbles have been used in immersed membrane systems exhibiting an enhanced efficiency in fouling removal compared to coarse bubbles due to higher shear stress fluctuations4-7. Empirical measurement of filtration performance as a function of bubble size and air intensity for different membrane fibre materials, dimensions, and module geometries is limited and is not clear how these variables influence time-averaged and the amplitude of wall shear stress. Current optical techniques used to observe particle deposition near the membrane surface have a limited in-plane view due to the low depth of field. Consequently, it is not possible to observe, by using non-intrusive measurement techniques, the concentration profile in the boundary layer adjacent to the membrane or cake layer or to estimate the cake layer thickness. Numerical techniques offer some insight into turbulence and mass transfer for flat sheet or tubular membrane configurations where the membrane position is fixed relative to the fluid flow. However, these models have limited relevance to the more widely used hollow fibre systems which are more complicated8-10. In this study, a three-dimensional Computational Fluid Dynamics (CFD) model was developed using ANSYS-FLUENT® (15.0) to study the hydrodynamic characteristics (time-dependent local velocity vectors and shear stresses) of industrial scale hollow fibres. Five tight hollow fibres with an effective length of 1.5 m and 1.3 mm in diameter were immersed in a water tank aerated by a rising single spherical cap bubble with volume of 100 ml. Volume of Fluid (VOF) method was coupled with RNG k – e turbulent model to simulate the transient behaviour of the cap bubble in the air-liquid two-phase flow. The

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magnitude of CFD modelled flow velocity was compared with experimental results reported in the literature4. CFD predictions exhibit similar trends to the experimental data. For instance, Fig. 1 shows velocity distribution when bubble reached the middle of tank at 1.4 sec. As can be seen in Fig. 1, the magnitude of velocity increases rapidly at the bubble (red point). Afterwards, the peak velocity is observed at the wake behind the bubble (yellow point) and it gradually decreases to the bottom of the wake (blue point). Similar distribution has been observed experimentally for small spherical bubbles11. It has been shown that wake zone are effective for fouling control because of the large and variable shear stresses generated in this zone12,13. Furthermore, CFD results shows that the shear stress is maximum in the centre hollow fibre, which is the closest to the rising bubble, and it rapidly decreases to the side of the tank. Fig. 2 shows the shear stress vs. time at a height of 0.75 m of three different fibre positions. This approach which combines numerical simulation with experimental observation provides a basis for systematic evaluation and optimisation of a range of design variables including bubble size, aeration intensity fibre properties and tank configuration in systems employing large spherical cap bubbles for fouling control.

Figure 1. CFD results of velocity at the centre of tank at 1.4 sec; a) velocity distribution, b) Spherical bubble shape and position

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Figure 2. CFD results of shear stress distribution induced by rising bubble at different fibres position REFERENCES 1. C.C.V. Chan, P.R. Bérubé, E.R. Hall, Water Res., 2011. 45(19): p. 6403-6416. 2. G. Ducom, F.P. Puech, C. Cabassud, Desalination, 2002. 145(1–3): p. 97-102. 3. C. Gaucher, P. Legentilhomme, P. Jaouen, J. Comiti, J. Pruvost. Exp. in Fluids, 2002. 32(3): p. 283-293. 4. S. Jankhah, P.R. Berube, Water Res., 2013. 47(17): p. 6516-6526. 5. S.Z. Abdullah, H.E. Wray, P. R. Bérubé ,R. C. Andrews, Desalination, 2015. 357: p. 117-120. 6. D. Ye, S. Saadat-Sanei, P.R. Bérubé, Sep. and Purification Tech., 2014. 123: p. 153-163. 7. K. Zhang, Z. Cui, R.W. Field, J. of Membrane Sci., 2009. 332(1-2): p. 30-37. 8. P. Wei, K. Zhang, W. Gao, L. Kong, R. Field, J. of Membrane Sci., 2013. 445: p. 15-24. 9. Y. Wang, M. Brannock, Sh. Cox, G. Leslie, J. of Membrane Sci., 2010. 363(1-2): p. 57-66. 10. X. Liu, Y. Wang, T. D. Waite, G. Leslie, Water Res, 2015. 75: p. 131-145. 11. D. Bhaga, M.E. Weber, Chem. Eng. Sci., 1980. 35 (12), 2467-2474. 12. N. Ratkovich, P.R. Berube, I. Nopens, Chem. Eng. Sci., 2011. 66(6): p. 1254-1268. 13. N. Ratkovich, C. C. V. Chan, P.R. Berube, I. Nopens, Water Sci. & Tech., 2011. 64(1): p. 189-198.

ELHAM RADAEI Title: Ms. PhD Candidate, Country: Australia Phone: +61469281851; E-mail: [email protected] 2006-2010

B.Sc. of Civil Engineering, Amirkabir University of Technology, Tehran, Iran 

2010-2012

M.Sc. of Environmental Engineering, Amirkabir University of Technology, Tehran, Iran

2012-2015

Technical expert of Southern Tehran’s Wastewater Treatment Plant, Ab,Sazeh,Fazelab Consultant Engineers Company, Tehran, Iran

Since 2015

PhD candidate, UNESCO Centre for Membrane Science & Technology, School of Chemical Engineering, University of New South Wales, Sydney, Australia

Research interests:Water and Wastewater treatment, Numerical modelling, Fluid dynamics of membrane systems

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TH1.7 JINGWEI HOU EXPLORING THE DUALITY OF JANUS MEMBRANES: A PATHWAY TO REALIZE HIGHLY EFFICIENT SEPARATIONS

JINGWEI HOU1, HAO-CHENG YANG2, WENWEI ZHONG1, ZHI-KANG XU2 AND VICKI CHEN1 1 UNESCO Centre for Membrane Science and Technology, the University of New South Wales, Australia 2 Zhejiang University, China Like the ancient Roman god, a Janus membrane has different properties on each side, including chemical or physical aspects like chemical component, surface morphology, wettability, surface charge and so forth. In a broader sense, this definition includes the conventional asymmetric membranes. However, a more specific definition conceptually that the Janus membrane should have opposing properties on each side, usually hydrophilicity/hydrophobicity or positive/negative charges. As a result, the Janus properties are limited to the membrane surface properties. Nature has provided several representative examples of using the Janus concept to realize advanced functions. For example, in animal tissues, the carbonic anhydrase, an enzyme catalyzing the CO2 hydration into blood, is immobilized on the Janus cell membrane or lung endothelial surface. The Janus configuration of these CO2 permeable layers minimized the CO2 mass transfer [1] Another example is the spontaneous water transport through the aquaporin [2]. As a result, the Janus membranes can be used for directional transport, oil-water separation, as well as performance optimization of the conventional membrane processes. Usually, the fabrication of Janus membrane can be challenging. Due to the porous nature of membranes, a wet chemistry process modification usually leads to the homogeneous modification of the whole membrane due to the capillary effect. Other common fabrication approaches include single-side photo-degradation, cross-linking, single-side coating and sequential surface modification [2]. For example, in our earlier research we coated a hydrophilic carbon nanotubes layer on a superhydrophobic PVDF membrane support for biocatalytic Janus membrane fabrication. However, the complicated fabrication process makes the scale-up difficult. On the other hand, the application of the mussel-inspired polydopamine (PDA) for membrane surface modification shows great potential [3,4]. The deposited PDA layer is hydrophilic and the presence of amine and catechol groups can induce further mineralization of inorganic nanoparticles. We have developed a facile single-side PDA deposition technique for the Janus membrane fabrication, simply by immersing the hydrophobic polymer support into PDA solution. During the PDA deposition process, the surface would be gradually wetted. Thus the PDA deposition depth can be tuned by simply applying different deposition time. Our initial attempt with the PDA-based Janus membrane was to explore its application in a GOLD bubble aerator [5]. The Janus membrane was fabricated by floating aSPONSOR flat sheet PP MF membrane on the surface of a PDA solution under room temperature. Then the

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Figure 1. Schematic diagram of the CO2 aerator with Janus membrane, and CO2 hydration rate with nascent and Janus membranes.

We further applied the Janus concept to promote the membrane distillation (MD) performance. During the MD process, the thicker membrane would lead to higher thermal resistance, which is beneficial for keeping the MD driving force. However, this is accompanied by the loss of mass transfer efficiency. At the same time, we discovered the heat is mainly conducted via the membrane matrix while the water vapour is transported via membrane pores. As a result, we strategically modified hollow fiber hydrophobic PP membranes with PDA: the PDA solution would gradually wet the hydrophobic membrane pores, leading to a time-dependent increment of the hydrophilic layer thickness (Figure 2). The resultant membrane exhibited improved water flux in direct contact MD, and the stable salt rejection was observed over a 24 h continuous MD test with saline feed [6].

Figure 2. Schematic diagram of the Janus membrane fabrication process, and the MD water flux using Janus membrane with different PDA deposition time.

The presence of catechol in the PDA deposition layer can form covalent bonding with the amine groups of a protein molecule. In view of this, the PDA-based Janus membrane can be a promising platform for biocatalytic membrane contactor. For example, the oxidation of phenolic components catalyzed by laccase requires the involvement of dissolved oxygen. After immobilizing laccase onto the PDA-based Janus membrane, the enzyme would locate at the gas-liquid interface. The abundance of the local dissolved oxygen level could promote the biocatalytic reactor efficiency. This line of research is currently being carried out.

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REFERENCES 1

J. Hou, C. Ji, G. Dong, B. Xiao, Y. Ye, V. Chen, Biocatalytic Janus membranes for CO2 removal utilizing carbonic anhydrase, J. Mater. Chem. A. 3 (2015) 17032–17041. doi:10.1039/C5TA01756D.

2

H.-C. Yang, J. Hou, V. Chen, Z.-K. Xu, Janus membranes: exploring duality for advanced separation, Angewandte Chem. Int. Ed, in press. doi: 10.1002/anie.201601589

3

H.-C. Yang, J. Hou, V. Chen, Z.-K. Xu, Surface and interface engineering for organic–inorganic composite membranes, J. Mater. Chem. A. 4 (2016) 9716–9729. doi:10.1039/C6TA02844F.

4

H.-C. Yang, J. Luo, Y. Lv, P. Shen, Z.-K. Xu, Surface engineering of polymer membranes via musselinspired chemistry, J. Membr. Sci. 483 (2015) 42–59. doi:10.1016/j.memsci.2015.02.027.

5

H.-C. Yang, J. Hou, L.-S. Wan, V. Chen, Z.-K. Xu, Janus Membranes with Asymmetric Wettability for Fine Bubble Aeration, Adv. Mater. Interfaces. 3 (2016) 1500774. doi:10.1002/admi.201500774.

6 H.-C. Yang, W. Zhong, J. Hou, V. Chen Z.-K. Xu, Janus hollow fiber membrane with a mussel-inspired coating on the lumen surface for desalination. J. Memb. Sci. Submitted.

JINGWEI HOU Title: Dr UNESCO Centre for Membrane Science and Technology, the University of New South Wales, Australia Phone: +6193854341 E-mail: [email protected] 2014

Research Associate

2010-2014

PhD student

Research interests: Janus membrane, Antibacterial membrane, Oil-water separation Gas separation, Biocatalytic membrane reactor

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TH1.8 SANKHA KARMAKAR REMOVAL OF REACTIVE BLACK DYE USING MIL-101-CR METAL ORGANIC FRAMEWORK IMPREGNATED CELLULOSE ACETATE PHTHALATE MIXED MATRIX ULTRAFILTRATION MEMBRANE

SANKHA KARMAKAR AND SIRSHENDU DE* Department Of Chemical Engineering, Indian Institute Of Technology, Kharagpur ABSTRACT:

Toxic and carcinogenic reactive dyes are abundantly used in textile industries due to their wide variety of colour and texture. MOF is a (potentially) porous coordination network built from metal (cluster) nodes with bridging organic ligands which exhibit high surface area, easily tuneable pore size and various degrees of stability. Application of MOF in water treatment is scant in literature. In this study, metal organic framework (MOF) impregnated flat sheet mixed matrix membrane was used to remove reactive black dye from aqueous solution. Synthetic solution of this dye was subjected to filtration using a MIL-101-Cr embedded cellulose acetate phthalate (CAP) flat sheet membrane. MIL-101-Cr had been prepared indigenously using solvo-thermal method, having a surface area of 2410 m2/g. The membrane was characterized using scanning electron microscopy (SEM), contact angle, permeability, molecular weight cut off, pore size, mechanical strength and zeta potential. Reactive black dye was completely removed by adsorption at pH 7. Maximum Langmuir adsorption capacity of nascent MIL-101-Cr for this dye was 250 mg/g at room temperature (30°C). Effects of trans-membrane pressure drop and cross flow rate on the throughput of the process was investigated. Three different washing protocols were tested for their efficiency and the acid-alkali wash was found to be the most effective. Leaching of the concerned MOF in the permeate was tested and it was found out to be negligible. Key Words: Metal organic framework, mixed matrix membrane, adsorption, ultrafiltration, dye rejection

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TH1.9 MRINMOY MONDAL REMOVAL OF CONGO RED DYE USING MAGNETIC NICKEL–IRON OXIDE (NFO) NANOPARTICLE INCORPORATED POLYSULFONE (PSF) MIXED MATRIX ULTRAFILTRATION HOLLOW FIBER MEMBRANE

MRINMOY MONDAL AND SIRSHENDU DE Department of Chemical Engineering, Indian Institute of Technology, Kharagpur Hollow fiber mixed matrix membrane (MMM) of PSF and magnetic NFO nanoparticle was prepared. The membrane was characterized by scanning electron microscopy, atomic force microscopy, contact angle, permeability, molecular weight cut off, pore size, mechanical strength and zeta potential. Hydrophilicity, permeability, molecular weight cut off and zeta potential of MMM increased with NFO concentration. The hollow fibers had negatively charged surface at pH 7 due to the point of zero charge of NFO at pH 3.7. Performance of the membranes was tested in terms of removal of congo red dye, monovalent and divalent salt. Rejection of 1000 mg/l sodium chloride solution was in between 25 to 30% at pH7, and for divalent sodium sulphate, it was in the range of 35 to 40%. Rejection of 200 mg/l dye congo red was found to be 100% at pH 7. Salts and dyes are rejected by the membranes due to charge interaction. NFO incorporated membranes showed reasonable antifouling characteristics having flux recovery ratio of more than 85% and a flux decline ratio of less than 15%. These hollow fibers have great potential in textile effluent treatment. Key Words: Magnetic nanoparticle, hollow fibers, mixed matrix membrane, ultrafiltration, dye rejection

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TH2.11 SHANSHAN ZHAO GAS FIELD PRODUCED/PROCESS WATER TREATMENT USING FORWARD OSMOSIS HOLLOW FIBER MEMBRANE: MEMBRANE FOULING AND CHEMICAL CLEANING

SHANSHAN ZHAO1,JOEL MINIER-MATAR2, RONG WANG1,3, ANTHONY GORDON FANE1,3, SAMER ADHAM2 1 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Cleantech Loop, Singapore 637141, Singapore 2 ConocoPhilips Global Water Sustainability Centre, #109, Tech 2 Bldg., Qatar Science & Technology Park, PO Box 24750, Doha, Qatar 3 School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore Large amounts of produced and process water (PPW), generated from the oil and gas exploration and production, has become a worldwide problem. The PPW Management is one of the key challenges for the sustainable development of oil and gas industry. At present, the most common managing method of these streams onshore is by deep-well injection. However, the process is costly and its long-term adverse impacts to the environment are not well understood. Therefore, reducing disposal volume is considered to be crucial to make the deep-well injection a cost-effective option and to minimize its potential environmental impacts. In Qatar, a specific target was set to reduce the injection volumes by 50% to ensure the sustainable development1. Forward osmosis (FO) is an emerging membrane technology for water treatment driven by osmotic pressure gradient across the membrane2. Employing FO for PPW treatment has been gaining momentum recently because of its ability to recover a large amount of water for reuse as well as to reduce the volume of these waste streams for disposal. Although flat sheet FO membranes have been reported for treatment of wastewater from shale gas and coal bed methane exploration3, the feasibility of FO process for treating PPW from conventional gas fields and the fouling behavior of the membrane in hollow fiber configuration warrants to be further investigated because the feed constituents vary significantly depending on the different feed sources. Moreover, fouling inevitably occurs in the FO process, and a systematic comparison of the cleaning efficiencies of various chemical cleaning agents is needed in order to provide an optimized cleaning protocol for potential long-term operation.

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In this work, the fouling behavior of an in-house fabricated thin-film composite (TFC) FO hollow fiber membrane in the application of reducing volume of PPW from a real gas field was investigated and the chemical cleaning protocols for water flux recovery was systematically studied. Specifically, the fouling behavior of the FO hollow fiber membrane during PPW treatment was firstly observed. The result shows that membrane fouling happens immediately once the process starts. The water flux drops fast in the first one hour and, subsequently, the flux decline rate decreases. The foulants may deposit and entrap within the selective layer, resulting in the decrease of the water permeability and the increase of the salt rejection. To investigate the foulants on membrane surface, a series of characterization tools including scanning electron microscope (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were used. Table 1 summarizes the detailed changes of the surface compositions of the membrane after fouling. The results indicate the deposition of organic species on the membrane surface after the PPW filtration. The foulants may contain aromatic and/or aliphatic carbon groups, hydroxyl and/or ether groups, and C-O/-COOH groups. Table 1 The chemical state and surface compositions of the virgin and fouled membranes a

Virgin membrane

Fouled membrane

Components

Peak binding energy (eV)

Composition (Atom %)

Peak binding energy (eV)

Composition (Atom %)

C 1s C-C/C-H

285.0

60.7

285.0

68.7

C 1s C-N

286.1

7.3

N.A.b

N.A.b

C 1s C-O

N.A.b

N.A.b

286.8

3.6

C 1s -COOH/N-C=O

288.4

8.7

288.5

5.7

O 1s O=C-N/-COOH c

531.8

11.2

531.6

9.0

O 1s O-C/-COOH d

533.5

4.7

533.4

6.9

a Exclude N 1s result, b N.A.=Not applicable, c Oxygen double bonded to carbon, d Oxygen single bonded to carbon.

In order to recover membrane performance, the cleaning efficiencies of various cleaning agents, including sodium dodecyl sulfate (SDS), ethylenediaminetetraacetic (EDTA) and NaOH, have been systematically studied. Cleanings were performed for 15 and 30 min durations, respectively. Fig. 1 illustrates the cleaned membrane performance in both RO and FO modes. The results show that cleaning with SDS for 15 min is the most effective method for restoring membrane performance in comparison with EDTA and NaOH.

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(a) 1.2

1.0

(b)

30 min

0.8 0.6 0.4 0.2 0.0

SDS

(c) 1.0

EDTA

15 min Fouled membrane

60 40 20 0

SDS

0.20(d)

30 min

30 min

80

NaOH

EDTA

15 min Virgin membrane

NaOH

30 min

0.15

0.8 0.6 0.4

0.10 0.05

0.2 0.0

15 min

100 Virgin membrane

NaCl rejection (%)

15 min Fouled membrane

Js/Jv (g/L)

Normalized water flux (Jv/Jv0)

Normalized water permeability

THEME: MIXED SESSION ON MEMBRANES

SDS

EDTA

NaOH

0.00

SDS

NaOH

EDTA

Figure 1. A comparison of the cleaning efficiencies of 10 mM SDS (pH=9.4, without adjustment), 1 mM EDTA (pH=11) and NaOH (pH=11) solutions at different cleaning durations (a) and (b): in RO mode using DI water and 500 ppm NaCl as feed under 1 bar, respectively, (c) and (d): in FO mode using DI water as feed water and 1 M NaCl as draw solution.

(b)

20 Run 1 Run 2 Run 3 Run 4 Run 5

1.0

Fouled membrane

Cleaned membrane

0.8

15

0.6

10

0.4

5 0

Normalized water flux (Jv/Jv0)

Water flux (LMH)

(a) 25

0.2

0

2

4

6

8 10 12 14 16 18 Time (h)

0.0

1

2

3 4 Running cycles

Figure 2. FO performance of the membrane during batch cycle treatment of PPW (a) raw PPW as feed water and 1 M NaCl as draw solution with 50 % volume reduction, (b) DI water as feed water and 1 M NaCl as draw solution.

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The FO performance of the membrane during batch cycle treatment of the gas field PPW was also investigated and shown in Fig. 2. For each cycle, the fouled membrane was cleaned using 10 mM SDS solution for 15 min. It can be seen that the FO performances are very stable during periodical treatment. The FO membrane can reduce 50 % volume of the waste stream at a relatively high average water flux of 15.6 L·m-2·h-1 using 1 M NaCl as draw solution at active layer facing feed solution (AL-FS) orientation. In conclusion, SDS cleaning is more effective for restoring membrane performance during treatment of the gas field PPW. This study suggests great potential of FO membrane technology for PPW volume reduction. REFERENCES 1

J. Minier-Matar, A. Santos, A. Hussain, et al., Environ. Sci. Technol., 2016, 50, 6044-6052.

2 R. Wang, L. Shi, C.Y.Y. Tang, et al., J. Membr. Sci., 2010, 355, 158-167. 3 B.D. Coday, P. Xu, E.G. Beaudry, et al., Desalination, 2014, 333, 23-35.

SHANSHAN ZHAO Title: Research Fellow Nanyang Technological University (NTU), Singapore Phone: +65-98685131 E-mail: [email protected] 2013-present

Research Fellow, Singapore Membrane Technology Centre, NTU

2008-2013

Ph.D. in Environmental Science and Engineering, HIT

Research interests: FO and NF membrane fabrication and modification

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TH2.12 SHUAIFEI ZHAO MEMBRANE TECHNOLOGY FOR WATER AND HEAT RECOVERY FROM POWER STATION FLUE GAS

SHUAIFEI ZHAO1,2, TAO WU2, MAOWEN YUE3, HONG QI3,PAUL HM FERON4 1 Department of Environmental Sciences, Macquarie University, Sydney 2109, New South Wales, Australia 2 Collaborative Innovation Centre of Membrane Separation and Water Treatment, Zhejiang University of Technology 3 Membrane Science and Technology Research Centre, Nanjing Tech University, Nanjing 210009, Jiangsu, China 4 CSIRO Energy, Newcastle 2300, New South Wales, Australia ABSTRACT

Waste gaseous streams from industrial processes, such as power generation and dry operations, contain large quantities of water vapor and thus represent large losses of latent heat. They can be considered to be a valuable alternative source of water and process heat if cost-effective recovery approaches can be developed. Membrane processes have been used for water and/or heat recovery from gaseous streams (e.g. flue gas). These membrane processes are mainly based on water vapor condensation on the feed side using hydrophobic porous membranes1 or on the permeate side using hydrophilic nanoporous membranes 2, 3. 20 - 60% water recovery and 30 - 80% heat recovery from flue gas between 50 and 90 °C are achievable4, 5. Such performances can significantly improve thermal efficiency of the boiler and make the power plant se lf-efficient in terms of water. In this study, we employed both monochannel and multichannel tubular membranes as the condenser to recover water and heat from water vapor saturated gas streams, and compared their performances in terms of water and heat transfer rates and recoveries. It shows that nanostructured tubular ceramic membranes can be effectively used for simultaneous water and heat recovery from power station flue gas. The multichannel membrane has much larger mass and heat transfer resistances, leading to lower mass and heat transfer rates. The multichannel membrane shows larger volumetric mass and heat transfer coefficients, comparable water recoveries, but lower heat recoveries compared with the monochannel tubular membrane. 20-65% water recovery and 20-85% heat recovery are achievable when using cold water as the coolant.

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Figure 1. Schematic illustration of the membrane condensation process for water and heat recovery from coal-fired power station flue gas.

Figure 2. Water and heat fluxes as functions of: (A) air velocity, (B) water velocity, (C) transmembrane pressure difference, and (D) inlet gas temperature.

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Figure 2. shows that operational parameters (e.g. fluid velocity and transmembrane pressure) have less effects on mass and heat transfer rates in the multichannel membrane, suggesting that transfer resistance from the membrane itself rather than the boundary layers dominates mass and heat transfer in membrane condensation using multichannel membranes; while membrane resistance dominates mass and heat transfer when using monochannel membranes. REFERENCES 1

Macedonio, F.; Brunetti, A.; Barbieri, G.; Drioli, E., Ind. Eng. Chem. Res. 2012, 52, 1160-1167.

2

Wang, D.; Bao, A.; Kunc, W.; Liss, W., Appl.Energy 2012, 91, 341-348.

3

Bao, A.; Wang, D.; Lin, C.-X., Int. J. Heat Mass Transfer 2015, 84, 456-462.

4

Wang, T.; Yue, M.; Qi, H.; Feron, P. H. M.; Zhao, S., J. Membr. Sci. 2015, 484, 10-17.

5

Yue, M.; Zhao, S.; Feron, P. H. M.; Qi, H., Ind. Eng. Chem. Res. 2016, 55, 2615-2622.

DR SHUAIFEI ZHAO Macquarie University, Sydney Australia Phone: +61 2 98509672, E-mail: [email protected] 2016-now

Research Fellow at Macquarie University

2015-2016

Visiting scholar at Nanjing Tech University

2012-2015

Postdoctoral Fellow at CSIRO

2009-2012

PhD student at University of South Australia

Research interests: forward osmosis, membrane distillation, membrane condensation, pressure driven membrane processes, membrane fabrication, desalination and water treatment.

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TH2.13 DIPL. -ING. SERKAN ARSLAN INTERNAL APPLICATION OF NANOFIBER OSMOTIC MEMBRANE IN MEMBRANE BIOREACTOR

DIPL. -ING. SERKAN ARSLAN1, MR. MSC. TAHA ASLAN2, MS. SEDA GAZIOĞLU2, MR. PHD MURAT EYVAZ1, MS. PHD DERYA İMER2, MR. PHD EBUBEKIR YÜKSEL1, MR. PHD İSMAIL KOYUNCU2 1 Gebze Technical University 2 İstanbul Technical University, 3 National Research Center on Membrane Technologies, Istanbul Technical University

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TH2.14 ENDRE NAGY INTEGRATION OF FOULING INTO MODELS OF OSMOTICALLY DRIVEN MEMBRANE PROCESSES

ENDRE NAGY1,, IMRE HEGEDÜS1, EMILY W. TOW2, JOHN H. LIENHARD V2 1 Research Institute of Chemical and Process Engineering, University of Pannonia, Egyetem u. 10, H-8200, Veszprém, Hungary 2 Rohsenow Kendall Heat Transfer Laboratory, Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, USA The performance of forward osmosis (FO) and pressure retarded (PRO) osmosis can be significantly affected by membrane fouling due to the accumulation of deposited particles, colloids, organic macromolecules, inorganic solutes, microorganisms, etc. in a mass transfer boundary layer adjacent to the membrane surface. The resulting concentration of dissolved molecules at the membrane as well as the pressure drop through the fouling layer reduce the chemical potential of the solvent and thus the solvent flux through the membrane. Modeling of salt and water transport through the fouling layer can be used to predict the effect of fouling on the solvent flux and solute rejection of FO and PRO processes. Recently Tow and Lienhard [1] developed a model for quantifying porous foulant accumulation on semipermeable membranes in terms of two parameters that capture both osmotic and hydraulic causes of flux decline. Applying the salt transfer rate given for every single mass transfer layer [2], including that for the fouling layer [1], the salt flux and water flux will be expressed by two algebraic equations that capture the effect of five transfer layers: the membrane active and support layers, two external boundary layers and the fouling cake layer. Through these equations, the effect of fouling on membrane performance can be predicted easily. Two operating modes will be discussed in this presentation: (i) the FO process, in which the feed is facing the selective membrane layer, and (ii) the PRO process, in which the feed solution is facing the support layer. Modeling fouling in PRO orientation is more complex because foulant can accumulate both inside and outside of the porous support layer. Results of the model are compared with experimental data. The National Development Agency grant, Hungarian Research Fund (OTKA 116727) greatly acknowledged for the financial support. REFERENCES

286

1

Tow, E. W., Lienhard V. J.H. Quantifying osmotic membrane fouling to enable comparison across diverse processes. J. Membr. Sci. 511 (2016) 92-107.

2

E. Nagy, A general, resistance-in-series, salt- and water flux models for forward osmosis and pressure retarded osmosis for energy generation, J. Membr. Sci., 460 (2014) 71-81

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ENDRE NAGY Title: Integration of fouling into models of osmotically driven membrane processes University of Pannonia, Hungary Phone: +36203518725 Fax: +3688624040 E-mail: [email protected]; [email protected] 1969

Veszprém University of Chemical Engineering Degree: M. Sc

1973

degree of dr. techn

2000

degree of habilitation

2002

full professor at University of Pannonia (previously: Veszprém Univ.)

2005-2011 director 2016

Emeritus professor

Research interests: 1. Pervaporation process: separation of two-component mixtures (1971-)

2. Enzyme catalyzed reactions: hydrolysis of maltodextrin, hydrolysis of triglicerid esters, enzyme membrane bioreactors (1985-)

3. Heterogeneous catalytic reaction: isomerization of n-hexane on zeolite catalyst (1979-1990)

4. Mixing in fermentation reactors, scale-up (1991-1994)



5. Mass transfer and separation by membrane processes (1971-)



6. Separation of optically active components by membrane processes (2000-2011)



7. Controlled drug release (2002-2008)



8. Biomass utilization, bioethanol, biochemicals production (2005-)



9. Investigation of enzyme nanoparticles (2005-)

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TH2.15 ALI ALTAEE PERFORMANCE OF FO-RO AND RO FOR SEAWATER DESALINATION

ALI ALTAEE AND JOHN ZHOU University of Technology Sydney, School of Civil and Environmental Engineering, Ultimo. NSW 2007, Australia ABSTRACT

Forward Osmosis (FO) has been proposed as an alternative for seawater desalination using Reverse Osmosis (RO) membrane technology for regeneration of the draw solution. Regeneration process is considered the most energy intensive step in the FO-RO system. Previous studies have shown that RO is more energy efficient than an FO-RO system due to the high energy demands of the regeneration process and suggested FO-RO should be focused on high salinity feeds. Model calculations were performed to evaluate the performance of both FO-RO and RO, including the impact of seawater salinity, Energy Recovery Device (ERD), pretreatment cost, and membrane fouling. Results suggested that the optimized Forward Osmosis-Reverse Osmosis system was still less energy efficient than conventional Reverse Osmosis particularly at ERD efficiency more than 80%. However, for desalination plants without ERD system, FO-RO was more energy efficiency than conventional RO. This holds for small capacities desalination plants since most large seawater desalination plants are provided with ERD. Simulations results also revealed that FO-RO system requires more membrane area than conventional RO system which may compromises the desalination cost.

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION W1.2 DUC THUAN BUI EFFECT OF HYGROSCOPIC MATERIALS ON WATER VAPOR PERMEATION AND DEHUMIDIFICATION PERFORMANCE OF PVA MEMBRANES

DUC THUAN BUI, YONGHUI WONG AND KIAN JON CHUA Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore A systematic study on the characterization and testing of the permeation and dehumidification properties of PVA composite membranes with varying hygroscopic materials content was conducted. Triethylene glycol and lithium chloride were selected as two representative organic and inorganic hygroscopic chemicals. Enhanced hydrophilicity and sorption characteristics were observed for high content of the hygroscopic components in the membrane. Water vapor permeation of the membranes were investigated under different feed relative humidity and temperatures. It was specifically noted that the hygroscopic materials content influenced the thermodynamics of the water vapor permeation. The water permeation energy gradually changes from positive to negative with the addition of the hygroscopic chemicals. This observation is attributed to a lower diffusion energy and a relatively constant sorption energy when hygroscopic contents increases. The membranes were observed to be highly durable and suitable for air dehumidification applications.

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.3 PATRICK DE WIT AN ORGANIC-SOLVENT-FREE METHOD TO FABRICATE INORGANIC POROUS HOLLOW FIBERS

PATRICK DE WIT1, FREDERIQUE VAN DAALEN1, HUSSEIN QASSAB1, SUSHUMNA SHUKLA, MIEKE W.J. LUITEN2, NIECK E. BENES,1 1 Films in Fluids, University of Twente 2 Inorganic Membranes, University of Twente Organic hollow fiber membranes with small radial dimensions are ubiquitous in medical and industrial applications. One of their main advantages is the high surface-to-volumeratio that results from their small radial dimension. These small radial dimensions can be achieved by the dry-wet spinning technique, in which the solid fiber is formed by nonsolvent induced phase separation (NIPS) of a polymer solution. As compared to polymer fibers, inorganic porous hollow fibers potentially provide better thermal, chemical, and mechanical stability. Various studies can be found in literature on the fabrication of inorganic porous hollow fibers.1 All these fibers have been prepared by adding inorganic particles to a polymer solution prior to dry-wet spinning, and subsequently removing the organic components from the obtained fiber via a thermal treatment. Many successful recipes for the particle-loaded polymer solutions are known; all of these involve the use of an organic solvent such as dimethyl formamide, N-methyl-2pyrrolidone, and dimethyl acetamide. These solvents dissolve a vast variety of polymers, and their solutions readily coagulate upon contact with water. However, the use of organic solvents involves inherent drawbacks related to, for instance, their toxicity and environmental impact.2 Here we present an alternative method for the fabrication of inorganic hollow fibers, that completely avoids the use of organic solvents. In addition, it inherently avoids the manifestation of so-called macro voids and allows the facile incorporation of additional metal oxides in the inorganic hollow fibers.2 The ionic crosslinking requires that the sodium ions in the polymer are replaced by multivalent cat ions. These multivalent cations can be supplied from a coagulation bath, or alternatively from an insoluble carbonate salt in the polymer solution that is decomposed by a switch in the pH. By adding the multivalent cations to the polymer solution, we are able produces fibers with superior properties, in particular with respect to mechanical strength.3 A detailed statistical comparison of the mechanical strength of fibers prepared using non-solvent induced phase separation and the newly developed ionic crosslinking is provided. Finally, two illustrative applications of the fibers will be presented. The first is the filtration of “produced water” by silicon carbide fibers,4 the second is the exceptionally efficient electro-catalytic reduction of carbon dioxide to carbon monoxide with copper hollow fibers.5

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REFERENCES 1

X. Tan, S. Liu, K. Li, Preparation and characterization of inorganic hollow fiber membranes, J. Memb. Sci. 188 (2001) 87–95. doi:10.1016/S0376-7388(01)00369-6.

2

S. Shukla, P. de Wit, M. W. J. Luiten-Olieman, E. J. Kappert, A. Nijmeijer, and N. E. Benes, “Synthesis of porous inorganic hollow fibers without harmful solvents.,” ChemSusChem, vol. 8, no. 2, pp. 251–254, Jan. 2015.

3

H. Q. Hussein, P. de Wit, E. J. Kappert, and N. E. Benes, “Sustainable Route to Inorganic Porous Hollow Fibers with Superior Properties,” ACS sustainable Chemistry and Engineering, vol. 3, no. 12, pp. 3454–3460, 2015.

4

P. de Wit, E. J. Kappert, T. Lohaus, M. Wessling, A. Nijmeijer, and N. E. Benes, “Highly permeable and mechanically robust silicon carbide hollow fiber membranes,” J. Mem. Sci., vol. 475, no. C, pp. 480–487, Feb. 2015.

5

R. Kas, K. K. Hummadi, R. Kortlever, P. de Wit, A. Milbrat, M. W. J. Luiten-Olieman, N. E. Benes, M. T. M. Koper, and G. Mul, “Three-dimensional porous hollow fibre copper electrodes for efficient and high-rate electrochemical carbon dioxide reduction,” Nat Comms, vol. 7, p. 10748, Feb. 2016.

PATRICK DE WIT Title: PhD Candidate University of Twente, The Netherlands Phone: +3153 489 2998 E-mail: [email protected] Research interests: inorganic hollow fibers, mechanical strength

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W1.4 ANTHONY SZYMCZYK DEGRADATION OF POLYETHERSULFONE / POLYVINYLPYRROLIDONE MEMBRANES BY SODIUM HYPOCHLORITE

YAMINA HANAFI1,2, PATRICK LOULERGUE1, MURIELLE RABILLERBAUDRY1, BART VAN DER BRUGGEN3, ANTHONY SZYMCZYK1 1 Université de Rennes 1, Université Bretagne-Loire, Institut des Sciences Chimiques de Rennes (UMR CNRS 6226), 263 Avenue du Général Leclerc, CS 74205, 35042 Rennes, France 2  Unité de Recherche Matériaux Procédés et Environnement, Université M’hamed Bougara, Boumerdes, Algeria 3 Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F, B-3001 Heverlee, Belgium Due to its chemical, thermal and mechanical stability, polyethersulfone (PES) is often used to synthesis ultrafiltration and nanofiltration membranes. However, its main drawback is its hydrophobicity, which limits permeation fluxes and increases membrane fouling. The incorporation of a hydrophilic polymer such as polyvinylpyrrolidone (PVP) in the membrane matrix is the simplest method to increase membrane hydrophilicity. Nevertheless, during onsite operation the use of oxidants, generally sodium hypochlorite, to sanitize the processing equipment is known to impair the integrity and lifespan of PES/PVP membranes. It is well-known that the pH of sodium hypochlorite solution is of crucial importance on the ageing rate. However, the complex effects of sodium hypochlorite solution on the molecular degradation mechanisms of PES/PVP membranes remain unclear1-3. The present work aims to provide a deeper understanding of PES/PVP membrane degradation upon exposure to sodium hypochlorite. We first investigated molecular changes of commercial UF membranes resulting from exposure to sodium hypochlorite solutions at different concentrations (200-400 ppm in total free chlorine) and pHs (6, 8 and 11.5) by means of tangential streaming current measurements, combined with X-ray Photoelectron Spectroscopy, Size Exclusion Chromatography and Attenuated Total Reflection Fourier Transform InfraRed spectroscopy. PVP oxidation, leading to an increase in the negative charge density of aged membranes, was pointed out whatever the ageing solution pH although different mechanisms might be involved depending on the ageing pH. PES degradation was also demonstrated. Streaming current measurements highlighted the formation of functional groups with very weak acid properties on the surface of membranes aged in sodium hypochlorite at pH 8.0 and to a lesser extent at pH 6.0 and 11.5. These results were found to be consistent with the formation of phenol groups due to

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the radical hydroxylation of PES aromatic rings4. Moreover, the disappearance of the isoelectric point of membranes aged in sodium hypochlorite at pH 6.0 and 8.0 gave evidence for the formation of strong acid groups such as sulfonic acids3. The disappearance of the membrane isoelectric point was not observed for membranes aged in sodium hypochlorite at pH 11.5, thus indicating that hypochlorite anions were not involved in the PES-chain scission mechanism (leading to the formation of sulfonic acid functions; see Fig. 1) for the ageing conditions considered in this work.

Figure 1. Formation of sulfonic acid groups (dissociated in sulfonate form in aqueous medium) as a result of PES-chain scission.

Moreover, streaming current measurements performed with the addition of tertiobutanol (acting as a free radical scavenger) in the ageing solutions and thermo-oxidation experiments revealed that, although both hypochlorous acid (HClO) and free radical species contributed to PES-chain scissions, HClO had the greater impact on PES degradation. Finally, the possible role of PVP in the degradation of PES was explored. To this end, pure PES membranes as well as PES/PVP membranes with different concentrations of PVP were prepared by non-solvent induced phase inversion, and further aged by filtration of sodium hypochlorite solutions. Streaming current measurements revealed that PES-chain scission occurred for all membranes, i.e. even in the absence of PVP. This means that possible degradation products of PVP are not responsible for initiating PES-chain scissions. REFERENCES 1 E. Arkhangelsky, D. Kuzmenko, V. Gitis. J. Membr. Sci. 2007, 305, 176. 2 Y. Hanafi, A. Szymczyk, M. Rabiller-Baudry, K. Baddari, Environ. Sci. Technol. 2014, 48, 13419. 3 R. Prulho, S. Thérias, A. Rivaton, J.L. Gardette, Polym. Degrad. Stab. 2013, 98, 1164. 4 Y. Hanafi, P. Loulergue, S. Ababou-Girard, C. Meriadec, M. Rabiller-Baudry, K. Baddari, A. Szymczyk, J. Membr. Sci. 2016, 501, 24.

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ANTHONY SZYMCZYK Prof. Dr. France Phone: +33 2 23236528 E-mail: [email protected] Anthony Szymczyk received his Ph.D. in Physical Chemistry in 1999 at the University of Franche-Comté. He is currently Full Professor of the University of Rennes 1 where he teaches Thermodynamics and Membrane processes. Prof. Szymczyk’s research lies at the interface of chemical engineering, chemistry of materials and physics of condensed matter. His main research activities focus on the modeling and simulation of membrane separations for desalination and water purification, and on the physico-chemical characterization of membrane materials with applications in functionalization, fouling, ageing... He published about 110 scientific papers and book chapters on these topics. In 2013 he was the recipient of the IUPAC distinguished Award for Novel Materials and their Synthesis for his work on ion transport through nanoporous membranes. He was a member of the council of the European Membrane Society (2011-2014) and he served as Vice-President in 2013 and 2014.

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W1.5 VALENTINA MUSTEATA SMALL ANGLE X-RAY SCATTERING AS CHARACTERIZATION FOR BLOCK COPOLYMER MEMBRANES

VALENTINA MUSTEATA,1BURHANNUDIN SUTISNA,1 GEORGIOS POLYMEROPOULOS,1 KLAUS-VIKTOR PEINEMANN,1 NIKOS HADJICHRISTIDIS1 AND SUZANA P. NUNES*1 1 King Abdullah University of Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia, *E-mail: [email protected] The self-assembly of block copolymers has been extremely useful for the preparation of highly porous membranes with sharp pore distribution and long-range order.1-4 These nanostructured materials can have applications in selective protein separation, drug delivery, development of new catalysis systems, sensors, etc. Using Small-Angle X-ray Scattering (SAXS) we demonstrated that order in block copolymers solutions leads to membranes with highly ordered porous surface, trough the phase inversion process by precipitation in a non-solvent.1,2,5 Here we study the solution morphology of new block copolymers with different molecular weight and different segment ratio. The self assembly into ordered polymer micelles in solution was promoted by the selection of selective solvents.6 We studied the solution morphology as a function of solvent composition and polymer concentration. By SAXS, we evidenced the formation of phase separated morphologies with the characteristic domain spacing correlated with the molecular weight. With increasing polymer concentration the morphology in solution changed from disordered spherical micelles to ordered morphology for specific polymer – solvent mixtures (Fig. 1a). Rheology measurements evidenced the formation of connected micellar networks for the solutions that showed order in the SAXS patterns. The porous membrane formation was investigated by in situ Grazing Incident Small Angle X-ray Scattering (GISAXS) on casted polymer solutions. GISAXS revealed a hexagonal micelle order with domain spacing correlated to the membrane interpore distances (Figs. 1 b and c).

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Fig. 1. (a) SAXS patterns for block copolymer solutions at increasing polymer concentration. (b) Scattering peaks of the horizontal cuts of GISAXS patterns. Inset is the scanning electron microscopy image of the obtained isoporous membrane surface. (c) Calculated d-spacing for thin casted films at varying evaporation times. Inset are the GISAXS 2D-patterns for thin films cast from solution with varying evaporation times.

Acknowledgement: This work was sponsored by King Abdullah University of Science and Technology (KAUST). The authors thank D. Smilgies from CHESS, Cornell University, USA, and F. Meneau from LNLS Brazil access to the synchrotron facilities and help during SAXS and GISAXS measurements. REFERENCES 1 S.P. Nunes, R. Sougrat, B. Hooghan, D.H. Anjum, A.R. Behzad, L. Zhao, N. Pradeep, I. Pinnau, U. Vainio, K.V. Peinemann, Macromolecules, 2010, 43, 8079–8085. 2 D.S. Marques, U. Vainio, N.M. Chaparro, V. M. Calo, A. R. Bezahd, J. W. Pitera, K. V. Peinemann, S . P. Nunes, Soft Matter, 2013, 9, 5557-5564. 3 S. P. Nunes, Macromolecules, 2016, DOI: 10.1021/acs.macromol.5b02579. 4 H. Yu, X. Qiu, S. P. Nunes, K. V. Peinemann, Nature Comm. 5: 4110 DOI:10.1038/ncomms5110. 5 R. M. Dorin, D. S. Marques, H. Sai, U. Vainio, W. A. Phillip,K. V. Peinemann, S. P. Nunes, U. Wiesner, ACS Macro Lett., 2012, 1, 614–617. 6 B. Sutisna, G. Polymeropoulos, V. Musteata, K.-V. Peinemann, A. Avgeropoulos, D.-M. Smilgies, N. Hadjichristidis and S. P. Nunes, Mol. Syst. Des. Eng, 2016.

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

VALENTINA MUSTEATA Title: Dr. King Abdullah University of Science and Technology (KAUST), Saudi Arabia Phone: +966 54 2512053, E-mail: [email protected] 2015-present

Postdoctoral Fellow, Biological and Environmental Science and Engineering Division, KAUST

2012-2015

Research Assistant, Petru Poni Institute of Macromolecular Chemistry, Iasi

2007-2012

Ph.D. in Polymer Chemistry, Petru Poni Institute of Macromolecular Chemistry, Iasi

2008-2009

M.S. in Biopolymers, Gh. Asachi Technical University of Iasi

2000-2004

B.S. in Physics, Al. I Cuza University, Iasi

Research interests: block copolymer self-assembly, porous membranes

GOLD SPONSOR

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.6 SALMAN SHAHID TAILORING THE IN-FILTRATION FLUX AND MWCO TUNEABILITY OF CONDUCTIVE POLYANILINE MEMBRANES: EFFECT OF DIFFERENT MOLECULAR WEIGHT ACID DOPANTS AND DOPING TEMPERATURES

SALMAN SHAHID, AGNIESZKA KINGA HOLDA, DARRELL ALEC PATTERSON Centre for Advanced Separation Engineering and Department of Chemical Engineering, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom Polyaniline (PANI) is one of the most promising conductive polymers due to its specific electrochemical and optical properties, and its reversible acid-base and redox chemistry.1,2 The sensitivity of PANI electronic properties to environmental stimuli has been exploited in the design of chemical and biological sensors3. In addition, PANI is an exciting prospective membrane material that exhibits several properties that are well-suited for membrane-based separations. PANI possesses the ability to modify its separation characteristics as a response to its oxidation/reduction states that demonstrates a key advantage in the ability to readily tune the properties of these polymer membranes. In liquid separations, PANI membranes have the added feature of being responsive to their environments, such as changing solution pH or applied electrochemical stimuli. Electrically conductive PANI membranes could possibly be dynamically responsive by applying an external electrical potential across the membrane, thus inducing several changes in membrane properties that could produce more general membrane tuneability beyond the ion separations that PANI membranes have in the main been applied to thus far. These electrically induced changes include: changing surface charge controlling Donnan exclusion, change in pore size/free volume (via incorporation or expulsion of ions from the acid dopant site) controlling pore flow transport, and chemical property changes controlling solution diffusion. Combined, these make polyaniline an excellent candidate for a more universally electrically tuneable membrane. Inorganic acids (such as HCl and H2SO4) and functionalized organic molecular acids (such as camphorsulfonic acid) are commonly used as the dopants for PANI to bring them into the electrically conductive emeraldine form. In order to keep PANI membranes electrically tuneable and conductive during the lifetime of the membrane and during membrane operation it is vital that these acid dopants remain stable in the membrane. However, low molecular weight acid dopants (LMAD) may leach out during the filtration process and cause deprotonation of PANI. Stability against deprotonation of PANI can be significantly improved by using high molecular weight acid dopants (HMAD). However, doping HMAD into PANI membrane is difficult because of their higher molecular size, which inhibits their diffusion in PANI membranes when mixing and casting. In this work, we investigate for the first time the electrical tuneability of PANI membranes doped with different LMAD and HMAD and at different doping temperatures. PANI was synthesised via

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

chemical oxidative polymerisation at 15°C. Subsequently, flat sheet PANI membranes were prepared via non-solvent induced phase separation. The prepared undoped PANI membranes were redoped with LMAD and HMAD at 25oC and 80oC. The specific characteristics of PANI redoped with different acid dopants were investigated by a multitude of characterization techniques (XPS, FTIR, cyclic voltammetry, SEM, UV-Vis spectroscopy etc.). It was found that a greater doping level was achieved at higher doping temperatures with HMAD compared to a room temperature doping process. Moreover, the HMAD doping process at 80oC was completed in shorter time compared to 25oC. Doping with LMAD showed no difference in doping levels with temperature. Membranes synthesised with HMAD were more stable that those doped with LMAD: it is likely that a lower mobility and therefore a slower diffusion rate of HMAD in the PANI membranes compared to LMAD during filtration experiments prevents it’s the release from redoped PANI membranes even at higher applied potentials. In terms of the electrical tuneability of the PANI membranes under filtration conditions, flux and molecular weight cut off (MWCO) of membranes were measured for neutrally charged PEG feed solutions as a function of the applied potential from 0 to 30 volts in cross-flow pressure cells at industrially relevant pressures (10 to 30 bar) with a recirculating flowrates of up to 1 L min-1. Results indicate that the electrical tuneability of PANI membranes can be tailored using the different acid dopants and doping conditions: under applied potential, PANI membranes showed a change in permeability and MWCO in the PEG cross-flow filtrations that was dependent on the acid dopant and doping temperatures. Overall, this work shows that the flux and MWCO of PANI membranes can be tuned by voltage and by the acid dopants that are used in membrane synthesis and fabrication. Using HMAD produces more stable membranes that retain dopant and electrical conductivity more than LAMD membranes. Consequently, this work helps to further open a “smart” window for the production of more universally applicable electrically tuneable membranes. REFERENCES 1

D.W. Hatchett, M. Josowicz, and J. Janata, J. Phys. Chem. B, 1999,103, 10992.

2

Y. Xia, J. M. Wiesinger, A. G. MacDiarmid, and A. J. Epstein, Chem. Mater., 1995, 7, 443.

3

T.A. Skotheim, R.L. Elsenbaumer, J.R. Reynolds, editors. Handbook of Conducting Polymers. Second Edition. Marcel Dekker; New York: 1998, pp 963-991.

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

SALMAN SHAHID Title: Dr. Affiliation, Country: Centre of Advanced Separation Engineering and Department of Chemical Engineering, University of Bath, United Kingdom. Phone: +00447467910467 E-mail: [email protected] 2010

University of Catholique Louvain,Belgium

2011-2012

University of Twente, Natherlands

2012-2013

University of Montpellier-2, France

2013-2014

University of Leuven, Belgium

2014-2015

Technical university of Delft, Netherlands

Since Dec 2015

PDRA at University of Bath, UK

Research interests: Membranes, Liquid separations, Gas separation, MOFs, Catalysis

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.7 LIANG LIU PREDICATION OF GAS AND VAPOUR SORPTION IN GLASSY POLYMERS THROUGH A PC-SAFT BASED MODEL

LIANG LIU, SANDRA KENTISH Department of Chemical and Biomolecular Engineering, the University of Melbourne, Vic. 3010, Australia The sorption of small molecule penetrants into glassy polymers is of great interest in many applications such as membrane separation1, 2 and packaging materials3. Although several phenomenological models (e.g. dual mode sorption, GAB and ENSIC model) have been developed, one clear drawback of these models is that they lack predictive ability. Recently, it has been reported that the NET-GP (non-equilibrium thermodynamics of glassy polymer) model in combination with a relevant equation of state (e.g. Lattice Fluid EoS) has been successfully applied to model gas/liquid sorption in glassy polymers4. However, this model does not give satisfactory results for water solubility in polymers because this EoS does not take into account association interactions (i.e. hydrogen bonding) between water molecules and the polymer chains 5. Perturbed-chain Statistical Associating Fluid Theory (PC-SAFT) is an advanced EoS that can tackle different interactions (e.g. association, polar and Coulomb interactions) and is widely applied in polymer systems6. In this work, the PC-SAFT model and related NET-GP framework were initially validated by modelling literature data for gas sorption in both rubbery and glassy polymers. The PC-SAFT model with association contributions was then used to predict water sorption isotherms in glassy polymers such as PMMA. The results were compared with those from the NET PC-SAFT model as shown in Fig. 1. It is surprisingly that the PC-SAFT model provided better results than the non-equilibrium NET PC-SAFT although PMMA is in a glassy state. This suggests that the influence of the non-equilibrium excess free volume was marginal. Finally, the contributions of self-association (i.e. water clustering) and induced-association between water and the functional groups of polymers were analysed to provide better understanding of water sorption behaviour in glassy polymers.

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

Figure 1. Modelling results of water sorption in PMMA by the PC-SAFT model (solid lines) and the NET PC-SAFT model (dashed lines). Experimental data (symbols) are obtained from the literature7. REFERENCES 1

Y. Tsujita, Prog. Polym. Sci., 2003, 28, 1377-1401.

2

C.A. Scholes, W.X. Tao, G.W. Stevens, S.E. Kentish, J. Appl. Polym. Sci., 2010, 117, 2284-2289.

3

A. Polyakova, R. Liu, D. Schiraldi, A. Hiltner, E. Baer, J. Polym. Sci. Part B: Polym. Phys., 2001, 39, 1889-1899.

4

M.G. De Angelis, G.C. Sarti, Annu. Rev. Chem. Biomol. Eng., 2011, 2, 97-120.

5

M. Minelli, G. Cocchi, L. Ansaloni, M.G. Baschetti, M. De Angelis, F. Doghieri, , Ind. Eng. Chem. Res., 2013, 52, 8936-8945.

6

J. Gross, G. Sadowski, Ind. Eng. Chem. Res., 2001, 40, 1244-1260.

7

E.M. Davis, Y.A. Elabd, Ind. Eng. Chem. Res., 2013, 52,12865-12875.

LIANG LIU Title: Dr The University of Melbourne, Parkville, Vic, Australia Phone: +61 8344 8863 E-mail: [email protected] 2015.09-

Research Fellow, The University of Melbourne.

2012.04-2015.08 PhD candidate, The University of Queensland. Research interests: gas separation, pervaparation and desalination.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.8 ZHAOYANG LIU A NEW COMPOSITE FORWARD OSMOSIS MEMBRANE WITH LOW FOULING TENDENCY AND HIGH SEPARATION EFFICIENCY Qatar Environment and Energy Research Institute, HBKU, Qatar Foundation Compared to pressure-driven membrane techniques, forward osmosis (FO) is an osmosis driven process that can separate clean water from contaminated sources via a semipermeable membrane by the osmotic gradients across the membrane. By leveraging recent advance of nanotechnology1,2, a new nanocomposite FO membrane was designed to consist of double layers: an underwater oleophobic selective layer on top of a nanomaterial infused polymeric support layer. Herein, graphene oxide (GO) nanosheets were selected to add into the polymeric support layer because GO nanosheets can dramatically enhance the water flux of this FO membrane via optimizing the pore structures of the support layer. And, polyvinyl alcohol (PVA) hydrogel was selected as the selective layer because hydrated and chemically-crosslinked PVA hydrogel is capable of simultaneously rejecting oil and salt. This new nanocomposite FO membrane was successfully fabricated, and its performances have been tested with simulated produced waters of high oil and salt contents. The important experimental results have been obtained as shown in below Figure 1 and 2. The membrane structure and surface wettability were systematically studied with FESEM, AFM, ATR-FTIR, contact angles, and zeta-potential analyser, as shown in Figure 1. And its separation efficiency, permeation flux and fouling tendency were also studied with a custom-built FO cross flow system, TOC, COD, and ICP-OES, as shown in Figure 2. The GO nanosheets infused in support layer can significantly reduce the structural parameter of the new FO membrane. And the hydrogel selective layer can present high antifouling property under saline oil/ water emulsions. Compared with commercial FO membrane, this new FO membrane possesses three times higher water flux, higher removal efficiencies for oil (>99.9%) and salts (>99.7% for multivalent ions), and significantly lower membrane fouling tendency (<10%).

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

Figure 1. (a) SEM top view of GO infused polymeric (PES) support layer (scale bar, 100 nm). (b) SEM side view of GO infused polymeric (PES) support layer (scale bar, 20 μm). (c) The effect of GO concentration on the water permeability of the polymeric support layers. (d) SEM top view of nanocomposite FO membrane (scale bar, 100 nm). (e) Enlarged SEM side view of the nanocomposite FO membrane (scale bar, 100 nm). (f, g) Underwater oil contact angle and water contact angle in air of the nanocomposite FO membrane, respectively. (h, i) Underwater oil contact angle and water contact angle in air of commercial cellulose FO membrane, respectively.

304

Figure 2. (a-d) Optical microscopic images of different solutions, wherein, (a) 173 g/L dissolved inorganic salts in DI water, (b) 25 g/L hexadecane-in-water emulsion with 1.25 g/L surfactant and 0 g/L dissolved inorganic salts, (c) 25 g/L hexadecane-in-water emulsion with 1.25 g/L surfactant and 173 g/L dissolved inorganic salts, and (d) draw solution at the end of fouling test. (e) FO water fluxes and fouling ratios of the nanocomposite and commercial HTI FO membranes under feed solution of 25 g/L hexadecane-in-water emulsion with 1.25 g/L surfactant and 173 g/L dissolved inorganic salts, which is used to simulate onshore oil/gas produced water. (f) Concurrent removal ratios of oil and dissolved inorganic salts from simulated onshore oil/gas produced water by as-synthesized nanocomposite and commercial Cellulose FO membranes.

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

ZHAOYANG LIU Title: Senior Scientist Qatar Environment and Energy Research Institute (QEERI), HBKU, Qatar Foundation, Qatar. Phone: +974-33097879 Fax: +974 4454 0547 E-mail: [email protected] 2014-now

Dr. Liu works in QEERI as Senior Scientist focusing on membrane technologies for water treatment.

Research interests: membrane, water reuse, desalination

GOLD SPONSOR

305

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.9 ZE-XIAN LOW1 3D PRINTING FOR MEMBRANE SEPARATION SYSTEMS

ZE-XIAN LOW1, ABOUTHER THALIB HALBOOSE1, YEN THIEN CHUA1, DAVIDE MATTIA1, IAN METCALFE2 AND DARRELL ALEC PATTERSON1 1 Centre for Advanced Separations Engineering and Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom 2 School of Chemical Engineering and Advanced Materials, Newcastle University Merz Court, Newcastle upon Tyne NE1 7RU, United Kingdom Additive manufacturing, likewise known as three-dimensional (3D) printing and rapid prototyping has the ability to create almost any geometrically complex shape or feature in a range of materials across different field. Various 3D printing techniques are currently available in the market, including 3D printers based on photo-polymerization, powder, extrusion and lamination (Fig. 1). It has found its applications in various areas, such as medicine, art, manufacturing and engineering. On the other hand, its use in separation membrane engineering is relatively new. The use of additive manufacturing techniques could provide more control over precision towards the design of separation membrane system and offers new membrane preparation techniques that are able to produce membranes of different shapes, types and designs where conventional techniques such as phase inversion method could not achieve.

Figure 1. Various 3D printing techniques.

Here we design a 3D-printed membrane (3DPM) with different pore shapes and sizes and membrane thicknesses using material jetting-based 3D printer (Projet 3500 HDMax, 3D

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

Systems) for oil water coalescence. A 25 mm disc membrane with hexagonal pore of 300 µm and different thickness (1 mm, 3 mm and 5 mm) was designed and printed to enhance the coalescence of oil drops. The separation of oil was measured by means of UV vis spectroscopy and by observation of oil layer thickness in a burette. The feed solutions of three different oil concentrations (2500, 3320, and 4150 mg/L) were prepared by homogenizing sunflower oil and water. Using the 3D-printed membrane, we showed that the oil/water coalescence process was improved in terms of separation efficiency and time. For instance, similar separation efficiency was achieved about 4 times faster using the optimised 3D-printed membrane than natural coalescence (Fig. 2a). The 3DPM with thickness of 5 mm showed similar oil layer separation at 30 min as that of the natural coalescence without a 3DPM at 2 h. On the other hand, Oil separation generally increases with feed oil concentration as well as thickness of the 3DPMs (Fig. 2b), further confirming the effectiveness of 3DPM-based coalescence. The increase in oil separation with increasing 3DPM thickness can be explained by the increase oil-water contact time and contact area within the 3DPM.

Figure 2. (a) thickness of the oil layer in a burette after filtering through 3DPM-5mm (oil concentration: 3320 mg/L); and (b) oil removal (%) as a function of oil concentration (mg/L) for 3DPM-based coalescence and natural coalescence of sunflower oil droplets.

ZE-XIAN (NICHOLAS) LOW Title: Postdoctoral Research Associate Centre of Advanced Separations Engineering, University of Bath, U.K. E-mail: [email protected], Website: www.nicholaslow.com 2012-2015

Ph.D. in Chemical Engineering, Monash University

Research interests: gas separation, engineered osmosis, 3D printing

GOLD SPONSOR

307

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.11 JIE ZHAO PREPARATION OF NOVEL PVDF HOLLOW FIBER MEMBRANES FROM A TERNARY SYSTEM VIA COMBINED THERMALLY AND NONSOLVENT INDUCED PHASE SEPARATION (TIPS-NIPS) METHOD

JIE ZHAO1,2, LEI SHI1, RONG WANG1,2* 1 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Ceantech Loop, Singapore 637141, Singapore. 2 School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore. ABSTRACT

The key challenge in the development of microporous fabricated by thermally induced phase separation (TIPS) method is to control the pore formation on the surface of membrane. Meanwhile, the nonsolvent induced phase separation (NIPS), which is another widely adopted membrane fabrication method, has been demonstrated to be versatile in controlling the surface pore structure. In an attempt to combine the features of both TIPS and NIPS method, in this work, novel microporous polyvinylidene fluoride (PVDF) hollow fiber membranes with prominent permeability and mechanical strength were fabricated via a combination of TIPS and NIPS method from a ternary system containing two diluents. In the preparation of membranes, two kinds of diluents were carefully selected based on their miscibility with water, which was used as the coagulant. In particular, waster-immiscible solvent dimethyl phthalate (DMP) was selected as the diluent for TIPS process while water-miscible solvent triethyl phosphate (TEP) was used to induce the NIPS effect to the TIPS process. The effect of TEP addition on membrane formation and properties were thoroughly investigated. It was found that a more interconnected micro-structure was formed on the outer surface with TEP addition, leading to a narrower distribution of pores and a much higher overall porosity of 75.9%. By controlling the TEP addition and phase separation kinetics, the tensile strength was significantly improved from 3.5 to 6.0 MPa. The membranes developed in 60˚C coagulant exhibited remarkably high water permeabilities up to 7670 LMH/bar with narrow pore size distributions.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

NAME: JIE ZHAO Title: Mr Singapore Membrane Technology Centre, Nanyang Technological University, Singapore Phone: +65 91299505 Fax: +65 67910756 E-mail: [email protected] 2008-2012

B.E., Sichuan University, China

2012-2013

MSc, Nanyang Technological University, Singapore

Since 2014

PhD student, Nanyang Technological University, Singapore

Research interests: Membrane development, water treatment, desalination * Corresponding author’s e-mail address: [email protected] (R. Wang), phone number: (+65)67905264/5327.

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309

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.12 M. RABILLER-BAUDRY MICRO-WAVES TO STUDY THE LONG TERM STABILITY OF A MEMBRANE: WHY NOT ?

M. RABILLER-BAUDRY 1*, C. LEPEROUX1, J. GIRARD1, P. LOULERGUE1 1 Université de Rennes 1- Université Bretagne Loire, Institut des Sciences Chimiques de Rennes, UMR-CNRS, Rennes, France At industrial scale, membranes slowly aged leading to variations in theirs performances (rejection, fouling, and difficulty in cleaning) up to final disruption. The actual lack of efficient tools to appreciate the membrane ageing is a limitation for a better process mastering. It is a preliminary need to have ageing protocols useful at lab. scale to establish better procedures for both the production and the cleaning steps. This will allow to propose adaptations of the process control with the membrane age in a similar way as what is already done in NF of surface water to take into account the seasonal variability of water quality inducing fouling variations. In the case of UF of skim milk, PES/PVP membranes are commonly used (Fig.1). The main origin of membrane degradation is known (NaOCl treatment for disinfection) and lead to PVP disappearance and PES skeleton modification (Fig.1) but disruption always occurred at unpredictable time. Consequently membranes are often changed in emergency.

PES

PVP

Figure 1 PES and PVP: the two polymer constituting the active layer of the UF membrane (HFK-131, Koch) and degradation of PES skeleton by NaOCl according to [1, 2, 3]

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

In this paper we propose different methodologies to obtain controlled aged membranes at lab. scale. Several physico-chemical characterizations were used (FTIR-ATR, SEM-EDX, SIMS, contact angles) together with the determination of flux and rejection not systematically correlated with evolution of physico-chemical data. To confirm the representativeness of obtained aged membranes comparisons between pristine, lab. aged membrane and an industrial membrane at end of its service-life were achieved. Proposed ageing methods discussed in this paper are: • membrane immersion in an appropriate solution under micro-waves to accelerate the chemical degradation, allowing to quickly reach the target chemical degradation but not the flux increase • semi-continuous UF of the ageing solution during about 10 days at appropriate pH and concentration allowing to study the critical and limiting fluxes evolution with ageing together with the increase in cleaning difficulty • coupling of the two previous protocols to obtain in less than 2 days both the chemical and mechanical degradation of a membrane at half of its service-life. Fig.2 shows the FTIR-ATR spectra used for a pristine membrane and the reference membrane aged at industrial scale (Membrane U) and the acceleration of ageing due to micro-waves in immersion experiments. Finally coupling short UF and micro-waves appears as a promising protocol thanks to FTIR-ATR and flux measurements (Fig.3).

Figure 3. Water permeability of aged membranes according different protocols

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

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PVP disappearance: see band at 1660 cm-1 / PES evolution (two possibilities of Fig. 1): see band at 1030 cm-1 and FTIR-ATR data for membrane aged by immersion with or without micro-waves in NaOCl 400 ppm Acknowledgement to the French National Agency for Research for financial support: ANR-Blanc-Meduse REFERENCES

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1

K. Yadav et al., Polymer Degrad. Stab. 2009, 94, 1955-1961

2

R. Prulho et al., Polymer Degrad. Stab. 2013, 98, 1164-1172

3

Y. Hanafi et al. , Environ. Sci. Technol. 2014, 48, 13419-13426

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

MURIELLE RABILLER-BAUDRY Title: Professor Université Rennes 1- Université Bretagne Loire, Institut des Sciences Chimiques de Rennes, UMR-CNRS, Rennes, France Phone: +33223235752 Fax: +33223234031 E-mail: [email protected] Since 1991 UF, NF, RO (mainly food fluids) 2002

Professor at Rennes 1 University

Since 2005

OSN for fine chemistry (toluene)

Since 2006

Chair of the membrane group in Rennes 1 University

Research interests: UF of dairy fluids (mechanism, cleaning, ageing), OSN

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THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

W1.13 LUCA ANSALONI HYBRID POLYMER-LIQUID MEMBRANES: EFFECTS OF LOW MOLECULAR WEIGH MOLECULES AND WATER VAPOR

ZHONGDE DAI, LUCA ANSALONI, LIYUAN DENG Department of Chemical Engineering, Norwegian University of Science and Technology, 7491 Trondheim, Norway Among the approaches to tackle the upper bound limit imposed on gas separation membranes, the concept of using hybrid membranes has appeared to be very promising, as it improves the separation performance due to the simultaneous exploitation of the best features of different phases present within the membrane matrix. Polymer-liquid hybrid membranes is a very promising approach to achieve superior performances, as the presence of the liquid phase will improve consistently the diffusion coefficient of small molecules thro ugh the selective layer, allowing to reach a high membrane productivity. Even though the approach of embedding liquid phase in porous membranes (i.e. supported liquid membranes) has been found to be unsuccessful due to instability issues 1, recently the addition of liquid phases to dense polymeric layers has been reported to be promising, both from the separation and stability performances point of view2. In this morphology the liquid phase is trapped within the molecular chains of the membrane matrix, thus ensuring a better stability. In addition, small molecules with reduced volatility, such as ionic liquids (ILs) 3, 4, can be used to prevent the evaporation of the liquid outside the membrane phase. Furthermore, stronger interaction between the polymer matrix and liquid additives (e.g., charge interaction) will also contribute to achieve better membrane stability.

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In the present research work, two different approaches have been used to improve the gas transport properties of pure polymeric membrane by embedding molecules with low molecular weight within the matrix. In the first approach liquid-state PEGDME (Polyethylenglycol dimethylether, Mn ~250) is embedded in a PEG-based matrix obtained using different crosslinkers (A-amine, 2,2’-(Ethylenedioxy) bis(ethylamine, and [TETA][Tfa], Triethylenetetramine trifluoroacetic acid). In particular, the PEGDME is added in the polymer solution before the polymerization step, thus ensuring a better dispersion of the low molecular weight component in the matrix. The PEGDME content increase up to 80 wt% showed a two order of magnitude enhancement of the CO2 permeability (Fig. 1A), measured at 2 bar upstream side pressure. Simultaneously, also the CO2/N2 and CO2/ CH4 selectivities were enhanced, allowing the membranes to reach values above the 5 Robeson upper bound . Furthermore, the membranes showed a hydrophilic behavior, with a water uptake larger than 0.9 g/gpol. In this view, mixed gas tests have been performed under humid conditions for the membrane with a high content of PEGDME. After an initial decrease, the CO2 permeability coefficient showed a consistent upturn, reaching an almost double permeability under humidity conditions close to saturation (Fig 1B). Positive effects have been obtained also in terms of selectivity versus other gases. 9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DEVELOPMENT AND CHARACTERISATION

Figure 1. A) Effect of PEGDME content on the CO2 permeability for the membranes obtained with different crosslinkers. B) Effect of relative humidity on the CO2 permeability using different gas mixtures.

In the second approach commercial polymers with sulfonic groups on the side chains (namely Nafion® and Nexar®), have been embedded with different ILs and different ILs contents. It is believed that the presence of charges on the sulfonic groups on the side chains and the one on the IL structure will ensure a better stability of the membranes, for both high pressure and long terms operation stability. The results showed in Fig. 2A refers to the ones obtained by mixing Nafion with different content of [Bmim][BF4] (1-butyl-3methylimidazolium tetrafluoroborate): an increase of 2 orders of magnitude of the CO2 permeability has been obtained for an amount of IL up to 40 wt%, with a positive effect also on the gas selectivity. Furthermore, in view of the positive effect on the gas permeability of water vapor in the feed gas6, mixed gases tests under humid conditions have also been investigated for these hybrid membranes. As showed in Fig. 2B, a monotonous increase has been observed for the CO2 permeability coefficient in the entire humidity range, allowing the achievement of values as high as 400 Barrer.

Figure 2. A) Effect of IL ([Bmim][BF4]) content in the Nafion matrix on the CO2 permeability. B) Effect of relative humidity on the CO2 permeability for different content of IL in the matrix. GOLD SPONSOR

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Currently, investigations of membranes obtained with CO2-philic ILs are ongoing and can theoretically bring to a further improvement of the gas separation performance. The project is financed through the HiPerCap project from the European Union Seventh Framework Programme (FP7 / 2007-2013, Grant Agreement n° 608555). REFERENCES 1

Scovazzo, P., J. Membr. Sci. 2009, 343, (1–2), 199-211.

2

Friess, K.; Jansen, J. C.; Bazzarelli, F.; Izák, P.; Jarmarová, V.; Kačírková, M.; Schauer, J.; Clarizia, G.; Bernardo, P., J. Membr. Sci. 2012, 415–416, 801-809.

3

Tomé, L. C.; Mecerreyes, D.; Freire, C. S. R.; Rebelo, L. P. N.; Marrucho, I. M., J. Membr. Sci. 2013, 428, 260-266.

4

Dai, Z.; Noble, R. D.; Gin, D. L.; Zhang, X.; Deng, L., J. Membr. Sci. 2016, 497, 1-20.

5

Robeson, L. M., The upper bound revisited. J. Membr.Sci. 2008, 320, (1–2), 390-400.

6

Giacinti Baschetti, M.; Minelli, M.; Catalano, J.; Sarti, G. C., Inter. J. Hydrogen. Energ. 2013, 38, (27), 11973-11982.

LUCA ANSALONI Title: PhD, Postdoctoral Fellow Norwegian University of Science and Technology (NTNU), Norway Phone: +4773591807 Fax +4773594080 E-mail: [email protected] 2011-2013

PhD student at University of Bologna

2014-2015

Postdoctoral fellow at University of Bologna

Since 2015

Postdoctoral fellow at NTNU

Research interests: CO2 capture, gas separation membranes, membrane contactors, glycol dehydration

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W1.14 ILYA V. VOROTYNTSEV THE NOVEL GAS SEPARATION MEMBRANES FROM CHITOSAN MODIFIED BY ORGANIC AND INORGANIC MEDIA

ILYA V. VOROTYNTSEV1, KSENIA V. OTVAGINA1, ALLA E. MOCHALOVA2, TATYANA S. SAZANOVA1, ANTON N. PETUKHOV1 1 Nanotechnology and Biotechnology Department, Nizhny Novgorod State Technical University n.a. R.E. Alekseev, 24 Minina Str., Nizhny Novgorod, 603950, Russian Federation 2 Lobachevsky State University of Nizhny Novgorod, 23 Gagarin ave., Nizhny Novgorod, 603950, Russian Federation Acid gases separation, like CO2 and H2S from raw gas enhances the energy output of gas fuel and enable to decrease equipment deterioration. Moreover, CO2 is a greenhouse gas contained in increasing industrial and domestic emissions, which negatively affect the environmental situation. Chitosan (CS) is a promising matrix for carbon dioxide and other acidic gas separation from flue gases through the amino group in its repeating unit. Some of the most attractive features of materials based on CS are their biodegradability, non-toxicity impressive thermal properties and availability. However, CS has not found widespread use in gas separation thus far, due to formation of materials with low physicalmechanical properties and low stability due to the hydrophilic character of surface and the pH sensitivity of CS, which is ill-suited as a component for gas separation modules. CS properties can further be improved by copolymerization with vinyl monomers like acrylonitrile (AN) and styrene (S) or blending with synthetic polymers like polyvinyl alcohol (PVA). These methods are easy to implement, are possible for a wide range of monomers and have a significant influence on the basic properties of mucopolysaccharide. AN and S are large-capacity monomers and there polymerized properties are well studied. Copolymerization with AN and S will provide a stable polymer matrix resistant to mechanical and thermal influence. CS-PVA blends are also well studied and show improved mechanical strength. However, it is likely, the level of the free volume in such matrix will not be high as a result of high crystallinity, and as a consequence, low permeation ability is expected. In order to increase the free volume and adsorption capacity of the CO2 it is proposed to dope original copolymer with ILs or insert nanoobjects like modified fullerenes12 or carbon nanotubes. The scope of the present work is focused on the preparation and gas separation study of membranes based on CS graft and block copolymers with poly(acrylonitrile) (PAN) and poly(styrene) (PS) doped with IL13: [bmim][BF4], [bmim][PF6], [bmim][Tf2N] and CS-PVA blends modified be fullerenol acetate.

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The copolymers were obtained by the latest achievements in the field of copolymerization with CS - radical copolymerization using cobalt complexes and Red-Ox system (hydrogen peroxide - ascorbic acid) as an initiator. Fourier transform infrared spectroscopy analysis (FTIR) of the copolymer samples, purified by homopolymer extraction, in comparison to pure CS were used to support the successful modification of CS. The FTIR spectra of chitosan/poly(acrylonitrile) (CS-PAN) copolymers arise from the frequencies of the C≡N functional group (2241 cm-1), while the chitosan/ poly(styrene) (CS-PS) copolymers FTIR spectra shows bands corresponding to the stretching vibrations of the benzene ring (1570 cm-1); these findings support CS-PAN and CS-PS copolymer formation. From the results of the atomic force analysis (AFM)14, it can be concluded that the pure copolymers possess nodular microstructures, wherein nodules are observed as bright high peaks. The CS-g-PS has the most densely-packed surface structure. The detailed analysis of the membrane surface AFM profiles leads to the conclusion that there is no pores, thus membranes are non-porous. It is known that CS dissolves in ILs, while PAN and PS conversely. Thus, after IL doping and film formation the CS stay dissolved in IL and synthetic chains form stable net, which holds the liquid phase. This is confirmed by AFM, Fig 1. Pure copolymer CS-g-PAN

CS-g-PAN doped with [bmim][BF4]

CS-g-PAN doped with [bmim][PF6]

CS-g-PAN doped with [bmim][Tf2N]

Figure 1. AFM images of CS-g-PAN copolymers

Despite IL doping yielding a different influence on CS-PAN and CS-PS copolymer surfaces, generally, the incorporation of the ionic liquids in the copolymer matrix causes the formation of an explicit macrorelief, thus, the nodular structure remains in those samples at the micro level. The observed microstructure is formed due to the certain orientation of macromolecular chains while film formation. The surface chemical nature was investigated by wettability measurements. The samples surface has good wettability with CH2I2, a relatively nonpolar liquid: cosθ = 0.807 in the case of CS-b-PAN and cosθ = 0.724 in the case of CS-g-PAN; cosθ = 0.699 in CS-b-PS and 0.755 for CS-g-PS. Since the surface has good wettability with nonpolar liquid, it can be concluded that the observed microrelief is formed by orienting the synthetic polymer fragments to the surface and within the scope CS film. Furthermore, to determine the compatibility of copolymers with ILs the wettability of

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membranes with ILs was studied. It was found that all copolymers liquophilic for ILs, and wettability increases in the following order: [bmim][BF4]<[ bmim][PF6]<[ bmim][Tf2N] in all cases. By copolymerization of AN and S with CS the increase in mechanical strength up to CS was 3-4 times in comparison to the original CS membranes was achieved. With the doping of ILs mechanical strength of materials decreased again, however the presence of ILs coursed selectivity for CO2 and permeability growth.

Figure 2. The permeability coefficients.

The best permeance (400 Barrer) was achieved for composition CS-b-PS with [bmim][BF4], the best selectivity (CO2/CH4=14.6, CO2/N2=15.5) was for CS-b-PAN with [bmim][BF4], fig.2. The results obtained on the same level with the world’s best work on the design of gas separation membranes based on CS. This work was financially supported by Russian Science Foundation, project 15-19-10057. ILYA V. VOROTYNTSEV Title: Professor. Nizhny Novgorod State Technical University n.a. R.E. Alekseev (NNSTU), Nizhny Novgorod, Russian Federation Phone: +7 920 0609030 Fax: +78314360361 E-mail: [email protected] 2006

PhD in Physical Chemistry from Lobachevsky University

2004-2006

R&D and production manager of LH GermanLabs RUS, JV

2005-2006

Deputy Director on Science of Firm HORST, Ltd

2011-2013

Deputy Dean of Engineering Chemical Faculty of NNSTU

2014 – present Professor of Nanotechnology and Biotechnology Department of NNSTU Research interests: gas separation, process intensification, ionic liquids, polymers, membrane module, and membranes GOLD SPONSOR

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W1.16 SANGHYUN JEONG FUNCTIONALIZED CARBON NANOTUBE ELECTROSPUN MEMBRANE USED IN MEMBRANE DISTILLATION FOR SEAWATER DESALINATION

SANGHYUN JEONG1, ALICIA KYOUNGJIN AN2*, EUI-JONG LEE2, TOROVE LEIKNES1 1 King Abdullah University of Science and Technology (KAUST), Water Desalination and Reuse Center (WDRC), Biological and Environmental Science & Engineering (BESE), Thuwal 23955-6900, Saudi Arabia 2 School of Energy and Environment, City University of Hong Kong, Tat Chee Avenue Kowloon, Hong Kong, China The material of membrane for membrane distillation (MD) should be hydrophobic, larger pore size (but high rejection), narrow pore size distribution and tortuosity close to one (cylindrical) to get a higher permeability without membrane wetting. To improve the MD membrane properties, the incorporation of nanomaterials has been attempted. Of nanomaterials, carbon nanotubes (CNTs) are one of the favored candidates due to its unique properties such as an excellent adsorption capacity by high specific surface area, slippage effect on permeate flux by the molecular smoothness of nanotube wall (hydrophobicity) and availability to functionalization. CNTs also employed to modify the surface pores inside membrane. Thus, CNTs can make the MD membrane, which have the favorable physical/chemical properties. The CNT enhanced membranes showed an increased hydrophobicity, larger pore size, high porosity and sponge-like pores, resulting in the fast water vapor transport through membrane pores. A recent study reported that thin CNTs layer on the polyvinylidene fluoride-co-hexafluoropropylene (PcH) nanofiber membrane fabricated by an electrospinning method showed a higher porosity (> 85 %) and hydrophobicity (158.5 °). In seawater desalination by MD, the incorporation of CNTs led to a significant increase in flux, probable by generating the additional diffusion path and enhancing pore hydrophobicity. In addition, some studies suggested that CNT promotes the transport of water vapor and gas across membranes 1-3. Addition of only 0.5 wt% of CNTs to a PVDF hollow fibre membrane enhanced the water flux by double and the authors believed that CNT facilitates the water flux possibly by enhancing diffusion of water vapor activated on CNT surface, fast diffusion on CNT surface or enhancing the overall membrane hydrophobicity 3. The development of CNT incorporated membrane has been proved of somewhat benefits to the realm of MD and there are still many research opportunities yet to be explored. As inspired by those previous researches, the present study attempts to introduce CNTs into PcH copolymer for the fabrication of superhydrophobic membrane by electrospinning technique. The idea is currently lack of scientific evidence, perhaps due to the difficulty in CNT dispersion for electrospinning. Therefore, this study demonstrates the synthesis and characteristics of functionalized CNT composited electrospun copolymer membrane for MD with the concern of CNTs

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dispersion. Different concentrations of CNTs were incorporated into the PVDF-HFP membrane and they tested in DCMD to examine the role of CNTs membrane in MD performance. In addition, theoretical modeling approaches including mass and heat transfer and transport were employed. METHODOLOGY

Materials A commercial polymer polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) was purchased from Fisher Scientific and was vacuum-dried at 50 °C before being utilized as the raw material for the fabrication of PVDF-HFP electrospun membrane and functionalized CNT electrospun PVDF-HFP membrane (namely PcH membrane and F-CNT membrane, respectively in this study).

Fabrication of 3D superhydrophobic membrane by electrospinning Two types of electrospun membrane were fabricated. The first type of membrane was prepared solely with PVDF-HFP (namely PcH membrane). The polymer dope was prepared by dissolving 20 wt% of PVDF-HFP into a mixture of DMF and acetone (4:1 by weight). The F-CNT membrane was prepared with PVDF-HFP and functionalized CNT (namely F-CNT membrane). The functionalized CNT (i.e., 0.5 or 1 wt%) was mixed with the polymer dope. The polymer solution was electrospun at a rate of 0.5 ml/h and was ejected onto a non-woven textile pre-attached on a rotating collector 15 cm away from the tip of the nozzle. A positive voltage of 18 kV was applied across the tip-to-collector. The solvents in the nascent nanofibers evaporated and nanofibers curled up concurrently at a rotational speed of 500rpm. In order to eliminate the residual solvent remains in the membrane, the PcH membrane was subsequently placed in a fume cupboard under a vacuum condition at 60 °C overnight. The membrane was then underwent a heat-press post-treatment at 170 °C to improve its mechanical strength.

Characterization of electrospun membranes The surface morphology of the resultant membranes was conducted by scanning electron microscopy (Carl Zeiss, EVO MA 10) and transmission electron microscopy (Philips CM20 TEM). A capillary flow porometer (Porometer, POROLUX™ 1000) was used for the measurement of membrane pore size, pore size distribution and liquid entry pressure (LEP). A tensile test was conducted by Tensile strength measurement (Lloyd-Ametek LS1 material testing machine) for the measurement of membrane mechanical properties. The topography of membranes was characterized by an atomic force microscopy (AFM, Bruker Dimension Fast Scan AFM). The water contact angle was measured by a Contact Angle Meter (KRUESS GmbH DSA25S).

Operation of membrane distillation Air gap membrane distillation and direct contact membrane distillation (DCMD) were applied in this study. The configuration of the membrane flow channel is 62 mm × 15 mm × 5 mm with an effective membrane area of 9.3 cm2. The feed solution contains 35 g/L of NaCl and was heat up to either 40 or 60 °C. The permeate solution is DI water and was maintained to 20 °C. Both solutions were allowed to circulate through the flat sheet GOLD SPONSOR

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membrane cell at a rate of 400 ml/min for 12 h. The flux was recorded in real time by a data-logging system.

Theoretical approach In order to theoretically investigate the performance of the PVDF-HFP membrane and F-CNT membranes, one (1)-dimensional simulation model, which considered the heat and mass transfer and transport model was employed. Both of the mass and heat transfers significantly affected to the DCMD performances such as permeate flux and thermal efficiency. In other word, the membrane geometrical variables and operating conditions could be determined the performance of the DCMD system. The difference in water vapor pressure as the driving force of process was generated by the temperature difference of liquid-vapor interface between the feed and permeate sides. However, the temperature of liquid-vapor interface could not measure thus those temperatures can be predicted by the rigorous theoretical approaches to predict the system performance. RESULTS AND DISCUSSION

CNT functionalization and dispersion To employ CNTs as effective reinforcement in polymer nanocomposites, proper dispersion and appropriate interfacial adhesion between the CNTs and polymer matrix have to be guaranteed. To modify CNT to become hydrophobic, first, defect functionalization was applied due to its advantage of chemical transformation of defect sites on CNTs. The defects sites at the open ends on CNTs created by oxidants are stabilized by bonding with carboxylic acid (–COOH) group. Then, this modified CNTs can be precursors for further chemical reaction such as silanation. POTS was used for the surface modification of CNT. POTS possesses a low surface free energy and the carbon-fluorine bond formed on the CNT surface is stable. When POTS hydrolyses in wet environment, a silane based film formed from the hydrolysis and polycondensation of POTS, which provides an additional hydrophobicity to the CNTs. Such combination of functionalization poses an insignificant damage to CNTs, inhibits the re-agglomeration of CNTs, produce strong interfacial bonds with polymer and facilitates further on the fabrication of a well dispersed membrane. As shown in the TEM images (Fig. 1), the dispersion of CNTs was improved after the functionalization (a) compared with the pristine CNTs as received (b).

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(a)

(b)

Figure 1. TEM images of (a) F-CNT dispersed (b) Pristine CNT dispersed.

The chemically functionalized CNTs can produce strong interfacial bonds with many polymers, allowing CNT- based nanocomposites to possess high mechanical and functional properties.

Hydrophobicity of F-CNT electrospun membrane The water contact angles of the commercial PVDF membrane and PcH membrane are 123° and 142°, respectively. On the other hand, the water contact for F-CNT membrane with 0.5 wt% of CNTs is 146°, indicating the improvement of membrane hydrophobicity by the functionalized CNTs. As the content of functionalized CNTs increases to 1 wt%, the water contact angle for the membrane further increases to 149°. The enhancement in water contact angle marks the significant role of functionalized CNTs in membrane hydrophobicity. With 1 wt% of CNTs, the F-CNT membrane approaches superhydrophobic. It is believed that the superhydrophobic property can be achieved by increasing the content of CNTs. However, further study is required to overcome the agglomeration effect of CNTs upon higher concentration. The surface morphology of the F-CNT membrane and the PcH membrane are shown in Fig. 2. The morphology of F-CNT-1% membrane comprises larger surface of prominence than that of PcH membrane. With the imposed nano-scaled protrusions, the roughness of membrane was enhanced in the presence of CNTs.

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(a)

(b)

Figure 2. SEM images of (a) F-CNT membrane and (b) PcH membrane.

Diameter, pore size distribution and liquid entry pressure On top of the surface morphology, the SEM images show the changes in dimension of nanofiber after incorporating functionalized CNTs into PcH membrane (Fig. 2). It was found that the nanofiber diameter of F-CNT-1% membrane is generally less than that of PcH membrane. The average fiber diameter of the electrospun membranes was measured. PcH membrane is comprised of the thickest fiber among the others with an average fiber diameter of 253.9±59.5 nm. F-CNT-0.5% and F-CNT-1% membranes possess fibers with an average diameter of 244.0±62.2 and 218.8±86.5 nm, respectively. The pore size of the commercial PVDF membrane is ranged from 0.5 to 0.8 µm with 70% of pore dominated at 0.66 µm. Compared with the commercial PVDF membrane, the pore size distribution of the membrane fabricated in this study is more uniformed and comprises of larger average pore size. The largest pore size was achieved for F-CNT-1% membrane and 90% of its pores are 0.88 µm in size. In order to quantify the long-term stability of the membranes for MD application, LEP of all membranes were measured. The LEP for the commercial PVDF, PcH, F-CNT-0.5% and F-CNT-1% membranes are 105, 86.4, 87.1 and 89.5, respectively. In the context of LEP, the commercial membrane performs slight better than the electrospun membranes and enables a higher hydraulic pressure on the membrane surface of the feed side. Accordingly to the Laplace equation, the LEP is directly proportional to the cosine of water contact angle and inversely proportional to the largest pore size. Although the water contact angle has been improved after incorporating functionalized CNTs into PcH membrane, the LEP slightly dropped.

MD performance The MD experiments using DCMD were performed with the commercial PVDF, PcH and F-CNT-1% membranes. The water flux for the F-CNT-1% membrane with 60°C applied on the feed for DCMD provided the largest average flux of 32 kg∙m2/h. The flux is about 60% higher than that of the commercial PVDF membrane (i.e., 20.2 kg∙m2/h). In addition, the water flux was relatively stable throughout the 12 h of operation, as compared with other

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membranes. The rejection rates of all membranes are above 99.98%, indicating that the membranes fabricated in this study are suitable for seawater desalination in different MD operations.

Effect of carbon nanotubes (CNTs) In this study, the CNTs enhanced membranes, which mixed the different concentrations of CNTs ranging from 0 to 2% with PcH were employed. In the experimental results, the effect of the concentrations of CNTs on the mean permeate flux (kg/m2h) has clearly revealed that the mean permeate flux increased with an increase in the concentrations of CNTs. In order to explain the reason of this increase, many researchers have been studied and also provided the several theoretical theories. Among those theories, two theories have been adopted: (i) the water vapor molecular could be slip on super hydrophobic pore innerwalls. It means the water vapor molecule has the smallest travel distance in the pores between feed and permeate sides compared with the Knudsen and molecular diffusion; and (ii) super hydrophobic membrane can be achieved the enhancement of the condensation at the liquid vapor interface at the permeate side. Thus in this paper, in order to consider the effect of CNTS on the mean permeate flux, the dusty gas model (as a mass transfer coefficient) is modified.

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REFERENCES 1. A. Striolo, The mechanism of water diffusion in narrow carbon nanotubes, 6 (2006) 633–639. 2. A. Fujiwara, K. Ishii, H. Suematsu, H. Kataura, Y. Maniwa, S. Suzuki, et al., Gas adsorption in the inside and outside of single-walled carbon nanotubes, Chem. Phys. Lett. 336 (2001) 205–211. 3. K. Gethard, O. Sae-Khow, S. Mitra, Carbon nanotube enhanced membrane distillation for simultaneous generation of pure water and concentrating pharmaceutical waste, Sep. Purif. Technol. 90 (2012) 239–245.

SANGHYUN JEONG Title: Postdoctoral Research Fellow King Abdullah University of Science and Technology, Saudi Arabia Phone: +966 (0)12 808 7504 E-mail: [email protected] 2013-2015

Research Associate, University of Technology Sydney, Australia

Since 2015

King Abdullah University of Science and Technology, Saudi Arabia

Research interests: Desalination, Pretreatment, Water treatment, Filtration, Biofouling

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W1.17 NUR IZWANNE MAHYON CERAMIC HOLLOW FIBRE CATALYTIC CONVERTERS FOR AUTOMOTIVE EMISSIONS CONTROL

NUR IZWANNE MAHYON, KANG LI Imperial College London Expansion of automotive sector since 1940, lead to a major transformation to the world economy. As the world demand for automobiles increases each year, concern on health and environmental impacts caused by tailpipe gases being emitted also now a major issues which lead to a restriction in emissions abatement falls to a tighter range of allowable emissions. To tackle the problem, catalytic converters have been used for exhaust treatment. A catalytic converters consist of two major components; a substrate which commonly a dense ceramic honeycomb monolith and catalytically active washcoat for reaction purposes. The substrate which consist of huge number of channels in which the gasses pass is responsible to provide a large Geometric Surface Area (GSA) for the oxidation of carbon dioxide (CO), Hydrocarbons (HC) and reduction of nitrous oxide (NOx) reactions. Catalytic converters using a ceramic hollow fibre substrate an attractive goal, but to-date there has yet to be a system that can demonstrate the required emissions conversion efficiency, engine performance or be manufactured at a reasonable cost. The importance of substrate development is crucial as large geometric surface area for deposition of active catalyst helps in reducing the catalyst loading in the system as it is well known price volatility of the precious metals used is the main problem in catalytic converters development. Figure 1 represents our current hollow fibre substrate design. Extrusion of ceramic induced by phase inversion process is used to fabricate this structure. It is worth mentioning that the new substrate structure offers a 7 – 8 fold increases in the GSA as a result of the high density self-organized micro-channels inside the lumen side. There are several key features worth mentioning in these new innovation substrate structure: i) porous ceramic monolith can possess a relatively high open frontal area where pressure loss of gases flowing through it will be low thus reducing the back-pressure effects as it is crucial to keep efficiency losses as minimum as possible, ii) reduction in the substrate volume, iii) reduction in precious metal catalyst loading as a much thinner catalyst washcoat is needed for the reaction.

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Figure 1: Cross-section SEM images of Ceramic hollow fibre substrate developed.

The versatile fabricating technique delivers a structured micro-channels which the process are continuous, scalable and cost effective. This contribute to the considerable reduced production time and costs NUR IZWANNE MAHYON Affiliation, Country: Imperial College London, United Kingdom Phone: +44-07546260670 E-mail: [email protected] Research interests: Ceramic and polymeric membrane, catalytic converters, catalyst.

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W1.18 I. A. IKE THE EFFECTS OF DISSOLUTION CONDITIONS ON THE PROPERTIES OF PVDF MEMBRANES FOR WATER FILTRATION

I. A. IKE1, A. GROTH1, J. D. ORBELL1, AND M. DUKE­ 1 Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, Melbourne, Victoria 8001, Australia. Poly (vinylidene fluoride) (PVDF) membranes find application in a number of water treatment and separation processes and are an ongoing subject of much research interest. The inherent properties of PVDF membranes are dependent on several variables including the conditions of initial polymer dissolution. Earlier works1,2 have shown that major morphological changes can be achieved when PVDF is dissolved under different temperature conditions but only limited attention was focused on the effects of dissolution conditions on the membrane properties of relevance to water filtration. This work reports the study of PVDF membranes produced from dopes dissolved by stirring the polymer in the solvent N-methyl-2-pyrrolidone at 24 °C, 90 °C and 120 °C. A fourth membrane produced by continuous sonication of PVDF in the solvent was also evaluated. All membranes were formed under the same phase inversion conditions in room temperature water. The results showed that very high water flux of more than 600 Lm-2h-1 at a transmembrane pressure (TMP) of 30 kPa was obtained for the membranes produced from dopes dissolved at 24 °C and 120 °C. The lowest water flux of about 180 Lm-2h-1 resulted for the sonicated membrane. However, the sonicated membrane exhibited outstanding performance (Fig.1) during the crossflow filtration of a synthetic oily emulsion (with oil droplet size between 20 – 500 nm) employed as a model foulant at TMP of 30 kPa. The mass of the permeate collected for the sonicated membrane was more than double the permeate mass for the other membranes at the end of the filtration period of 120 min. The sonicated membrane exhibited not only the highest permeate flux but also the highest flux recovery of 63% while the membrane produced at 24°C had the lowest flux recovery of 26%. Flux recovery was determined by comparing clean water flux before fouling and after fouling and membrane cleaning with 0.1 M NaOH solution for 30 min at 30 kPa. The TOC rejections for all the membranes were about 92 %.

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Figure 1. Permeate flux during crossflow filtration of oily emulsion

Although high permeate flux under severe fouling conditions and enhanced flux recovery is often associated with hydrophilicity improvement3, membrane wettability differences cannot explain the flux results obtained in this work since the average water contact angle (CA) for the sonicated membrane with the best flux recovery was 86° while the membrane dissolved at 24 °C with the worst flux recovery had a slightly lower average water CA of about 82°. The wettability values are practically identical but a lower CA for the sonicated membrane would have been expected based on the filtration results. However, a consideration of the membranes skin layer pores (Fig.2) suggests that the key performance differences may have arisen from the smaller size pores and narrower pore size distribution of the sonicated membrane when compared to the larger pores and wider pore size distributions for the other membranes. It appears that the narrow pore diameter range (<25 nm) for the sonicated membrane allowed for adequate percolation of water molecules but was less accessible to the oil droplets in the emulsion resulting in sustained high water permeation and low membrane fouling as oil droplets were substantially excluded from the membrane pores. The other membranes with pore diameter up to 70 nm were more exposed to oil droplet pore blocking resulting in reduced flux and limited flux recovery. In addition, the relatively smooth surface for the sonicated membrane as may be seen in the SEM images of Fig.3 may have contributed significantly to its better flux recovery. Consequently, membrane skin layer pore tailoring is potentially an important tool for designing low fouling membranes for handling highly fouling feed as was demonstrated for the sonicated membrane. On the other hand, the high permeability membranes (24 °C and 120 °C) may be suitable for treating water with reduced contaminate load at very high flux.

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Figure 2. Skin layer pore size distribution generated from skin layer SEM images with Image J

Figure 3. Membrane skin layers SEM images for 24 °C (a), 90 °C (b), 120 °C (c) and Sonic (d) REFERENCES 1 D. J. Lin, K. Beltsios, et al., J. Membr. Sci. 2006, 274, 64-72. 2 X. Wang, X. Wang, et al., J. Macromolecular Sci, Part B. 2009, 48, 696–709. 3

L. Yan, S. Hong, et al., Separation and Purification Tech., 2009, 66, 347–352

IKECHUKWU ANTHONY IKE Title: Mr Institute for Sustainability and Innovation, Victoria University, Australia Phone: +61 450 294 694 E-mail: [email protected] 2010-2011

Completed Masters in Petroleum Engineering at AUST, Abuja

Since 2013

PhD study in chemical engineering at Victoria University

Research interests Waste water management using membrane and catalysis

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W1.19 X. YANG DEMONSTRATION OF AMMONIA CAPTURE FROM INDUSTRIAL EFFLUENTS

X. YANG1, A. LIUBINAS2, MIKEL DUKE1 1 Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, P.O.BOX 14428, Melbourne, Victoria 8001, Australia; 2 City West Water, Melbourne, VIC 3020, Australia The loss of nitrogen (ammonia and other forms) to wastewaters has been a major threat to the aquatic environment and poses a challenge to wastewater treatment [1]. As one of the major metropolitan water retailers in Victoria, City West Water (CWW) has an interest to remove ammonia from trade waste as it presents a safety risk to sewer workers, and is costly and energy intensive to remove from wastewater prior to discharge to the environment. An environmentally-friendly solution is sought after to isolate ammonia from wastewater, potentially capturing it for direct reuse with simple operation and low energy use. Although the concept of ammonia capture was demonstrated commercially viable through selective ion exchange in the early 1980s [2], lower cost and simplified approaches are needed. Membrane distillation using hydrophobic membranes is effective in removing ammonia from wastewater [3]. Only synthetic feeds with pH ranging from 10-14 and high ammonia content have been investigated. A commercial liquid-Cell system (hydrophobic membrane contactor) from Membrana uses acid solutions to strip ammonia only from pH>10 waters due to the higher proportion of volatile free ammonia according to the pH-free ammonia equilibrium relationship [4]. However, most industrial effluents containing ammonia nitrogen are in the pH range 6-10, and may also be adjusted to these lower pH values to meet water utility discharge requirements. This study attempts to recover ammonia nitrogen from various industry point sources in Western Melbourne using membrane distillation with commercial hydrophobic membranes. The feasibility of ammonia capture at unadjusted water chemistry and direct reuse in various scenarios based on pilot trials will be discussed. Initially, laboratory studies were conducted to investigate ammonia removal/capture from real industrial wastewaters under unadjusted water chemistries (e.g., pH and TDS) using membrane distillation. Anaerobic digester supernatants from wastewater treatment and foods processing plants, as well as power station ion exchange regeneration effluent, were tested. The pH of these solutions ranged from pH 6 to pH 11. Synthetic solutions with low and high pH were also studied. Overall, membrane performance data showed that the total flux increased with increasing feed temperature. However, the ammonia enrichment into the permeate initially increased and then decreased with increasing operating temperature, where the optimal thermal condition was identified at 40-45 ºC. This temperature is conveniently a common low grade waste heat temperature available at industry sites and can be a source of energy for the MD process. Typically higher ammonia removal occurs at pH values higher than 10, as indicated by the synthetic solution testing

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shown in Fig. 1. Ammonia recovery reached 90% with high ammonia selectivity in the testing period. However, several industry samples also showed ammonia capture at pH as low as 6. For example in our previous pilot trial work, direct contact MD (DCMD) testing on industry effluent showed the ability of capturing the majority of ammonia (70%~90%) at pH of around 7 as a clean water-ammonium solution [5]. A separate study showed that unique water chemistries enable this capture at pH values lower than predicted by the conventional pH-free ammonia equilibrium relation. With the promising results so far, in order to demonstrate the concept of ammonia capture resource recovery, a survey of various sites will be conducted to highlight relevant case studies. The case studies will show key features including availability/amount of waste heat, effluent chemistry, reuse of captured ammonia and other site specific issues. A pilot trial at one of these sites is currently being considered to practically demonstrate the concept in terms of long term performance and practical ammonium reuse viability. A process diagram was designed to extend this concept to industrial application, as shown in Fig 2.

Fig. 1 NH3 enrichment factor, total flux and recovery % in VMD using commercial hallow fibre membrane for synthetic ammonia solutions at and pH 11 (ammonia concentration 300ppm, feed temperature 45 ºC, vacuum pressure =0.39±0.2 kPa)

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Fig 2 Flow diagram of ammonia capture process in industrial application REFERENCE: 1

Paerl, H. W., Cultural eutrophication of shallow coastal waters: Coupling changing anthropogenic nutrient inputs to regional management approaches, Limnologica - Ecology and Management of Inland Waters, 1999, 29 (3) p.249-254

2

Liberti, L., in Studies in Environmental Science, L. Pawlowski, Editor. 1982, Elsevier. p. 225-238.

3

El-Bourawi, M.S., et al., Application of vacuum membrane distillation for ammonia removal. Journal of Membrane Science, 2007. 301(1-2): p. 200-209

4

Ulbricht, M., et al., Ammonia Recovery from Industrial Wastewater by TransMembraneChemiSorption. Chemie Ingenieur Technik, 2013. 85(8): p. 1259-1262.

5

Dow, N. and M. Duke, The potential for membrane distillation of industrial wastewaters. WaterJournal of the Australian Water Association, 2011. 38(6): p. 78-82.

XING YANG Title: Dr Affiliation, Country: Victoria University, Australia Phone: +61 3 99197690 Fax: +61 3 9919 7696 E-mail: [email protected] 2012-2013

Nanyang Technological University, Singapore

Since 2013

Institute for Sustainability and Innovation, Victoria University

Research interests: Membrane technology for water treatment and reclamation, Membrane distillation and low-energy resource recovery from wastewaters Zero liquid discharge and mineral extraction; Process simulations and modeling

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THEME: ADVANCES IN MF AND UFMEMBRANES

THEME: ADVANCES IN MF AND UFMEMBRANES W2.2 ANBHARASI VANANGAMUDI ENHANCED ANTIFOULING OF NOVEL NANOFIBROUS BI-LAYER COMPOSITE ULTRAFILTRATION (UF) MEMBRANES

ANBHARASI VANANGAMUDI1,2, LUDOVIC F. DUMÉE 2, MIKEL DUKE1, XING YANG1 1 Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, Melbourne, Victoria 8001, Australia 2 Deakin University, Institute for Frontier Materials, Waurn Ponds, Victoria 3216, Australia One major drawback of Ultrafiltration (UF) membranes is related to surface fouling leading to deteriorating performance over time, in the form of rejection impairment, flux reduction and membrane damage. These issues are thus increasing the operational costs and shortening membrane lifespan1. Membrane organic fouling originates from the surface deposition of natural organic matter (NOM) and extracellular polymeric substances (EPS) across the membrane surface2. Altering membrane hydrophilicity is one of the key research efforts to mitigate membrane fouling. In this research, novel nanofibrous bi-layer composite UF membranes were prepared by consecutive electrospinning and polymer phase inversion to form a dual layer membrane material with enhanced permeability and antifouling properties. Also, the degree of integration of the layers depending on the PVDF concentration and its effect on permeability and membrane fouling were studied. Firstly, nanofiber layers were fabricated via electrospinning a mixed dope solution of hydrophilic nylon and chitosan polymers. Secondly, a support layer was introduced via conventional casting of different concentrations of poly(vinylidene fluoride) (PVDF) solutions (12, 15, 18, 21 and 24 in wt%) onto the nanofiber layer, thus forming novel bi-layer composite membranes with tuneable pore morphologies and surface energies. The high surface area of the nanofibers forms a good platform for enzyme attachment to further reduce organic fouling. The membranes were characterized for their morphology using scanning electron microscopy (SEM). The SEM images illustrate that, as the PVDF concentration in the composite membrane increases, the degree of integration of nanofiber layer and the casted layer decreases with different pore arrangement. However, the optimum integration based on the permeability and rejection parameters was found to occur in the composite membranes with 18 wt% PVDF concentration, as indicated by the membrane morphology shown in Fig.1. Fourier transform infrared (FTIR) spectroscopy analysis confirmed the presence of hydroxyl and amine functional groups from nylon and chitosan across the surface of the membranes. The measurements on contact angle of water GOLD SPONSOR

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(CAw) revealed that the composite membranes exhibited improved hydrophilicity in the order of PVDF < PVDF-Nylon < PVDF-Nylon-Chitosan membranes at varying PVDF concentrations, as shown in Fig.2. In general, the hydrophilicity of the membranes decreased with increasing PVDF concentration due to lower degree of integration between the hydrophobic PVDF and the hydrophilic nylon/chitosan layers, resulting in less hydroxyl and amine functional groups present on the membrane surface. Furthermore, the overall water permeability decreased with increasing PVDF concentration for each type of membrane. The addition of nylon and chitosan nanofibers affected the water permeability. Initially, at low PVDF concentration (12 and 15 wt%), the control membrane showed the highest flux, followed by the composite membranes. As the PVDF concentration further increased to 18 wt% and above, the PVDF-Nylon-Chitosan membrane started to outrun the control membrane and exhibited the highest permeability. Hence, the PVDF concentration could be optimized as 18 wt% based on the bi-layer integration and membrane hydrophilicity as measured through polyethylene glycol (PEG) rejection experiments. Also, the antifouling evaluation test using a dead-end filtration system performed with bovine serum albumin (BSA) contaminants demonstrated an increased fouling resistance for the PVDF-Nylon-Chitosan membrane compared to the control membrane at 18 wt% PVDF concentration. In addition, antibacterial study was performed for the optimized membrane by evaluating the zone of inhibition with E.coli. Overall, the novel bi-layer composite UF membranes exhibited enhanced antifouling properties attributed to the optimized degree of integration and morphological properties such as improved hydrophilicity and pore structure. However, the size and nature of foulants play an important role in altering the membrane fouling property that extends the concept of material functionality and surface modification to other prospective applications.

Casted support layer

Integrated nanofiber and casted layer Figure 1. (a) Surface (left) and (b) cross sectional (right) SEM images of the bi-layer PVDF-Nylon-Chitosan membrane with 18 wt% PVDF concentration Figure 2. Pure water permeability and water contact angle of the control PVDF, PVDF-Nylon and PVDF- Nylon-Chitosan composite membranes

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REFERENCES 1 X. Shi, G. Tal, N.P. Hankins, V. Gitis, Journal of Water Process Engineering. 2014, 1, 121-138. 2 S.T. Kelly, A.L. Zydney, Journal of Membrane Science. 1995, 107, 115-127. 3 P. Le-Clech, V. Chen, T.A.G. Fane, Journal of Membrane Science. 2006, 284, 17–53

ANBHARASI VANANGAMUDI Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, Melbourne, Victoria 8001, Australia Phone: +61 3 9919 8248 Fax: +61 3 9919 7696 E-mail: Anbharasi. [email protected] 2010

Completed Master of Engineering and graduated from National University of Singapore (NUS)

2010-2015

Worked as research associate in Centre of Innovation (Membrane Technology group) in Singapore

Since 2015

PhD in Victoria University

Research interests: Nanomaterials, Polymeric membrane development for air and water purification, drug delivery and responsive and biological membranes

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THEME: ADVANCES IN MF AND UFMEMBRANES

W2.3 BURHANNUDIN SUTISNA DESIGN OF BLOCK COPOLYMER MEMBRANES USING A MASTER CURVE FOR VARIOUS COPOLYMER ARCHITECTURES

BURHANNUDIN SUTISNA,1VALENTINA MUSTEATA,1KLAUS-VIKTOR PEINEMANN,1AND SUZANA P. NUNES1 1 King Abdullah University of Science and Technology (KAUST), 23955-6900 Thuwal, Saudi Arabia Membranes with an ultrahigh porosity and uniform pore size distribution can be fabricated using the combination of block copolymer self-assembly and non-solvent induced phase separation (SNIPS) method.1-3 Functionality and selectivity of the membranes can be controlled for specific separations using a broad range of tailor-made block copolymers with various configurations. We have investigated poly(styrene-b-4-vinylpyridine),1,4 poly(styrene-b-ethylene oxide),5 poly(styrene-b-acrylic acid),6-7 and polysulfone-based copolymers8 to fabricate self-assembled membranes demonstrating various stimuli responsive and separation performances. The extension of SNIPS method to any new copolymer is however challenging and time consuming due to the complex interplay between the influencing parameters, such as copolymer structures and molecular weights, solvent properties, casting solution concentration, and evaporation time. We proposed an effective method for designing new block copolymer membranes using a predetermined trend line (Fig. 1a) of previously-investigated isoporous membranes as a guide to obtain the preparation conditions for new membranes.9 The trend line was obtained by computing enthalpic (polymer-solvent interactions) and enthropic (copolymer block sizes) contributions of the successful systems. We applied the method to diblock and triblock copolymers, such as a commercial poly(styrene-b-ethylene oxide) and a newly synthesized poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer (Fig. 1b and c). The trend line can be used as a master curve for other new systems with different copolymer architectures for targeted membrane performance as well as tailored pore sizes and functionalities, and is expected to dramatically shorten the path of isoporous membrane manufacture.

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Figure. 1. (a) Trend line fitted from the filled data points (P1-P6) of dimensionless parameter versus for various polymer-solvent systems previously confirmed as leading to isoporous membrane; unfilled data points corresponding to unordered systems. (b) AFM and (c) SEM images of PS-b-P2VP-bPEO membrane surface (b) and cross section (c). REFERENCES 1 S. P. Nunes, R. Sougrat, B. Hooghan, D. H. Anjum, A. R. Behzad, L. Zhao, N. Pradeep, I. Pinnau, U. Vainio and K.-V. Peinemann, Macromolecules, 2010, 43, 8079-8085. 2 P. Madhavan, K.-V. Peinemann and S. P. Nunes, ACS Appl. Mater. Interfaces, 2013, 5, 7152-7159. 3 S. P. Nunes, Macromolecules, 2016, 49, 2905-2916. 4 Nunes, S. P.; Behzad, A. R.; Hooghan, B.; Sougrat, R.; Karunakaran, M.; Pradeep, N.; Vainio, U.; Peinemann, K.-V., ACS Nano, 2011, 5, 3516-3522. 5 Karunakaran, M.; Nunes, S. P.; Qiu, X.; Yu, H.; Peinemann, K.-V., J. Membr. Sci., 2014, 453, 471-477. 6 Yu, H.; Qiu, X.; Nunes, S. P.; Peinemann, K.-V., Nat. Comm., 2014, 5 7 Yu, H.; Qiu, X.; Moreno, N.; Ma, Z.; Calo, V. M.; Nunes, S. P.; Peinemann, K. V., Angew. Chem. Int. Ed., 2015, 54, 13937-13941. 8 Xie, Y.; Moreno, N.; Calo, V.; Cheng, H.; Hong, P.-Y.; Behzad, A. R.; Tayouo, R.; Nunes, S., Polym. Chem., 2016. 9 B. Sutisna, G. Polymeropoulos, V. Musteata, K.-V. Peinemann, A. Avgeropoulos, D.-M. Smilgies, N. Hadjichristidis and S. P. Nunes, Mol. Syst. Des. Eng, 2016.

BURHANNUDIN SUTISNA Title: Mr. King Abdullah University of Science and Technology (KAUST), Saudi Arabia Phone: +966 12 8082146, E-mail: [email protected] 2013-present

PhD Student in Chemical and Biological Engineering, KAUST

2011-2013

Trainee Design Engineer, TU Eindhoven

2009-2010

M.S. in Chemical and Biological Engineering, KAUST

2005-2009

B.S. in Chemical Engineering, Institut Teknologi Bandung

Research interests: block copolymer self-assembly, ultra/nanofiltration membranes

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W2.4 LISA LECKIE APPLYING ADVANCED AERATION DESIGN TO DOUBLE-ENDED SUBMERGED FILTRATION

LISA LECKIE1, STEVEN CAO, AARON BALCZEWSKI 1 Evoqua Water Technologies Membrane Systems Pty. Ltd 2 Evoqua Water Technologies LLC This paper introduces a new approach to submerged hollow fibre membrane filtration using double-ended filtration, thereby removing the length limitation from pressure losses. This approach provides challenges in how to provide membrane cleaning air which is typically supplied through a static bottom end of the module, and requires the development of compact and cost-effective components to deliver the air. Operationally, the biggest limitation of submerged systems is the available operating pressure range for suction, which for submerged systems is the driving force for filtration. A compounding factor is the need for a static module end to facilitate solids removal during cleaning, so filtration is only from one end of the module. When modules lengths are increased, the pressure losses down the module become prohibitive and the gains are limited. This is a problem for submerged because it limits improvements in some of its key applications, namely deep filter bed retrofits. Being able to take filtrate from both ends of the module therefore yields many benefits for submerged systems. A commercially available module, typically used for pressurized applications, was used to demonstrate the efficacy of the concept. This facilitated rapid operational improvements through the elimination of module design development requirements. The main design challenge was the delivery of air to the module for cleaning, and this was achieved through the development of an integrated aerator. Operational trials have been conducted in Australia and California. The configuration of the aerator was found to deliver air at a higher cleaning efficiency than traditional aeration delivery methods, thereby making this approach to submerged filtration viable. LISA LECKIE R&D Program Manager Evoqua Water Technologies Membrane Systems Pty. Ltd, Australia Phone: +61 2 4577 0822 Fax: +61 2 4577 0919 E-mail: [email protected] 1998 - Present Evoqua Water Technologies Membrane Systems Pty Ltd (inc. roles in project management, membrane manufacturing, water and wastewater operating processes for membranes, systems and applications engineering, and sales and marketing. 1994-1997

Bachelor of Chemical Eng. (Hons 1), UNSW

2008

Cert IV Project Management - ACPM

Research interests: Hollow fibre membrane processes and manufacturing, accelerated product commercialisation

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THEME: ADVANCES IN MF AND UFMEMBRANES

W2.5 JIA WEI CHEW EFFECT OF SPACER AND CROSSFLOW VEL ITY ON THE CRITICAL FLUX OF BIDISPERSE SUSPENSIONS IN MICROFILTRATION

HENRY J. TANUDJAJA1, WENXI PEE2,3, ANTHONY G. FANE2, JIA WEI CHEW1,2,* 1 School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore 2 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore 3 School of Civil and Environmental Engineering, Nanyang Technological University, Singapore Crossflow microfiltration is a popular application spanning various industries. Although the impacts on fouling of feed bidispersity, crossflow velocity (CFV) and spacer, all of which are present in practical operations, are known separately, the understanding of the interplay of these three factors on fouling is lacking. Accordingly, this study used the Direct Observation Through the Membrane (DOTM) technique to characterize the critical flux of monodisperse and bidisperse polystyrene particles in both the absence and presence of a spacer over a range of CFV values. The particles investigated was polystyrene (also known as latex); the monodisperse particle had a particle diameter (dp) of 3 µm, while the bidisperse mixture was an equal volume ratio of dp = 3 µm and 10 µm. To understand the enhancement effects of bidispersity and spacer, Fig. 1 displays the enhancement factors with respect to the monodisperse particle system (Jcrit,3μm+10μm/ Jcrit,3μm) and the system without a spacer (Jcrit,spacer/Jcrit,no spacer) respectively in Figs. 1a and b. Both sub-plots have the same ranges of x- and y-axes for easier comparison. In Fig. 1, all the values are above one, which implies the expected beneficial effects of bidispersity and spacer. Fig. 1a shows that the enhancement factor, Jcrit,3μm+10μm/Jcrit,3μm, was greater in the absence of spacer at lower CFVs (i.e., < 0.15 m/s), which affirms that the spacer diminished the shear-induced diffusion enhancement of the smaller particles by the larger particles; however, the impact of spacer was negligible at higher CFVs (i.e., > 0.15 m/s). On the other hand, Fig. 1b shows that the enhancement factor, Jcrit,spacer/Jcrit,no spacer, was greater for the monodisperse rather than the bidisperse system at lower CFVs, which indicates that the spacer was more effective for the monodisperse system; however, higher CFVs similarly diminished the difference between the two systems. Comparing the two sub-plots in Fig. 1 reveals that (i) the enhancement induced by bidispersity (Fig. 1a) was greater than by spacer (Fig. 1b) at lower CFVs, and (ii) the effect of CFV on diminishing the enhancement induced by bidispersity (Fig. 1a) was more severe than that by spacer (Fig. 1b).

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Figure 1. Enhancement of critical flux (Jcrit): (a) effect of bidispersity in the presence and absence of a spacer; (b) effect of spacer on monodisperse and bidisperse particle systems.

In conclusion, four observations are worth highlighting. The results show that: (i) the combined effects of both bidispersity (dp = 3 µm and 10 µm) and spacer were the most beneficial in mitigating membrane-fouling in terms of the highest Jcrit values, whereas the case of a monodisperse particle with dp = 3 µm in the absence of a spacer gave the lowest Jcrit values; (ii) whereas bidispersity was more effective at enhancing Jcrit at a lower CFV (which means a lower energy requirement), the presence of a spacer was more effective at a higher CFV which augmented the eddy formation effects; (iii) the enhancement induced by bidispersity was diminished at α high CFV and, to a lesser degree, by the spacer; and (iv) comparisons between model predictions and experimental data reveal that shear-induced diffusion models based on monodisperse particles are deficient for bidisperse mixtures, due to the lack of consideration of effects unique to non-monodisperse systems like particle size segregation. Regarding the impact of bidispersity, the presence of larger particles improved the Jcrit values due to the associated higher shear-induced diffusivity. However, the beneficial effects are limited to lower CFV magnitudes, because both the Reynolds number and segregation effects dictate the diminished influence of the larger particles at higher CFVs. With respect to spacer, the presence of a spacer on one hand enhanced the Jcrit values for both monodisperse and bidisperse mixtures, but on the other hand reduced the enhancement factor induced by bidispersity (i.e., the enhancement of Jcrit value for the bidisperse mixture was lowered in the presence of a spacer). It should be noted that the shear-induced diffusion models are largely for laminar flows, so the local eddies induced by spacers are not well characterized by the mechanistic basis of these models.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ADVANCES IN MF AND UFMEMBRANES

CHEW, JIA WEI Title: Assistant Professor Nanyang Technological University, Singapore Phone: +65 6316 8916 E-mail: [email protected] 2011

Ph.D., Chemical Engineering, U of Colorado at Boulder, U.S.A.

2011-2013

Research Scientist, MEMC-SunEdison, U.S.A.

Since 2013

Assistant Professor, Nanyang Technological University, Singapore

Research interests: Particle Technology, Membrane Technology

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THEME: ADVANCES IN MF AND UFMEMBRANES

W2.6 XING DU PARTICLE DEPOSITION ON FLAT SHEET MICROFILTRATION MEMBRANES UNDER BUBBLY AND SLUG FLOW AERATION: EFFECTS OF PARTICLE SIZE AND PORE BLOCKING

XING DU1,3, YUAN WANG1, PEYMAN MOSTAGHIMI2, GREG LESLIE1, HENG LIANG3 1 UNESCO Centre for Membrane Science & Technology, School of Chemical Engineering, University of New South Wales, Sydney 2052, Australia 2 School of Petroleum Engineering, The University of New South Wales, NSW 2052, Sydney, Australia 3 State Key Laboratory of Urban Water Resource and Environment (SKLUWRE), Harbin Institute of Technology, 73 Huanghe Road, Nangang District, Harbin, 150090, P.R. China Particle deposition on submerged flat sheet microfiltration membranes in a flow field induced by bubbly and slug flow was investigated for the purposes of optimizing membrane filtration in drinking water applications. Fouling propensity of the flat sheet membranes on three feed waters was measured for nine separate operating regimes, while a two phase flow Computational Fluid Dynamics (CFD) model (Figure 1) coupled with a user defined particle migration model, was used to investigate the effects of particle size distribution in the feed water and hydrodynamic conditions on pore blocking and cake formation during MF processes. Particle size distributions of the three different feed water were measured using Malvern Mastersizer 2000. The geometry used in the particle migration model was built based on the real porous structure of the MF membrane, which was obtained using high-resolution Scanning Elelctron Microscopy (SEM). The particle (floc) size distribution of the three influent was shown in Figure 2. (a). It can be seen that average particle size of the feed flow, the PACl dose flow and PACl+PAM dose flow was 2.55 μm, 117.28 μm and 161.02 μm, respectively. After microfiltration, the coverage deposited mass presented a similar trend, with the coverage deposited mass in the range of 52-56 g/m2 in case of synthetic raw water irrespective of hydrodynamic condition (i.e., no aeration, bubbly flow and slug flow), which was similar to that of MF filtrating coagulation or coagulation aid solutions without aeration (Figure 2 (b)). The aeration was more efficient for particles removal in case of MF filtrating coagulation or coagulation aid solutions, the coverage deposited mass was 1-3 g/m2, 6-8 g/m2 under bubbly flow and slug flow conditions, respectively.

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Flow direction

Membrane

Air inlet

Volume(%)

12 Feed water Coagulation Coagulation aid

8

4

0

0.1

1

10

size (mm)

100

1000

Deposited coverage mass (g.m-2)

Figure 1. Schematic of (a) geometry and (b) mesh of MF tank with bubbly flow

60

No aeration

Bubbly flow

Slug flow

40 8 6 4 2 0

ater d w e e F

aid tion tion gula gula Coa a o C

Figure 2. The particle size distribution of initial aggregates (a) and (b) deposited coverage mass under nine kinds of operation condition

Simulation results showed that when the bubbly flow was used and the air flow rate was 0.1 m3/h, in the upper zone of the tank, the liquid velocities were in the range of 0.06-0.12 m/s, while in the lower zone, the liquid velocity exhibited a comparatively lower range (0.020.06 m/s) (Figure 3). It should be also noted that the velocity distribution on membrane surface was not uniform under these conditions.

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Figure 3. Flow field in the membrane tank(A) y= 0 and (B) y+ = 0.04 m (on the membrane surface)(XZ)

CFD calculated velocity profiles were integrated with the particle migration model to assess the effects of flow patterns and particle size distribution of the feed. The results quantitatively indicated the proportion of particle deposited on membrane surface to form cake layer or trapped by membrane pores. A consistent trend has been found when compared with the experimentally measured hydraulic resistances of the membranes. This study has been the first in the literature to model the particle movement inside the porous structure of MF processes. XING DU Title: Mr. UNESCO Centre for Membrane Science & Technology, Austrian, Phone: +86 13644617496 +61 0457675387 E-mail: [email protected] 2015-2016

International practicum student in UNESCO Centre for Membrane Science & Technology, School of Chemical Engineering, University of New South Wales

2011-2015

Master Degree and Ph.D. candidate Harbin Institute of Technology, China (Sep. 2011-Nov. 2015) Major: Civil Engineering,

2007-2011

Bachelor of Engineering Harbin Institute of Technology, China (Sep.2007- 2011.July) Major: Water Supply and Drainage Engineering

Research interests: He has a strong interest in the research areas related to CFD and membrane fouling, and has been working on issues related to membrane fouling and hydrodynamic conditions in the field of water and wastewater treatment.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ADVANCES IN MF AND UFMEMBRANES

W2.7 J.P. DIJKSHOORNA DETERMINISTIC RATCHET USING SIEVE STRUCTURED OBSTACLES FOR LARGE-SCALE SEPARATION OF PARTICLE SUSPENSIONS

J.P. DIJKSHOORNA1, M.A.I. SCHUTYSER1, R.M. WAGTERVELDA AND R.M. BOOM1 1 Wetsus, European Centre of Excellence for Sustainable Water Technology, Oostergoweg 9, P.O. Box 1113, 8900 CC, Leeuwarden, The Netherlands 2 Food Process Engineering Group, Wageningen University, PO Box 17, 6700 AA Wageningen, The Netherlands Deterministic ratchets are microfluidic separation devices that employ periodic arrays of obstacles, spaced such that the gaps between obstacles are larger than the largest suspended particle. Separation principle is based on interaction of particles that are larger than the critical diameter with obstacles. This principle lowers the risk of particle accumulation compared to conventional membrane filtration and is one of the reasons why the deterministic ratchet has potential for large-scale separation of particles from suspensions 1. However, a major hurdle is the translation of the microfluidic device designs into large-scale designs that can handle high capacities.

Figure 7: A deterministic lateral displacement array with a large particle (red) that is being displaced in the same direction as the obstacles (grey) and a small particle (green) that follows the flow direction. All particles are smaller then G and λ so it has a lower risk of clogging (Adjusted from Morton et al. 2).

In our previous work we showed that at increased flow rates (moderate Reynolds numbers) fluid inertia positively influenced particle separation3,4. In addition, it was shown that a deterministic ratchet configuration with fewer obstacles could be used to separate particles while reducing the pressure drop5_ENREF_5. The latter observation suggested that GOLD SPONSOR

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it could be a feasible strategy to scale deterministic ratchets by employing (micro) sieves in the large-scale design. Here, we report on this strategy and we show that it is feasible to concentrate particles by using stacked sieves in a deterministic ratchet configuration. Both experiments and numerical simulations were carried out to study the influence of design on particle separation efficiency. With the design of sieves that mimic deterministic ratchet obstacles, it was found that especially the porosity of the sieve has large influence on the separation performance. REFERENCES 1

Kulrattanarak, T., van der Sman, R. G. M., Schroën, C. G. P. H. & Boom, R. M. Classification and evaluation of microfluidic devices for continuous suspension fractionation. Advances in Colloid and Interface Science 142, 53-66, doi:10.1016/j.cis.2008.05.001 (2008).

2

Morton, K. J. et al. Hydrodynamic metamaterials: Microfabricated arrays to steer, refract, and focus streams of biomaterials. Proceedings of the National Academy of Sciences 105, 7434-7438, doi:10.1073/pnas.0712398105 (2008).

3

Lubbersen, Y. S., Schutyser, M. A. I. & Boom, R. M. Suspension separation with deterministic ratchets at moderate Reynolds numbers. Chemical Engineering Science 73, 314-320, doi:10.1016/j. ces.2012.02.002 (2012).

4

Lubbersen, Y. S., Dijkshoorn, J. P., Schutyser, M. A. I. & Boom, R. M. Visualization of inertial flow in deterministic ratchets. Separation and Purification Technology 109, 33-39, doi:http://dx.doi. org/10.1016/j.seppur.2013.02.028 (2013).

5

Lubbersen, Y. S., Fasaei, F., Kroon, P., Boom, R. M. & Schutyser, M. A. I. Particle suspension concentration with sparse obstacle arrays in a flow channel. Chemical Engineering and Processing: Process Intensification 95, 90-97, doi:10.1016/j.cep.2015.05.017 (2015).

JAAP DIJKSHOORN Title: MSc Wetsus, European Centre of Excellence for Sustainable Water Technology and Wageningen University, The Nederlands Phone: +31582843188 E-mail: [email protected]

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W2.8 HUI LIU PREPARATION AND CHARACTERIZATION OF PVDF HOLLOW FIBER MEMBRANE WITH GRADIENT PORE STRUCTURES

HUI LIU 1,2*, ZHE ZHEN DAI 1,2, MIN FANG 1,2 1 Zhejiang Chemical Industry Research Institute Co., LTD., Hangzhou, P. R. China. 310023 2 SINOCHEM LANTIAN CO., LTD., Hangzhou, P. R. China. 310051 Gradient pore structures of PVDF hollow fiber membranes were prepared via thermally induced phase separation (TIPS) methods with diphenyl carbonate (DPC) solid as the diluent. The DPC diluent on the membrane morphology of cross section was bicontinuous. The diluents and temperature of the system are the two key parts of the TIPS methods to make excellent membrane morphology. Gradient pore structures of inner side were prepared by controlling the inner coagulation temperature. Gradient pore structures of outer side were prepared by controlling both the die temperature and the bath temperature.

Figure.1. The morphology of PVDF hollow fiber membrane. A: original method; B: optimized method; (1) cross section ×50; (2) inner side ×1000; (3) outer side ×3000. REFERENCES 1

F. Liu, N. A. Hashim, K. Li, J. Membr. Sci., 375, 1 (2011).

2

Y. Lin, Y. H. Tang, X. L. Wang, J. Appl. Polym. Sci., 114, 1523 (2009). GOLD SPONSOR

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W2.9 TIARA PUSPASARI CHARGE AND SIZE-SELECTIVE MOLECULAR SEPARATION USING ULTRATHIN CELLULOSE MEMBRANES

TIARA PUSPASARI, HAIZHOU YU, KLAUS-VIKTOR PEINEMANN Advanced Membranes and Porous Materials Center, King Abdullah University of Science and Technology (KAUST), Kingdom of Saudi Arabia The interest in membrane-based separation of nanoparticles and biomolecules like proteins, peptides and viruses is growing. Low-cost membranes with fast and highly selective transport profile are essential for successful membrane processes. Cellulose has emerged as an important membrane material due to its low price, availability, compatibility, antifouling feature, thermal and mechanical stability. Existing state-of-theart cellulose membranes are predominantly based on integrally skinned asymmetric membranes prepared using selected solvents and water induced phase separation. However, this usually leads to a porous separation layer with a thickness of a few hundred nanometers that suffer from excessive shrinkage under dry conditions. In addition, only few solvents for cellulose are known and these often suffer from high reactivity and toxicity1. The challenges lie in the use of low cost and less-harmful solvents, which produce stable membranes with high separation performance. Here we focus on the preparation of ultrathin cellulose films using trimethylsilyl cellulose (TMSC) as a precursor (Fig. 1A). TMSC was prepared through a straightforward functionalization of accessible cellulose hydroxyl groups leading to a highly soluble derivative in commonly used solvents such as tetrahydrofuran, hexane and acetone as described in previous work2. The elegance of the method lies in the in situ transformation of TMSC back to cellulose after membrane formation, which is reproducible, relatively simple and can be mass-produced. This stage has a great influence on the membrane performance. In this study, the membrane was prepared by spin coating of TMSC onto a glass substrate followed by subsequent film detachment in water; it was then transferred onto either a polyacrylonitrile (PAN) or a porous Anodisc® alumina support (0.2 µm pore size). The transferred freestanding film as thin as 10 nm can cover the micropores of the alumina surface (Fig. 1B) (4.1 cm2) with a good adhesion without defects (Fig. 1C), as confirmed by rejection analysis. Fig. 1D shows a smooth nano-membrane detained on a metal ring of 1.5 cm in diameter, illustrating an excellent integrity even though the membrane was only 40 nm thick.

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Fig. 1 (A) Silylation of cellulose and the subsequent regeneration with acid. Cross-sectional SEM images of (B) an alumina disc support and (C) freestanding cellulose nano-membrane on an alumina disc. (D) Photograph of a 40 nm thick TMSC membrane on a metal ring.

Molecular permeation through polymeric membranes is governed by steric and electrostatic effects. Provided that the membrane carries nanopores and negative charges both size- and charge- based separations are expected. Fig. 2A depicts the UV-Vis absorbance of filtration solutions containing vitamin B12 (MW = 1,355 Da; D = 1.5 nm) and myoglobin (MW = 16,700 Da; D = 3.5 nm).. By comparing the spectra of feed and permeate, we can see that vitamin B12 freely passed through the membrane (R ≈ 0%) while the protein was completely blocked (R ≈ 100%). Taking into account that both solutes differ only 2 nm in size we conclude that the membrane exhibits sharp sieving ability with around 2 nm effective pore diameter. More experiments were carried out using a pair of neutral (α-cyclodextrin, MW = 973 Da; D = 1.4 nm) and anionic (reactive black 5, MW = 997 Da; D = 1.3 nm) molecules with similar size. The filtration concentration was detected by a UV-Vis spectrophotometer for reactive black 5 and by gel permeation chromatography for α-cyclodextrin, respectively. From Fig. 2B, it is clear that the neutral molecule could easily permeate with no rejection (R ≈ 0%) while the negatively charged one was completely retained by the membrane (R ≈ 100%). No molecule adsorption was observed during experiment. These results clearly demonstrate that our membranes can perfectly separate similarly sized molecules on the basis of their charges. Given that cellulose naturally exists as an anionic polymer due to its hydroxyl and carboxyl groups, molecules that carry negative charges will be electrostatically repelled during filtration, while the neutral molecules will permeate solely as a function of their size. To the best of our knowledge, this is the first use of a polymeric membrane for the separation of similarly sized molecules smaller than 3 nm based on charge. GOLD SPONSOR

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Fig. 2 (A) Size- and (B) charge-selective separation of regenerated cellulose membrane

Composite membranes prepared from 0.3% TMSC solution in n-hexane on top of a PAN support exhibited a flux of 65 Lm-2h-1bar-1. When the membrane was prepared as a free-standing film and then transferred to an alumina disc, an extreme flux improvement to 700 Lm-2h-1bar-1 could be achieved due to the low resistance of the support. No pore penetration of the coating material occurred using this procedure. Moreover, the membrane can be dried without loss of performance and performed stable in aqueous solutions for more than 60 days. In summary, membranes manufactured form a low-cost and renewable material using a straightforward fabrication process showed highly selective separation of nano-sized molecules based on size and charge differences combined with a remarkable flux, excellent stability and high scale-up potential. REFERENCES 1

E. Kontturi, T. Tammelin, M. Österberg, Chem. Soc. Rev. 2006, 35, 1287. (2) T. Puspasari, N. Pradeep, K.-V. Peinemann, J. Membr. Sci. 2015, 491, 132.

TIARA PUSPASARI Title: Ms. King Abdullah University of Science and Technology (KAUST), Saudi Arabia Phone: +966128084961. Fax: +966128021328. E-mail: [email protected] edu.sa 2005-2009

BSc. in chemical engineering, Bandung Institute of Technology, Indonesia

2011-2012

MSc. in chemical engineering, Bandung Institute of Technology, Indonesia

Since 2013

PhD student in Advanced Membrane and Porous Materials Research Center, King Abdullah University of Science and Technology (KAUST), Saudi Arabia.

Research interests: biopolymer, membrane fabrication, nanofiltration, thin film composite

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W2.11 ANTHONY SZYMCZYK SEPARATION OF ORGANIC SOLUTES BY REVERSE OSMOSIS MEMBRANES: AN EXPERIMENTAL AND COMPUTATIONAL STUDY

AZIZ GHOUFI1, EMIL DRAZEVIC2, ANTHONY SZYMCZYK3 1 Université de Rennes 1, Institut de Physique de Rennes (UMR CNRS 6251), 263 Avenue du Général Leclerc, CS 74205, 35042 Rennes, France 2  Aarhus University, Department of Engineering, Hangøvej 2, 8200 Aarhus, Denmark 3 Université de Rennes 1, Institut des Sciences Chimiques de Rennes (UMR CNRS 6226), 263 Avenue du Général Leclerc, CS 74205, 35042 Rennes, France People’s access to drinking water is a major challenge for the coming decades, not only for the developing countries but also for the industrialized states1. The lack of global water is further aggravated by factors such as pollution and the inequality of its distribution. Moreover, ensuring safe future worldwide water supplies demands today for advanced and environmentally acceptable processes which allow one to preserve water and to reduce its consumption. Membrane separation processes are already recognized worldwide as promising tools for solving some of the major problems of our modern societies. These techniques are energy efficient (no phase change is required to operate the separation), environmentally friendly (in the sense that they require no or limited addition of chemicals), modular and compact. Reverse osmosis (RO) is one of these membrane processes. It is usually used to separate dissolved salts and small organic molecules. Its applications range from the production of ultrapure water for semiconductor and pharmaceutical use to the desalination of seawater for drinking water production and the purification of industrial wastewater. Nowadays, the RO membrane market is mainly dominated by thin-film-composite polyamide membranes containing three layers: a polyester web serving as the structural support (100-200 micrometers thick), a mesoporous polysulfone film acting as the supporting mid-layer (about 30-50 micrometers thick), and a selective ultra-thin barrier layer on the upper surface (100-300 nm thick). This latter is generally fabricated through interfacial polymerization of meta-phenylene diamine (MPD) and trimesoyl chloride (TMC) at the interface of two immiscible solvents. These two monomers can react to form linear chains as well as undergo two additional side reactions where the third acyl chloride group can either undergo hydrolysis to form carboxylic acid or react with another diamine molecule to produce cross-linking. Despite the technological importance of RO membrane separation processes, the molecular mechanisms of water and salt transport through RO membranes are not well understood, particularly at the molecular level2,3. Several studies showed that rejection of uncharged organic solutes by RO membranes cannot be described by a simple sieving GOLD SPONSOR

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effect ruled by the relative size of the solutes and the free volumes within the membrane active layer4-7. These works highlight the crucial role of physicochemical interactions between organic solutes and the membrane material. However, getting quantitative information regarding solute / membrane affinity is extremely challenging because RO membranes are essentially thin-film composite materials the skin layer of which does not represent more than ~ 0.1 % of the total membrane thickness. In this work we investigated the separation performance of a commercial thin-film composite polyamide RO membrane (SWC4+, Hydranautics/Nitto Denko, Oceanside, CA, USA) with respect to three organic molecules with identical molecular mass (100 g/mol): 4-aminopiperidine, pinacolone, and methylisobuthyl ketone. The interaction energy between the different solutes and the membrane phase was computed from molecular dynamics simulations. The resulting sequence was found to correlate well with experimental rejections. Sorption of the different organics within the membrane active layer was further determined from attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). A nice agreement was obtained between interaction energies computed from molecular simulations and the partitioning coefficients inferred from ATR-FTIR spectroscopy. Moreover, both ATR-FTIR and simulation results indicated a dramatic decrease in the organic solute diffusivity inside the RO membrane. REFERENCES 1

M.A. Shannon, P.W. Bohn, M. Elimelech, J.G. Georgiadis, B.J. Marinas, A.M. Mayes, Nature 2008, 452, 301.

2 M. Ding, A. Szymczyk, A. Ghoufi, F. Goujon, A. Soldera, J. Membr. Sci. 2014, 458, 236. 3 M. Ding, A. Szymczyk, A. Ghoufi,, J. Membr. Sci. 2016, 501, 248. 4 E. Drazevic, S. Bason, K. Kosutic, V. Freger, Environ. Sci. Technol. 2012, 46, 3377. 5 A.R.D. Verliefde, E.R. Cornelissen, S.G.J. Heijman, E.M.V. Hoek, G.L. Amy, B. Van der Bruggen, J.C. Van Dijk, Environ. Sci. Technol. 2009, 43, 2400. 6

E. Drazevic, K. Kosutic, V. Kolev, V. Freger, Environ. Sci. Technol. 2014, 48, 11471.

7 D.S. Dlamini, S. Levchenko, M. Bass, B.B. Mamba, E.M.V. Hoek, J.M. Thwala, V. Freger, Desalination 2015, 368, 60.

ANTHONY SZYMCZYK Prof. Dr. France Phone: +33 2 23236528 E-mail: [email protected] Anthony Szymczyk received his Ph.D. in Physical Chemistry in 1999 at the University of Franche-Comté. He is currently Full Professor of the University of Rennes 1 where he teaches Thermodynamics and Membrane processes. Prof. Szymczyk’s research lies at the interface of chemical engineering, chemistry of materials and physics of condensed matter. His main research activities focus on the modeling and simulation of membrane separations for desalination and water purification, and on the physico-chemical characterization of membrane materials with applications in functionalization, fouling, ageing... He published about 110 scientific papers and book chapters on these topics. In 2013 he was the recipient of the IUPAC distinguished Award for Novel Materials and their Synthesis for his work on ion transport through nanoporous membranes. He was a member of the council of the European Membrane Society (2011-2014) and he served as Vice-President in 2013 and 2014.

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W2.12 SURFACE MODIFICATION OF THIN FILM COMPOSITE MEMBRANES FOR FOULING REDUCTION AND ENHANCED CHLORINE STABILITY

DR JOCHEN MEIER-HAACK1, CHRISTIAN LANGNER1, KORNELIA SCHLENSTEDT1, DR MONA ABDEL REHIM2 1 Leibniz Institute of Polymer Research Dresden, 2National Research Center Key Words: RO membranes, surface modification, fouling reduction. Reverse osmosis is a well established technique to produce drinking water from sea water or brackish water. The membrane consists of three distinctive layers, namely a non-woven support, a porous middle layer made from poly(sulfone) or poly(ether sulfone), which can be used as an ultrafiltration membrane and a dense polyaramide top-layer prepared by interfacial polycondensation. While the first two layer act as support for the top layer, which is only 100-200 nm thick, determines the permeate flux and salt rejection. The most challenging issue in RO application today is the low chlorine stability of the polyaramide top layer. However, cleaning cycles with chlorine are necessary to remove biofouling from the membrane surface. Several methods like variation of amine component [1], variation of acid component [2] or use of sulfonated poly(ether sulfone)s [3] have been reported in the past to produce chlorine stable separation layers. However, from a performance point of view, thin film composite membranes with a polyaramide top-layer are still the benchmark. Two approaches are applied for the surface modification. Approach 1 is not preliminarily aimed at changing the chemical composition of the polyaramide top-layer itself but to make the surface less susceptible for fouling (e.g. protein adsorption). For this purpose, carbonyl chloride groups remaining at the surface after preparation of the polyaramide amide dense layer are used for a subsequent surface modification step. These groups are used for grafting hydroxyl or amine containing polymers like poly(ethylene glycol) or hyperbranched polyamine amide. In the second attempt 3-ethinyl aniline was used as comonomer for the preparation of the polyamide layer. Azide functionalized poly(ethylene glycol) and poly(methyl oxazoline) were grafted to the membrane surface by the well-known “click-reaction”. The membrane surfaces were more hydrophilic after the modification step as revealed by contact angle measurements. Modification with the hyperbranched poly(amine) resulted in shift of the isoelectric point to higher pH values (pH 6), while the poly(ethylene glycol) and poly(methyl oxazoline) modified membrane had an IEP at approx. pH 4.5. The effect of surface modification on membrane properties is further discussed in terms of permeate flux, salt rejection, chlorine stability and protein adhesion.

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ACKNOWLEDGEMENT

The financial support of this work by the German Egyptian Research Fund is gratefully acknowledged (EGY 10/029). REFERENCES

356

1

J. E. Cadotte, Reverse Osmosis Membrane, US Patent 4259183 (1981)

2

B. J. Trushinski, J. M. Dickson, T. Smyth, R. F. Childs, B. E. McCarry, Polysulfonamide thin-film composite reverse osmosis membranes, J. Membr. Sci (1998) 143:181-188

3

H. B. Park, B. D. Freeman, Z.-B. Zhang, M. Sankir, J. E. McGrath, Highly Chlorine-Tolerant Polymers for Desalination, Angew. Chem. Intern. Ed. (2007) 47: 6019 – 6024

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THEME: ADVANCES IN MF AND UFMEMBRANES

W2.13 DR SHUAIFEI ZHAO FABRICATION AND CHARACTERIZATION OF NEW CERAMIC NANOFILTRATION MEMBRANES

DR SHUAIFEI ZHAO1, 2, TAO WU2, HONGLIN GUO3, HONG QI3 1 Department of Environmental Sciences, Macquarie University, Sydney 2109, New South Wales, Australia 2 Collaborative Innovation Centre of Membrane Separation and Water Treatment, Zhejiang University of Technology 3 Membrane Science and Technology Research Centre, Nanjing Tech University, Nanjing 210009, Jiangsu, China ABSTRACT

Nanofiltration (NF) membranes are generally divided into two categories according to the material difference, including organic (polymeric) and inorganic ones. Commercial organic (i.e., polymeric) NF membranes have found various industrial applications. However, these organic membranes suffer from some disadvantages, such as low thermal and chemical stabilities and poor mechanical strength. These drawbacks can be overcome by developing more efficient ceramic NF membranes 1, 2. Polymeric NF membranes are generally used to treat liquids with temperatures below 70 °C, while inorganic NF membranes have larger working temperature range, typically can be up to 120 °C (liquids will be vaporized if the temperature is over 120 °C). In this study, TiO2/ZrO2 composite ceramic NF membranes with different pore sizes (i.e. TZ-5, TZ-8 and TZ-10) are successfully fabricated through the polymeric sol-gel route followed by the dip-coating technique. Disk type α-alumina supported mesoporous γ-alumina (pore size: 5 - 6 nm) is employed as the support in dip-coating. The unsupported and supported composite ceramic membranes are systematically characterized and evaluated in terms of phase composition, chemical stability, gas adsorption, molecular weight cut-off (MWCO), membrane pore size, water flux and salt rejection. It is found that the TiO2/ZrO2 ceramic membranes have amorphous phase at 400 and 500 °C, suggesting the high thermal stability. The fabricated membranes have the MWCO of 620 - 860 Da, corresponding to the membrane pore size of 1.2 - 1.5 nm. Relatively low water permeability can be attributed to the low microporosity of the membrane. Donnan exclusion is the dominant transport mechanism of the NF membrane in the singlecomponent system, and salt rejection is closely related to the hydration properties of the ions (e.g., the hydration radius).

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Transmembrane pressure / bar Figure 1.. Rejection performance of the TiO2/ZrO2 composite membranes to MgCl2. Test conditions:temperature 25±2 °C, feed solution pH = 6, feed concentration 0.005 mol/L, and stirring rate 200 r/min.

Figure 2. SEM images of the membrane cross-sections.

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REFERENCES 1

Benfer, S.; Popp, U.; Richter, H.; Siewert, C.; Tomandl, G.; Sep. Purif. Technol. 2001, 22–23, 231-237.

2

Van Gestel, T.; Vandecasteele, C.; Buekenhoudt, A.; Dotremont, C.; Luyten, J.; Van der Bruggen, B.; Maes, G. J.; Membr. Sci. 2003, 214, (1), 21-29.

DR SHUAIFEI ZHAO Macquarie University, Sydney, Australia Phone: +61 2 98509672, E-mail: [email protected] 2016-now

Research Fellow at Macquarie University

2015-2016

Visiting scholar at Nanjing Tech University

2012-2015

Postdoctoral Fellow at CSIRO

2009-2012

PhD student at University of South Australia

Research interests: forward osmosis, membrane distillation, membrane condensation, pressure driven membrane processes, membrane fabrication, desalination and water treatment.

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W2.14 DR JOCHEN MEIER-HAACK ULTRAFILTRATION MEMBRANES FROM PES-PEG LOCKCOPOLYMERS WITH IMPROVED FOULING PROPERTIES

DR JOCHEN MEIER-HAACK1, KORNELIA SCHLENSTEDT1 1 Leibniz Institute of Polymer Research Dresden Although subject to research for decades, fouling is still one of the major limiting factors in membrane applications. Numerous methods have been suggested to overcome this shortcoming, like crossflow filtration, backflushing, air sparging, all of them in combination with chemical cleaning. However many of these techniques imply off-production cycles, resulting in lower yield, shorter lifetime of membranes and therefore higher costs. Another approach to reduce fouling involves the modification of membranes with charged and / or hydrophilic polymers. These are either added to the casting solution or subsequently grafted onto the membrane surface. However, both methods have their specific drawbacks. Adding hydrophilic polymers to the dope solution leads to a significant loss during membrane preparation step (coagulation). On the other hand graft modification involves most often several steps and bears the risk of damaging (degrading) the membrane material resulting in loss of mechanical stability. In this work we report on UF membranes prepared from poly(ether sulfone)-poly(ethylene glycol) block copolymers. This approach has the advantage over surface modification that the degree of functionalization can be easily controlled by the monomer composition. Additionally, not only the outer surface is modified but also the pore surface. Block copolymers with poly(ethylene glycols) of molecular weights varying from 200 g/mol to 4000 g/mol but constant molar fraction of 5 mol% were prepared by nucleophilic displacement polycondensation process. UF-membranes from block copolymers were prepared by conventional NIPS process. The effect of PEG molecular weight on thermal properties, membrane morphology, surface and filtration properties as well as fouling properties were studied and compared with an UF membrane prepared from commercial PES. As a result, only one glass transition temperature (Tg) could be detected by DSC measurements for all synthesized block copolymers, indicating that no phase separation between PES and PEG occurred. However, the Tg decreases from 230 °C (pure PES) to 35 °C for the PES-PEG 4000. The incorporation of PEG into the membrane material resulted in an increase in pore size and smoother surface with increasing length of the PEG. All membranes showed a severe flux decline during protein filtratrion. However, the flux of membranes from PES-PEG 2000 could be recovered completely by rinsing with pure water.

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W2.16 M. RABILLER-BAUDRY IMPROVING ORGANIC SOLVENT NANOFILTRATION THROUGH PROCESS ENGINEERING: AN EXPERIMENTAL AND SIMULATION STUDY FOR OLEFIN METATHESIS

A. LEJEUNE 1, G. NASSER 1, T. RENOUARD 1, M. RABILLER-BAUDRY 1* 1 Université de Rennes 1- Université Bretagne Loire, Institut des Sciences Chimiques de Rennes, UMR-CNRS, Rennes, France This paper aims at studying the feasibility of OSN integration to design a sustainable process based on olefin metathesis a reaction allowing to prepare chemical intermediates by breaking/making carbon carbon double bonds. The catalytic system based on a soluble ruthenium complex (Grubbs Hoveyda II pre-catalyst, MW= 627 g.mol-1, Fig.1) can be achieved in toluene or in dimethylcarbonate (green solvent). For the demonstration a model reaction was chosen consisting in the ring closing metathesis of diethyl diallyl malonate (240 g.mol-1) leading to a product the MW of which is 212 g.mol-1 (Fig.1)

EtO2C

CO2Et EtO2C pre-catalyst: 0.5 mM

CO2Et

toluene, -C2H4 MW = 240 g.mol-1

MW = 212 g.mol-1

Diethyl Diallyl Malonate SUBSTRATE (DEDAM)

Cyclo-pentene form PRODUCT (c-DEDAM)

Grubbs-Hoveyda II Pre-catalyst

Figure 1. Catalytic reaction in toluene and pre-catalyst

The reaction can be performed at room temperature allowing several strategies to reach the goal of both catalyst reuse thanks to a high rejection by the OSN membrane (here Starmem 122 provided by Met-Evonik) and an efficient extraction of the product to avoid reaction inhibition due to its presence at too high concentration in the reaction medium. Two experimental approaches using the same amount of pre-catalyst were achieved. The first one is based on a semi-continuous membrane reactor running at 40 bar. After two cycles of synthesis + OSN separation and discontinuous diafiltration, 47% of the obtained product can be recovered in the cumulate permeate and 98% of catalyst is retained in the retentate. The second one is based on a continuous membrane reactor at 10 bar allowing to extract 31% of the synthetized product but with a smaller amount of added GOLD SPONSOR

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solvent compared to the previous reactor [1]. Finally, to improve the product extraction, simulations of OSN cascades, including recycling between stages, where done at 10 bar assuming constant retention for all solutes (Fig. 2). Some simulation results are shown in Table 1 evidencing quite appreciable improvement thanks to cascades and permeate recycling. Table 1. Simulation results for the 4 stages’ membrane cascade of figure 1 according to simulation Number of stages

1

2

3

4

Catalyst recovery (%)

97.3

97.2

97.2

97.2

Product recovery (%)

38

51

63

74

Figure 2. 4 stages’ membrane cascade at 10 bar with permeate recycling between stages

Acknowledgement to the French National Agency for Research for financial support: ANR-CP2D-NanoRemCat2 and ANR-MemChem

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REFERENCES 1

M. Rabiller-Baudry, G. Nasser, T. Renouard, D. Delaunay, M Camus., Sep. Purif. Technol. 2013, 46, 60-116

MURIELLE RABILLER-BAUDRY Title: Professor Université Rennes 1- Université Bretagne Loire, Institut des Sciences Chimiques de Rennes, UMR-CNRS, Rennes, France Phone: +33223235752 Fax: +33223234031 E-mail: [email protected] Since 1991

UF, NF, RO (mainly food fluids)

2002

Professor at Rennes 1 University

Since 2005

OSN for fine chemistry (toluene)

Since 2006

Chair of the membrane group in Rennes 1 University

Research interests: UF of dairy fluids (mechanism, cleaning, ageing), OSN

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W2.17 EVELIEN MAASKANT SEPARATION IN HARSH CONDITIONS: ULTRA-THIN LAYERS ON CERAMIC HOLLOW FIBERS

EVELIEN MAASKANT1, PATRICK DE WIT1, AND NIECK E. BENES1 1 Films in Fluids, University of Twente, Department of Science and Technology, MESA+ Institute of Nanotechnology, P.O. Box 217, 7500AE Enschede, The Netherlands Membrane separation in harsh environments, such as in aggressive solvents or at elevated temperatures, requires stable materials. Not only the stability of the separating top layer is limiting; the intermediate layers and support material will as well influence the stability and thus the performance of the membrane. Here we investigate the use of an inorganic membrane support as alternative for the commonly used polymeric membrane supports. Inorganic materials have superior mechanical, thermal, and chemical stability. Raaijmakers et al. (2014) showed that the combination of a flat ceramic support and hybrid top layer results in a very stable membrane that is able to separate gasses up to 350 °C.1 For upscaling membrane processes a tubular membrane geometry is a preferred alternative for the flat sheet geometry, due to mechanical considerations and the larger surface-to-volume ratio. The surface-to-volume ratio increases with decreasing diameter of the tube. Therefore we have chosen to use very thin tubes as support, in the form of porous ceramic hollow fibers.2 On the ceramic hollow fibers a classical polyamide top layer is made by interfacial polymerization of trimesoyl chloride with classical amines. We have identified a number of critical properties of the ceramic hollow fibers for preparing a high performance membrane. It is found that a multi-layered support, with a meso-porous intermediate layer, is most promising, and that in particular the surface roughness, particle size, and pore size of the intermediate layer affect the final separation performance. Due to the versatile nature of the fiber fabrication process, and the possibility to control the morphology of the intermediate layer, ceramic hollow fibers can be tailored as support for stable interfacial polymerization derived membranes.

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REFERENCES 1 M.J.T. Raaijmakers et al., J. Am. Chem. Soc. 2014, 136 (1), pp 330-335 2

M.W.J. Luiten-Olieman et al., J. Memb. Sci. 2012, 407-408, pp 155-163

EVELIEN MAASKANT Title: MSc University of Twente, The Netherlands Phone: +31 53 489 4595 Fax: +31 53 489 2336 E-mail: [email protected] 2008-2013

Chemical Engineering, University of Twente

Since 2014

PhD candidate in the Films in Fluids group, University of Twente

Research interests: organic solvent nanofiltration, film formation by localized reactions

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THEME: ADVANCES IN MF AND UFMEMBRANES

W2.18 ZE-XIAN LOW EVALUATING THE AGING OF ORGANIC SOLVENT NANOFILTRATION MEMBRANES

ZE-XIAN LOW1,*, ANDREW LIVINGSTON2 AND DARRELL ALEC PATTERSON1,* 1 Centre for Advanced Separations Engineering and Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom 2 Department of Chemical Engineering, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom Separation processes account for 40–70% of both capital and operating costs in industry.1 Consequently, there is an opportunity to reduce this using lower cost, lower energy, more efficient and sustainable separation technologies. Membrane separations such as organic solvent nanofiltration (OSN) have been considered as one of the emerging separation processes in pharmaceutical industries in particular, due to their lower temperature operation (compared to distillation and evaporations) and potential for new separations due to differing selectivity to conventional technologies. In pharmaceutical applications, organic solvent stable membranes are required as most of the synthesis of pharmaceutical products are performed in organic solvents. Therefore a range of organic solvent nanofiltration (OSN) membranes have over the last 20 years been developed and applied to pharmaceutically relevant separations (such as diafiltrations, fractionation cascades for low temperature isolation and purifications, organometallic catalyst separation and recycling, and active pharmaceutical ingredient isolation).2 Although initial and short term selectivity, flux and durability have been evaluated in the literature, the longer term performance of these membranes have not been comprehensively addressed. Like most (if not all) membranes, OSN membranes also suffer from performance degradation over time due to membrane fouling and aging. Consequently, this work aims to investigate if OSN membranes undergo performance loss and to determine if this is attributable to membrane aging in common organic solvents such as methanol, acetonitrile and toluene. Four different commercial OSN membranes (Duramem 200, Puramem 280, GMT-oNF2, and SolSep BV010206) were tested in crossflow filtrations (30 bar, 800 ml/min) in the organic solvents at different temperatures (30°C, 60°C and 5°C below the boiling temperature) over a month and results were compared to membranes treated in the same organic solvents at atmospheric pressure (static experiment). The membranes were characterized by their organic solvent flux, solute rejection, morphological changes, and stability in common organic solvents. Over a longer period of continuous crossflow operation, all commercial OSN membranes exhibited higher initial organic solvent flux decline that stabilized over time (Fig. 1). The permeability loss varies with the type of membranes as well as temperature. Membrane aging in OSN was confirmed for the first time through

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observable changes in membrane morphology and chemical properties. These results indicate that the actual fluxes of long term use of these OSN membranes could be lower than the values reported in many cases, strongly suggesting that long term testing of all OSN membranes need to be done to give representative and relevant separation parameters for industrial application.

6

Duramem 200 SolSep BV010206 Puramem 280 GMT-oNF2

Permeability (LMH/bar)

5 4

30°C

50°C

60°C

3 2 1 0

0

100

200 300 Aging time (h)

400

500

Figure 1. Methanol permeability of commercial organic solvent nanofiltration membranes up to 21 days. (Crossflow, 30 bar, 800 ml/min) REFERENCES 1 S. Adler, E. Beaver, P. Bryan, S. Robinson, J. Watson, Vision 2020:2000 Separations Roadmap; Center for Waste Reduction Technologies of the AIChE and Dept. of Energy of the United States of America, 2000. 2 P. Marchetti, M. Solomon, G. Szekely, A. Livingston, Chem. Rev., 2014, 114, 10735−10806.

ZE-XIAN (NICHOLAS) LOW Title: Postdoctoral Research Associate Centre of Advanced Separations Engineering, University of Bath, UK E-mail: [email protected], Website: www.nicholaslow.com 2012-2015

Ph.D. in Chemical Engineering, Monash University

Research interests: gas separation, engineered osmosis, 3D printing

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367

THEME: ADVANCES IN MF AND UFMEMBRANES

W2.19 REYHAN SENGUR-TASDEMIR COMPARISON OF AQUAPORIN Z EMBEDDED MEMBRANES FOR NANOFILTRATION APPLICATIONS

REYHAN SENGUR-TASDEMIR1,2,ENISE PEKGENC2,3, GULSUM MELIKE URPER2,3, ESRA TUTUNCU4, TULAY ERGON3, NEVIN GUL KARAGULER4, ESRA ATES GENCELI3, ISMAIL KOYUNCU2,3* 1 Nanoscience and Nanoengineering Department, Istanbul Technical University, Istanbul, Turkey 2 National Research Center on Membrane Technologies, Istanbul Technical University, Istanbul, Turkey 3 Environmental Engineering Department, Istanbul Technical University, Istanbul, Turkey 4 Molecular Biology and Genetics Department, Istanbul Technical University, Istanbul, Turkey Efficiency of membranes is generally related to the flux and the selectivity. Aquaporins which are integral membrane proteins are known to selectively allow water molecules through the plasma membrane and reject ions and other solutes. Due to their unique selectivity, high water transport capability and low activation energy possibility to use aquaporins in membrane applications is increased. Aquaporin embedded biomimetic membranes (Fig.1) are potential candidates for RO, FO and NF processes. A single aquaporin can transfer water molecules at a rate of 2-8 x 109 molecules per second (or 0.21–0.86 picoliters per hour), which equals to an osmotic permeability of 6–24 x 10−24 cm3 x s-1 1. In this study, performances of Aquaporin Z cloned; expressed and purified from E.Coli DH5α strain and commercial Aquaporin Z are compared. Flat sheet membrane is used to embed Aquaporin Z into membrane structure by interfacial polymerization method. Monomers used in interfacial polymerization are m-phylene diamine and trimesoyl chloride. Membranes are characterized by scanning electron microscopy; pure water permeability; MgSO4 and NaCl rejections and fluxes; FTIR and zeta potential. Aquaporin Z embedded membrane water permeability increased to 8.41 l/m2.h.bar. for commercial Aquaporin Z. MgSO4 fluxes are found as 8.40 l/m2.h and 12.98 l/m2.h at 6 bar for purified Aquaporin Z and commercial Aquaporin Z membranes, respectively. MgSO4 rejections are found 53.9 % and 10.7 % at 6 bar for purified Aquaporin Z and commercial Aquaporin Z membranes, respectively. NaCl fluxes are 9.53 l/m2.h and 12.98 l/m2.h at 6 bar for purified Aquaporin Z and commercial Aquaporin Z membranes, respectively. NaCl rejections are found 27.4 % and 30.6 % at 6 bar for purified Aquaporin Z and commercial Aquaporin Z membranes, respectively.

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500nm

2000nm

Figure 1. Aquaporin embedded biomimetic membrane (courtesy of MEM-TEK). ACKNOWLEDGEMENT

The authors are grateful to TUBITAK (The Scientific and Technological Research Council of Turkey) for their financial support under grant (Project No: 113Y359). Authors also thank to Abdulhalim Kilic and Fatma Nese Kok for their supports on liposome production. REFERENCES 1

R. Sengur-Tasdemir, S. Aydin, T. Turken, E. Ates Genceli, & I. Koyuncu (2016) Separation & Purification Reviews, 45:2, 122-140

REYHAN SENGUR-TASDEMIR Research assistant, PhD candidate, Istanbul, Turkey Phone: +902122853473 Fax: +902122856667 E-mail: [email protected] 2010-2013

MSc, Nanoscience and nanoengineering department, Istanbul technical University

2013-

PhD, Nanoscience and nanoengineering department, Istanbul Technical University

Research interests: membrane fabrication, aquaporins

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THEME: MEMBRANE FOULING

THEME: MEMBRANE FOULING W3.2 S. JEONG FOULING REDUCTION BY MEMBRANE BIOREACTOR USED AS A PRETREATMENT IN DESALINATION

S. JEONG1, 2, G. NAIDU1, S. VIGNESWARAN1 1 FEIT, University of Technology, Sydney, Broadway, NSW 2007 Australia, 2 King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia Reverse osmosis (RO) is considered as the most efficient technique for seawater desalination. However, RO undergoes membrane fouling that adversely affects its performance. Especially, biofouling will cause a decrease in membrane flux, which in turn will result in an increase in operational pressure, and an increase in the frequency of membrane cleanings. This incurs a higher energy demand. For effective control of biofouling, membrane bioreactor (MBR) is a suitable and environmentally friendly pretreatment because it can remove the biodegradable organic matter and at the same time inactivate the microbes. Previously, we investigated a lab-scale MBR with powder activated carbon (PAC) addition (referred to as submerged membrane adsorption bioreactor; SMABR) as a pretreatment to RO with optimal PAC replacement. In SMABR, PAC was used for organic adsorption (large molecular weight organics) and microbial development to degrade the organics (low molecular organics). SMABR required only 2.4–8.0 g of PAC to treat 1 m3 of seawater. In this study, an automated pilot-scale SMABR system was operated to find optimal backwashing condition. Different intervals and durations of backwashing were tested to minimize the increase in the transmembrane pressure (TMP). Bioactivity was monitored in SMABR during the operational period of 12 weeks. Organic removal was evaluated in terms of dissolved organic carbon (DOC)1 and assimilable organic carbon (AOC)2. SMABR effluents collected at different stages of operation were filtered through a pilot-scale RO system to test fouling reduction on RO membrane. SMABR AS PRETREATMENT TO ROC

After the 12 weeks of operation, DOC reduction remained constant at 44±6%. Biopolymer (BP) removal efficiency by SMABR was more than 50%. The removal efficiencies of BP, humic substances (HS) and LMW-N were 54±29%, 45±17% and 46±12%, respectively. HS removal efficiency decreased slightly while the increase of LMW organic removal was observed with operational time.

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Similar to LMW organics removal, Assimilable Organic Carbon (AOC) reduction was improved with operational time2. It showed that SMABR produced the effluents with low concentration of AOC (around 10-20 µg-C glucose equivalents/L during operational period. The concentration of LMW organics is found to be closely associated with AOC concentration (Fig. 1).

Fig. 1 The variation of AOC concentration in RSW and SAMBR effluents. RO AS POST TREATMENT TO SMBR

Reduced DOC concentration by SMABR did not affect the initial flux of RO. It was around 24 LMH with RO unit operated at 55 bar. However, the flux decline in RO with SMABR effluent was lower than that with raw seawater (RSW). RO flux decline with SMABR effluent (obtained after 12 weeks of operation) was only 65% while it was around 90% with RSW without any pretreatment. RO FOULANT

SMABR pretreatment helped to reduce organic fouling on RO membrane. Organic foulant on RO was mainly composed of HS and LMW organics. The amount of organic foulants on RO membrane with RSW was 2.88 g of DOC/cm2 of membrane. This decreased to 1.80~2.37 g of DOC/cm2 of membrane with SMABR effluents. The amount of LMW organics on RO membrane was also reduced, when SMABR pretreatment was applied. This also shows that SMABR pretreatment reduced initial biofouling development on RO membrane. This is because LMW organics are one of biofouling precursors (Table 1).

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THEME: MEMBRANE FOULING

Table 1 RO foulant and organic fractions.

(C-g/cm2 of membrane)

DOC

BP

HS

LMW organics

RSW

2.88

0.09

1.56

1.00

1

2.10

0.07

0.96

0.85

2

2.04

0.11

1.01

0.78

4

2.37

0.14

1.26

0.90

6

1.80

0.09

0.80

0.73

CONCLUSION

In this study, an automated pilot-scale SMABR system was operated to find optimal backwashing condition during the operational period of 12 weeks. Results showed that TMP development (or fouling) in SMABR system was decreased with increased backwashing. During the 12 weeks of operation, a consistent DOC removal at 44±6% was noticed. The removal efficiencies of BP, HS and LMW-N were 54±29%, 45±17% and 46±12%, respectively. Similar to LMW-N, AOC reduction was improved with operational time of SMABR. SMABR produced the effluents with low concentration of AOC (around 10-20 µg-C glucose equivalents/L). With SMABR as a pretreatment, the amount of LMW organics on RO membrane was also reduced. This shows that SMABR pretreatment is a suitable pretreatment to reduce biofouling development on RO membrane. REFERENCES 1

S. Jeong, G. Naidu, S. Vigneswaran, C.H. Ma, and S.Rice, Desalination 2013, 317,160-165.

2 S. Jeong, G. Naidu, S. Vigneswaran, Bioresour. Technol.2013, 141, 57-64.

NAME : S. VIGNESWARAN Title: Professor University of Technology Sydney (UTS), Australia Phone: +61-2-9514-2641 Fax: +61-2-9514-2633 E-mail: Saravanamuth. [email protected] 2009-present

Professor and Director of Centre for Technologies in Water and Wastewater Treatment, UTS

1996-2008

Professor and Deputy director of Institute for Water and Enviromental Resources Management, UTS

Research interests: Membrane technologies, Water reuse, Desalination, Biofouling

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

W3.3 BING WU ENHANCING MEMBRANE FOULING MITIGATION BY FLUIDIZED GRANULAR ACTIVATED CARBON

BING WU1, JINGWEI WANG1,2,3, JIA WEI CHEW1,3, YU LIU4,5, ANTHONY G. FANE1,5 1 Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Cleantech Loop, CleanTech One #06-08, Singapore, 637141 2 Interdisciplinary Graduate School, Nanyang Technological University, Singapore 3 School of Chemical and Biomedical Engineering, Nanyang Technological University, 637459, Singapore 4 Advanced Environmental Biotechnology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, 1 Cleantech Loop, CleanTech One #06-08, Singapore, 637141 5 School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798 INTRODUCTION

Anaerobic fluidized-bed membrane bioreactor (AFMBR) concept has been proposed by Kim et al.1 due to its low energy requirements (0.028-0.227 kWh/m3)1,2. However, the occurrence of membrane fouling due to the unfavorable interactions of the filtered substances with membranes reduces the membrane performance and increases the operating cost. In the AFMBR, the scouring shear force along the membranes is dependent with fluidization velocity and GAC configurations. As GAC particle size and amount determine the required minimum velocity to fluidize GAC particles, which is associated with minimize energy usage. Thus, the optimizations of GAC particle fluidization and membrane filtration conditions are necessary in order to achieve better membrane performance and less energy consumption in AFMBR. MATERIALS AND METHODS

Bench-scale hollow fibre and flat sheet membrane filtration assays were setup to investigate the membrane performance in the presence of GAC fluidization at a constant flux. Transmembrane pressure (TMP) was calculated as the difference of feed pressure and permeate pressure, which were measured by pressure transducers. The GAC particles purchased from Calgon Carbon Corporation (USA) were separated into different sizes by sieving (W.S. Tyler Industrial Group, USA).

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373

THEME: MEMBRANE FOULING

RESULTS AND DISCUSSION

In the GAC fluidization-hollow fibre membrane filtration system, three hollow fibre spacings (0, 2, and 5 mm) and three size ranges of GAC particles (0.5-1, 1-1.4, and 1.4-2 mm) were tested in this study. Fig. 1a shows that the optimal ratio of hollow fibre spacing to fluidized particle size is around 3-5 and the choice of hollow fibre spacing is dependent on the size range of the fluidized GAC particles. In addition, greater-sized GAC could significantly alleviate membrane fouling. Fig. 1b reveals that fluidized GAC particles could not further benefit fouling reduction during the idle period of permeate filtration.

Figure 1. GAC fluidization-hollow fibre membrane filtration system: (a) Effect of hollow fibre spacing and GAC size on cake layer resistances (v represents the liquid upflow velocity); (b) Effect of intermittent filtration on membrane fouling rate in the presence of fluidized GAC particles.

In the GAC fluidization-flat sheet membrane filtration system, Fig.2 shows that variations of the fouling rates with respect to height are apparent. This indicates that the membrane had non-uniform fouling throughout the active area. Secondly, dTMP/dt tended to increase as h/H increased, which indicate that the lower parts of the membranes were more effectively scoured by the greater GAC particles due to size-segregation effect. Thirdly, the expected negative correlation between dTMP/dt and Ul was consistent across all three particle size investigated only at the middle h/H of 0.57. This indicates that an increase in energy input through higher Ul did not always improve fouling mitigation, which could be tied to an interplay of particle velocity and concentration at different heights of the setup.

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THEME: MEMBRANE FOULING

Figure 2. GAC fluidization-flat sheet membrane filtration system: Fouling rates at different heights and superficial velocities for GAC with particle diameters of (a) 1.85 mm, (b) 1.55 mm, and (c) 1.015 mm. h is the height assessed while H is the total setup height. CONCLUSIONS

In this study, it was found that the greater-sized GAC particles with more packing amounts at higher particle velocity most benefited to membrane fouling control. However, the increased capital cost of GAC particles and energy consumption need to be considered. As weak and scattered correlation between dTMP/dt and power requirement was observed, which indicates that a higher energy input does not necessarily confer a more effective reduction in membrane fouling. Thus, identification of the optimal minimum levels of these three parameters is necessary in GAC fluidization-membrane filtration system. In addition, intermittent fluidization was proposed as an approach to reduce energy consumption. ACKNOWLEDGEMENTS

This research is supported by the Singapore National Research Foundation under its Environmental & Water Technologies Strategic Research Programme and administered by the Environment & Water Industry Programme Office (EWI) of the PUB. We also thank Prof Perry McCarty from Stanford University and Profs Jaeho Bae and Jeonghwan Kim from Inha University. REFERENCES 1

J. Kim, K. Kim, H. Ye, E. Lee, C. Shin, P.L. McCarty, J. Bae, Anaerobic Fluidized Bed Membrane Bioreactor for Wastewater Treatment, Environ. Sci. Technol. 2011, 45, 576-581.

2

C. Shin, P.L. McCarty, J. Kim, J. Bae, Pilot-scale temperate-climate treatment of domestic wastewater with a staged anaerobic fluidized membrane bioreactor (SAF-MBR), Bioresource Technol. 2014, 159, 95-103.

BING WU Title: Dr. Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore Phone: +(65) 91258929; Fax: +(65) 67910756; E-mail: [email protected] 09/2010 – now Research Fellow/Senior Research Fellow, Singapore Membrane Technology Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University 11/2008-08/2010 Postdoc Scholar, Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis 01/2007-09/2008 Project officer/Research Scientist, Institute of Environmental Science and Engineering , Nanyang Technological University

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THEME: MEMBRANE FOULING

W3.4 MUAYAD AL-SHAELI FACILE CONTROL OF ANTIFOULING AND HYDROPHILICITY IN BPPO ULTRAFILTRATION MEMBRANES VIA DIETHYLENETRIAMINE SURFACE MODIFICATION

MUAYAD AL-SHAELI1, STEFAN J. D. SMITH1, 4,EZZATOLLAH SHAMSAEI1, HUANTING WANG1, KIASONG ZHANG2, BRADLEY LADEWIG3 1 Monash University, Department of Chemical Engineering, Clayton, VIC, 3800, Australia 2 Institute of Urban Environment, Chinese Academy of Sciences, No. 1799, Jimei Road, Xiamen 361021, China 3 Department of Chemical Engineering, Imperial College London, Exhibition Road, London SW72AZ, United Kingdom CSIRO, Manufacturing, Private Bag 33, Clayton South MDC, VIC 3169, Australia ABSTRACT

Ultrafiltration membranes (UF) are implemented across a range of water treatment applications, including wastewater, protein separation applications as well as a pretreatment to reverse osmosis for pharmaceutical and biotechnological industries.1-8 Asymmetric Polymeric UF membranes are particularly attractive for their simple operation, potential for high permeability and lower energy consumption. Unfortunately many UF polymers are prone to fouling, in which the deposition and accumulation of particles, colloids and macromolecules on the membrane and pore surfaces, rapidly decreases a membrane’s flux and lifespan, and significantly increasing its operational costs. Developing membranes that exceed the permeability of current materials and exhibit excellent resistance to fouling is vital to improving UF performance; reducing membrane area and maintenance requirements9. Despite high flux, many hydrophobic UF membranes have unsatisfactory high fouling rates that prevent their use of UF technologies. Once such example is bromomethylated-polyphenylene-oxide (BPPO), which is outstanding ultrafiltration in terms of chemical and thermal stability, flexibility and film forming properties; 10 however its hydrophobic character makes it particularly susceptible to membrane fouling. Therefore, a BPPO UF membrane is a prime candidate for using surface modification to reduce fouling to a minimum. BPPO’s brominated functional (-CH2Br) group at the film surface enables directly grafting of amine or imidazole based hydrophilic species to the membrane, achieving a super-hydrophilic and fouling resistant surface11-13. In this study, the facile grafting of Diethylenetriamine (DETA) has been successfully grafted on the top surface of BPPO UF membranes, without using the use of pre-treatments or cross-linkers. DETA was chosen for this study based on its 1) low volatility, 2) reactive primary and secondary amine groups, 3) commercially availability, and 4) its solubility in polar organic solvents14. Our results show the hydrophilicity of the BPPO- DETA composites

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increased significantly, leading to a significant reduction in the adsorption of BSA in static protein adsorption tests over the pristine BPPO membranes (Figure 1A). The surface modified DETA/BPPO also has a much better flux recovery ratio (almost 100%) compared to the unmodified BPPO membranes at 45.3 % (Figure 1B). Although flux is reduced by the surface modification, the considerable improvement in anti-fouling will provide significantly greater lifetimes in water treatment applications. Furthermore, due to the effective rejuvenation of the composite UF membrane performance during normal cleaning processes, the modified BPPO will have higher performance than the pristine membrane after a couple of operation cycles (Table 1). These results highlight value of direct surface modification in the development of high performance UF membranes with excellent anti-fouling properties.

Figure 1 A, B; (left) Static contact angle of the pristine BPPO and Diethylenetriamine/BPPO composite membrane. (right) Flux recovery ratio of the pristine BPPO and Diethylenetriamine/BPPO composite membranes Table 1: BPPO Membrane flux and FRR% with DETA surface modification

Membrane

Flux (LMH)

Flux after physical and chemical cleaning

FRR % 45.31

Neat BPPO

197.01

89.268

BPPO/DETA-15 min

190.9589

131.2473

68.73

BPPO/DETA-30 min

164.7918

117.5342

71.32

BPPO/DETA-1hr

154.5019

119.9227

77.61

BPPO/DETA-1.5 hr

134.7962

111.7808

82.92

BPPO/DETA-2hr

129.0411

109.4794

84.84

BPPO/DETA-3 hr

119.4766

109.3146

91.49

BPPO/DETA-4 hr

111.8407

107.7297

96.32

BPPO/DETA-5 hr

94.87791

92.46575

97.45

BPPO/DETA-6 hr

88.89911

87.53425

98.35 99.23

BPPO/DETA-12 hr

80.34248

79.72603

BPPO/DETA-24 hr

79.72606

79.72603

99.9 GOLD SPONSOR

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THEME: MEMBRANE FOULING

REFERENCES 1. Baker, R., Membrane technology and Application. 3rd ed. 2012, United Kingdom: John Wiley & Sons. 2. Cheryan, M., Ultrafiltration and Microfiltration Handbook. 1998: Technomic Publishing Company, Inc., Pennsylvania. 3. Cassano, A., M. Marchio, and E. Drioli, Clarification of blood orange juice by ultrafiltration: analyses of operating parameters, membrane fouling and juice quality. Desalination, 2007. 212(1-3): p. 15-27. 4. Shen, J.n., et al., Purification and concentration of collagen by charged ultrafiltration membrane of hydrophilic polyacrylonitrile blend. Separation and Purification Technology, 2009. 66(2): p. 257-262. 5. Lee, C.W., et al., Application of ultrafiltration hybrid membrane processes for reuse of secondary effluent. Desalination, 2007. 202(1-3): p. 239-246. 6. Ulbricht, M., Advanced functional polymer membranes. Polymer, 2006. 47(7): p. 2217-2262. 7. Yan, L., Y.S. Li, and C.B. Xiang, Preparation of poly(vinylidene fluoride)(pvdf) ultrafiltration membrane modified by nano-sized alumina (Al2O3) and its antifouling research. Polymer, 2005. 46(18): p. 7701-7706. 8. Haoxia, Y., et al., Development of a hydrophilic PES ultrafiltration membrane containing [email protected] nanoparticles with both organic antifouling and antibacterial properties. Desalination, 2013. 326: p. 69-76. 9. Nair, A.K., et al., Antifouling and performance enhancement of polysulfone ultrafiltration membranes using CaCO3 nanoparticles. Desalination, 2013. 322: p. 69-75. 10. Tang B, Xu T, Gong M, Yang W (2005) A novel positively charged asymmetry membranes from poly (2,6-dimethyl-1,4- phenylene oxide) by benzyl bromination and in situ amination: Membrane preparation and characterization. Journal of Membrane Science 248 (1-2): 119-125. doi:10.1016/j. memsci.2004.09.027 11. Lin, X.; Liang, X.; Poynton, S. D.; Varcoe, J. R.; Ong, A. L.; Ran, J.; Li, Y.; Li, Q.; Xu, T. Novel alkaline anion exchange membranes containing pendant benzimidazolium groups for alkaline fuel cells. J. Membr. Sci. 2013, 443, 193-200. 12. Lin X, Varcoe JR, Poynton SD, Liang X, Ong AL, Ran J, Li Y, Xu T (2013) Alkaline polymer electrolytes containing pendant dimethylimidazolium groups for alkaline membrane fuel cells. Journal of Materials Chemistry A 1 (24): 7262-7269. Doi: 10.1039/c3ta10308k 13. Lin, X.; Wu, L.; Liu, Y.; Ong, A. L.; Poynton, S. D.; Varcoe, J. R.; Xu, T. Alkali resistant and conductive guanidinium-based anion- exchange membranes for alkaline polymer electrolyte fuel cells. J. Power Sources 2012, 217, 373-380. 14. Wang H, Paul DR, Chung TS (2013) Surface modification of polyimide membranes by Diethylenetriamine (DETA) vapor for H2 purification and moisture effect on gas permeation. Journal of Membrane Science 430:223-233. Doi: 10.1016/j.memsci.2012.12.008

MR. MUAYAD NADHIM ZEMAM AL-SHAELI Monash University, Australia. Phone: +61 416 604042, E-mail: [email protected] Research interests: Wastewater treatment, Membrane bioreactor, anti-biofouling, ultrafiltration, and membrane fouling

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

W3.5 QIANHONG SHE MEMBRANE FOULING IDENTIFICATION, MECHANISMS AND CONTROL FOR PRESSURE-RETARDED OSMOSIS (PRO) WITH REAL WASTEWATER RECLAMATION RETENTATE AS FEED

QIANHONG SHE, LIZHI ZHANG, RONG WANG, ANTHONY G. FANE Singapore Membrane Technology Centre, Nanyang Environment & Water Research Institute, Nanyang Technological University, Singapore 637141 Pressure-retarded osmosis (PRO) has attracted worldwide attention for its potential applications in the renewable salinity-gradient energy harvesting, waste industrial brine disposal, and low energy seawater desalination. Membrane fouling has been identified to be one of the major issues limiting the PRO performance. Although a number of studies have been performed to investigate the PRO membrane fouling, the majority of them focused on the use of synthetic water as feed which could not sufficiently represent a practical scenario. PRO membrane fouling by real waters is much more complicated. However, its cause and effect are much less understood. This study aims to systematically investigate the PRO membrane fouling by using a real impaired wastewater as feed. The specific objectives are to (1) identify the major types of fouling caused by the real wastewater, (2) explore the fouling mechanisms governing the mixed-fouling in PRO, and (3) develop effective strategies to mitigate the PRO membrane fouling. In this study, the real wastewater reclamation retentate (WWRR), a type of reverse osmosis (RO) concentrate from a local wastewater reclamation plant, was used as feedwater. Seawater desalination brine was used as the draw solution. Commercially available cellulose-triacetate (CTA) and thin-film composition (TFC) membranes were used in the bench-scale PRO membrane fouling tests with the membrane active layer facing draw solution (AL-DS). The fouling tests were performed at different initial water fluxes by varying the applied hydraulic pressures in the draw solution. The raw feedwater characteristics were analysed to identify the potential foulants by a series of instruments/techniques, such as liquid chromatography-organic carbon detection (LC-OCD), total organic carbon (TOC), inductively coupled plasma mass spectrometry (ICP-MS), ion chromatography (IC), pH, and conductivity. The fouled membrane was autopsied and characterized through optical observation and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX). It was found that the WWRR contained large quantities of multi-valent inorganic ions (e.g., calcium, magnesium, sulphate and phosphate ions) and organic compounds (e.g., humic substances and biopolymers). After the PRO fouling tests using WWRR as feedwater, severe membrane fouling and flux decline were observed. The autopsy of the fouled membranes identified both inorganic scaling (e.g., by calcium phosphates) and organic fouling (e.g., by humic substances) inside the membrane support layer, with the former playing a dominant role in water flux decline. The severe internal membrane fouling in PRO was GOLD SPONSOR

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attributed to the severe internal concentration polarization (ICP) which significantly elevated the concentration of scaling precursor ions organic macromolecules within the membrane support layer and thus increase the fouling tendency. This study revealed that the ICP-enhanced fouling is one of the major fouling mechanisms for PRO. This study also observed that the water fluxes at different applied pressures (or initial water fluxes) tended to decline to an identical limiting flux at the end of PRO fouling test. A pressureindependent PRO limiting flux theory was developed to explain this phenomenon and guide the PRO operation to improve the osmotic power output. After understanding the PRO membrane fouling types and mechanisms, several strategies were developed to mitigate fouling. Firstly, a novel backwashing method by utilizing the nature of the PRO process was developed for membrane cleaning. The results show that this method can restore over 90% water flux only by 15 mins cleaning. Secondly, feedwater chemistry was adjusted by reducing the pH to mitigate the alkaline scaling caused by phosphates and carbonates. The results indicate that reducing the pH below 5.5 can double the water flux and power density. Finally, changing the membrane orientation to active-layer-facing-feed-water (AL-FS) mode was demonstrated to be an effective and feasible approach for PRO fouling mitigation, although further studies are required to improve the membrane mechanical strength. This study provides significant implications for the practical applications of PRO when using real impaired waters as feed.

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W3.6 STUCKEY DAVID C FOULING IN ANAEROBIC MEMBRANE BIOREACTORS: TOWARDS A MORE NUANCED APPROACH

STUCKEY DAVID C.1,2 1 Nanyang Environment and Water Research Institute (NEWRI), Nanyang Technological University (NTU), Singapore. 2 Chemical Engineering Department, Imperial College London, UK. ABSTRACT

Fouling in both aerobic and anaerobic membrane bioreactors (MBRs) is generally considered undesirable as it leads to higher TMPs, and hence higher capital and operating costs. However, the fouling layer plays an important role in rejecting many soluble organics and colloids, and hence this work argues that we should develop a more nuanced approach to membrane fouling by demonstrating the ability of a fouling layer in a submerged anaerobic membrane bioreactor (SAMBR) to enhance reactor performance. It then goes on to examine a variety of methods to reduced membrane fouling so we can control its thickness and hence optimise it overall performance. INTRODUCTION

With the rapid introduction of membrane reactors, both aerobic and now increasingly anaerobic, to treat wastewaters engineers have focussed on “membrane fouling” as the single most important issue hindering their widespread use. Membranes “foul” by accumulating a layer of bacterial flocs, colloids (<0.45µm), and soluble microbial products (SMPs) due to rejecting these constituents by size exclusion. This layer builds up and increases the pressure drop across the membrane (transmembrane pressure-TMP), leading to higher pumping costs and lower membrane fluxes (litres per square meter per hourLMH). This in turn leads to lower fluxes and higher installed membrane area and hence higher capital and operating costs. Hence it appears that membrane fouling is an unmitigated drawback. Nevertheless, membrane fouling does lead to higher rejection of many constituents of wastewater, eg SMPs, that improves effluent quality. Hence, in this paper I will put forward a case for a more nuanced approach to membrane fouling, ie that fouling per se is a good thing in terms of effluent quality, BUT too much fouling is bad because it leads to lower fluxes and higher TMPs, and hence to higher costs. Therefore, the argument then becomes not whether we can remove ALL fouling, but at what “level” it is good and acceptable for reactor performance, and how can we control fouling to a degree that is optimal? In this instance I will focus on anaerobic membrane bioreactors as this is the area I have worked in for the last 16 years.

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RESULTS

1) Removal of SMPs from the reactor supernatant It has been known for many years that the COD of the reactor supernatant (the soluble and colloidal components in a reactor) in a membrane bioreactor is considerably higher than the effluent COD- by 5-10 times at steady state, while under shock loads this can reach as high as 100. In other words, the membrane (even microfiltration membranes with a pore size of 0.45µm) rejects many soluble constituents from passing through into the effluent. This is clearly due to the “fouling layer” (cake solids, biofilm, gel layer) on the surface on the membrane rather than the membrane pore size per se. This observation is reinforced after the membrane is chemically cleaned when for the first 5 minutes the effluent quality is very poor as the fouling layer builds up again. Hence what type of compounds are rejected by the fouling layer, and how are they “rejected” -by size exclusion, charge exclusion despite their low MW, or by metabolism within the fouling layer. Figure I from a submerged anaerobic membrane reactor (SAMBR) shows the reactor under a shock load which rises from 4 g/L to 20 g/L in a step change. At steady state the reactor has a soluble COD around 1 g/L and an effluent of 100 mg/L; hence 90% of the soluble COD is being rejected. However after the shock load the supernatant increases to over 6 g/L while the effluent only increases to 300 mg/L, and only after a lag phase-in this case 98% of the COD is being rejected.

Figure 1 COD in a SAMBR under shock loads.

2) Rejection of VFAs Another interesting observation is that under certain fouling conditions very small but highly charged VFAs (eg acetic acid) can be rejected by the fouling layer, and this is gassing rate dependent. Figure 2 shows that without biomass at 2LPM there was significant rejection by the membrane over more than a day, and the effluent VFAs were significantly lower than in the reactor; with biomass the difference was almost as large, but persisted over a shorter time. With 5 LPM the fouling layer would have been thinner, and the VFA difference was very small, and could probably be explained by VFA metabolism within the fouling layer. Hence increasing rates leads to thinner fouling layers and less rejection,

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although a small fraction of this rejection can be due to biological metabolism in the fouling layer as the VFAs pass through the membrane.

3) Rejection of phages (viruses) Small biological entities such as viruses can also be rejected by fouled membranes, and in some recent work in a SAMBR T4 phages (~200 nm) had removals up to 7 logs (complete removal), while even the small MS-2 (~22 nm) had removals of 1.7-5.5 logs, and this depended on the gassing rate in the reactor, although this relationship was considerably more complex.

4) Control of the fouling layer If the thickness/composition of the fouling layer does control the degree of rejection in an anaerobic membrane bioreactor, then how can we control this layer to achieve optimum operating conditions, ie low effluent CODs, while achieving acceptable TMPs and fluxes? There have been a variety of ways to control fouling in anaerobic MBRs; gassing strategy (volume and variations), addition of GAC/PAC to adsorb soluble organics/colloids, precipitation/agglomeration; • a) gassing strategy- this is also important in order to reduce the energy input to the SAMBR, and is the main way of reducing the thickness of the fouling layer. The volumetric flow per square metre of membrane area is one crude measure, but this ignore the fluid dynamics of the reactor which is complex being a three phase system with a non-Newtonian liquid • b) addition of PAC-work has shown that addition of PAC to the reactor contents (from 400-1600 mg/L) adsorbs many of the colloids and SMPs and leads to lower supernatant COD and hence reduces fouling and TMPs. • c) addition of polymers and precipitants-addition of FeCl3 and polymers also acts to reduce soluble constituents and minimise fouling and TMP. Key question is how long do these additives last in the SAMBR and what is their fate, eg degraded, adsorbed, washed out in the effluent?

Figure 2 The effect of biogas sparging rate on VFA rejection in a SAMBR with and without biomass.

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CONCLUSIONS

The fouling layer in a submerged anaerobic membrane bioreactor was shown to result in the rejection of a range of soluble organics, and colloids. In addition, under certain conditions it appears to even reject low MW highly charged organic acids such as acetic, and small phages. Hence, the properties of the fouling layer are very important in membrane bioreactors as they lead to its very high performance. It is important we understand more about the properties of this fouling layer in terms of how it rejects specific solutes, and how we can control its properties and thickness through optimising operating parameters such as gassing rate and sequence, and the use of specific additives. 1

A.R.D. Verliefde, E.R. Cornelissenb, S.G.J. Heijmana, J.Q.J.C. Verberk, G.L. Amy, B. Van der Bruggend, J.C. van Dijka. The role of electrostatic interactions on the rejection of organic solutes in aqueous solutions with nanofiltration. J. Memb. Sci. 2008, 322, 52–66.

2

A. L. Smith, S. J. Skerlosab and L. Raskin. Anaerobic membrane bioreactor treatment of domestic wastewater at psychrophilic temperatures ranging from 15 °C to 3 °C. Environ. Sci.: Water Res. Technol., 2015, 1, 56-65.

3

R. Fox, D. Stuckey. MS-2 and T4 phage removal in an anaerobic membrane bioreactor (AnMBR): effect of gas sparging rate. J Chem. Tech. Biotech., 2015, 90(3), 384-390.

DAVID STUCKEY Title: Professor NEWRI, NTU, Singapore; Imperial College London, UK Phone: +65 93750408 E-mail: [email protected]; [email protected]

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W3.7 HANS G. L. COSTER IN-SITU CHARACTERIZATION OF BIO-FOULING ON RO MEMBRANES USING ELECTRICAL IMPEDANCE SPECTROSCOPY: THRESHOLD FLUXES AND BIOFILM FORMATION

HANS G. L. COSTER1, JIA SHIN HO,2,3, LEE NUANG SIM3, ANTHONY G. FANE,3 1 School of Chemical and Biomolecular Engineering, University of Sydney, Sydney, Australia. 2 Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore. 3 Singapore Membrane Technology Centre, Nanyang Technological University, Singapore. Electrical impedance spectroscopy (EIS) was employed to monitor RO membranes in-situ during crossflow filtration using a membrane module fitted with suitable electrodes. EIS spectra can be analyzed in terms of layers and processes that are associated with 2.5 different electrical time constants1. A useful representation of the EIS data is the Nyquist plot of the negative Imaginary impedance vs the Real part of the impedance2. Such a plot immediately reveals the presence of layers with distinct electrical time constants; see 2 Figure 1.

-Imaginary Impedance (ohm.m2)

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Figure 1. A Nyquist plot of the (negative) Imaginary impedance as a function of the Real impedance for an RO membrane. The Nyquist plot consists of a series of overlapping semi-circles,; each semi-circle representing an electrical element (layer) with a different time constant or characteristic frequency. The points shown are the average for 3 spectra with error bars (usually smaller than the size of the symbols used). The full curve is a fit to the data based on an electrical model representing layers within the membrane and at its surface. The characteristic frequencies for the layers identified are indicated on the diagram. GOLD SPONSOR

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One such layer identified in the spectra at very low frequencies (1-10 Hz) is the AC diffusion polarization layer that forms at the surface of the membrane within the usual concentration polarization layer. The conductance, (GDP) of this layer provides an indication of the nature of the material accumulating very close to the surface. When the feed water contained bacteria the value of GDP gradually increased as the bacteria (with highly conducting cytoplasm) accumulated on the surface. However, once the bacteria began to produce extra cellular polymeric substances (EPS) and a biofilm formed, the value of GDP decreased as the biofilm has a higher electrical resistance, Figure 2.

Figure 2. The normalized conductance of the diffusion polarization layer, GDP, as a function of time in an experiment in which the feed contained bacteria (concentration ~ 105 cfu mL-1) Conditions: permeate flux = 30 L m-2 h-1, crossflow velocity = 0.15 m s-1, RO feed = 24 mg L-1 NB with 2000 mg L-1 NaCl. For the first 1.5 days the accumulation of bacteria on the membrane surface caused an increase in GDP but as EPS material was produced and a biofilm started to form, GDP began to decrease. Inset: CLSM images for live/dead staining of biofilm on RO membrane at the end of the 5 day experiment; live cells are shown in green whilst dead cells are in shown red.

The inflection point of GDP vs time was itself dependent on the value of the flux (decreasing with increases in flux) and crossflow velocity (increasing with increasing crossflow). It would thus appear that the inflection point for GDP corresponds to a threshold phenomenon where accumulation of individual bacteria changes to formation of a biofilm and that it is a relatively well defined phenomenon, at least under controlled experimental conditions. Experiments with dead bacteria with and without alginate to simulate EPS verified the conclusions drawn from the EIS measurements. The change in the nature of the biofouling could also be discerned in the TMP (transmembrane pressure) vs time which showed a change in slope at a similar point in time during the biofouling experiments (Figure 3), although not as sharply defined as the

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profile for GDP.

(b)

Figure 3. Normalized TMP profile as a function of time in the presence of bacteria (concentration ~ 105 cfu mL-1), other conditions as per Figure 2.

The concept of a “Threshold” point in biofouling , its relation to biofilm formation and its detection using EIS could be used for in-situ monitoring of RO membranes to optimize the timing and dosing levels of biostats in plants and monitor the effectiveness of biostats or biocides used to control biofouling. That could either be achieved using a “Canary” crossflow membrane module (fitted with suitable electrodes) connected in a side stream of a RO train or by suitable modification of the spiral wound modules themselves, REFERENCES 1

Coster, H. G. L., T. C. Chilcott and A. C. F. Coster (1996). Bioelectrochem. Bioenerg. 40: 79-98.

2

L.N. Sim, J. Gu, H.G.L. Coster, A.G. Fane, Desalination, 379 (2016) 126-136.

HANS G. L. COSTER Professor University of Sydney, Australia Phone: +619351 2256 E-mail: [email protected] Research interests: Novel membranes, Membrane characteriza

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W3.8 STEVEN CAO SCALE UP OF CHEMICAL CLEANING: SUCCESS FROM FIBRE CLEANING IN THE LAB TO A FULL MODULE CLEAN

ANH NGUYEN1, STEVEN CAO1, PAUL GALLAGHER2 1 Evoqua Water Technologies Membrane System 15 Blackman Crescent, South Windsor, NSW, Australia 2 Evoqua Water Technologies LLC, 558 Clark Road, Tewksbury MA 01876 Fouling of low pressure membrane used in municipal water treatment remains the main technical challenge. Although there has been numerous research focusing on foulant identification1,2,, and impact of membrane properties3,4 and feed water5 on membrane fouling, research on membrane cleaning especially on the impact of scale up from lab to full module on membrane chemical cleaning efficiency has been very limited. This study looks at the scale up effect from lab scale cleaning of small membrane surface area to a full module clean at pilot scale. Evaluation of a successful chemical clean was also discussed in this paper. This research study was conducted with fouled module and operated with naturally foul feed water, not usually available in many other research studies conducted elsewhere. Fibres were harvested from a module returning from site treating wastewater effluent. Three groups of chemicals were used including commonly used chemicals (sodium hypochlorite, and acid), proprietary commercial cleaners, as well as different blending of chemicals adjusted to different pHs. Chemicals were gradually eliminated until best cleaning protocols were identified. The effectiveness of the lab scale fibre clean was determined by comparing the clean water permeability (CWP) of the fibre (made to mini modules) prior and post chemical clean. The CWP was measured by an in-house testing rig. The best cleaning protocols were then applied at full module clean using an in house built pilot machine. The pilot cleaning procedure followed the same cleaning procedure at large scale. The effectiveness of the full module clean was determined based on two factors: the CWP prior and post chemical clean, and performance after chemical clean. The ultimate desired results of a successful chemical clean at full module scale are high permeability recovery and stable performance during the designed chemical clean interval. The pilot was operated at constant flux with periodic air and liquid backwash, mimicking large-scale operation. A scale up factor (SC) was calculated based on CWP of lab scale and CWP of full module to evaluate the impact of scale on fibre/module CWP and cleaning efficiency. Results from case cleaning study showed that there was a scale up factor from lab scale fibre level to pilot full module level when measuring clean water permeability in both prior and post chemical clean. The prior chemical clean scale up factor (SC0) was attributed to pressure loss through fibre lumen and pilot system. After chemical clean, the scale up

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factor SC1 became higher, i.e., more prominent effect of scale after module clean. The higher post clean scale up factor (SC1) suggested the less effective clean at pilot scale compared to lab scale. This was attributed to the limited chemical contact of each individual fibre at pilot scale compared to lab scale. Through lab scale results, two possible cleaning protocols were identified as best candidates and conducted at both lab and pilot scale. The two cleaning protocols, used different kinds of chemicals (one with acid + surfactant + oxidant and one with enzyme + oxidant), resulted in similar post clean CWP in both lab scale and full module scale. However, the operation of the module with fouling water was unstable after cleaning with acid + surfactant + oxidant while stable after cleaning with enzyme + oxidant. The results from this study suggests that a high CWP value after chemical clean does not necessarily represent a successful clean. It is recommended to follow up with fouling test, ideally full module operation with a foul water, to validate the effectiveness of a chemical clean. REFERENCES 1

C. Laabs, A. Gary, and M. Jekel, J. Water Science and Technology. 2006, 40 (14), 4495-4499

2 L. Villacorte, Y. Ekowati , H. Winters , G. Amy , J.C. Schippers & M.D. Kennedy, J. Desalination and Water Treatment. 2013 51 (4-6), 1021-1033 3 A. Zydney, L. Andrew, C. Ho, , 2003 Biotechnology and Bioengineering 83, 537-543 4 B. Kwon, J. Cho, N. Park, and J. Pellegrino, 2006 J. of Membrane Science, 279 (1), 209-219 5 G. Makdissy, J.P Croue, G. Amy, H. Buisson, 2004 J. of Water Science and Tech: Water Supply, 4 (4), 205-212

ANH NGUYEN Title: Senior Research Engineer Evoqua Water Technologies Membrane System, Australia Phone: +61 (2) 4577 0810 Fax: +61 (0) 2 4577-0919 E-mail: [email protected] Research interests: membrane fouling, use of membrane in water and wastewater treatment

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W3.9 FILICIA WICAKSANA NON-INVASIVE AND DIRECT MONITORING OF HOLLOW FIBRE MEMBRANE FOULING DISTRIBUTION

FILICIA WICAKSANA1, PETR BILEK2, LIU XIN3, WU BING3, LI WEIYI3, A. G. FANE3 1 Department of Chemical and Materials Engineering, the University of Auckland, Auckland 1142, New Zealand 2 Technical University of Liberec, Czech Republic, EU 3 Singapore Membrane Technology Center, Nanyang Technological University, 639798 Singapore, Singapore Fouling is inevitable in membrane filtration process, particularly in a submerged membrane system, where membranes are subjected to high concentration of suspended solid. In a submerged hollow fibre membrane system, the permeate is typically extracted from the top end of the module while the other end is sealed. Due to this configuration, the local flux at the section of the fibres closer to the suction point tends to be greater than the opposite end. Consequently, more severe fouling occurs at the region nearer to the suction point as compared to the other end of the module1. It is common knowledge that membrane fouling propensity is affected by various parameters. Hence, understanding key parameters that affect the local flux distribution is critical to enhance the membrane filtration performance and achieve sustainable operation. However, the majority of former studies on membrane fouling distribution focused on the development of mathematical models (simulation studies)2,3,4, which require further verification, only limited studies on fouling distribution that involved experimental work5,6. Hence, further study is essential to obtain better understanding of these complex phenomena. This study was aimed to provide better understanding of hollow fibre membrane fouling distribution which would help to develop fouling control strategy and to improve the membrane module design. The project involved the use of in-situ and online techniques (optical microscope and optical coherence tomography) to observe fouling distribution along a hollow fibre membrane (UF, polyacrylonitrile, Mann+Hummel). Bentonite (ECP ltd) was used as model feed at various concentrations. The filtration was performed at constant flux for up to four hours. Fouling progress was monitored at certain time interval by observing the thickness of cake layer at various locations along a hollow fibre membrane during filtration under various operating and hydrodynamic conditions. Images captured from in-situ observation (Fig 1) were analysed using ImageJ and Matlab to determine the thickness of cake layer.

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Fig 1. Fouling deposition upstream of a hollow fibre membrane observed with (a) optical microscope and (b) optical coherence tomography technique

Fig 2. Development of cake layer thickness at upstream, middle section and downstream of the hollow fibre membrane (50 cm fibre length, cross flow velocity 0.018 m/s, 60 LMH, 300 mg/L bentonite)

The analysis of optical microscopic images revealed that the upstream region had more severe fouling as compared to the middle section and the downstream of the hollow fibre membrane (Fig 2). Clearly, this was due to the upstream region was closer to the suction point. Hence, greater local flux caused more severe fouling1. It is interesting to observe that changes in fouling distribution occurred in response to changes in the cross flow velocity. Observation results with OCT indicated that at low cross flow velocity (0.018 m/s), the upstream region (closer to the suction point) demonstrated more severe fouling than the downstream of the hollow fibre membrane. When the cross flow velocity was increased to 0.033 m/s, more uniform deposition was observed, while opposite trend occurred at higher cross flow velocity (0.048 m/s) with the downstream region experienced more severe fouling than the upstream region. This suggests that fouling distribution can be controlled by altering the operating parameters. GOLD SPONSOR

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ACKNOWLEDGEMENT

The support of the Singapore Membrane Technology Centre for performing the OCT experiments is gratefully acknowledged. REFERENCES: 1 S. Chang, A.G.Fane, J. Membr. Sci., 2001, 184, 221-231. 2 X. Li, J. Li, H. Wang, X. Huang, B. He, AIChE J., 2015, 61 (12), 4377-4386. 3 T. Carroll, J. Memb. Sci., 2001, 189, 167-178. 4 S. Lee, P. Park, J. Kim, K. Yeon, C. Lee, Water Research, 2008, 42, 3109-3121 5 M. Lee, J. Kim, Separation and Purification Technology, 2012, 95, 227-234 6 W. Lee, W. Cheong, K. Yeon, B. Hwang, C. Lee, Journal of Membrane Science, 2009, 332, 50-55

FILICIA WICAKSANA Title: Dr Department of Chemical and Materials Engineering, the University of Auckland, New Zealand Phone: +64 9 923 1861 E-mail: [email protected] 2013 - present

Lecturer, the University of Auckland

Research interests: Membrane processes for various applications, fouling studies and fouling control strategies.

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W3.11 M. LE HIR FOULING OF DRINKING WATER PRODUCTION MEMBRANE BY NANOPARTICLES

M. LE HIR1, Y. WYART1, G. GEORGES2, L. SIOZADE2 AND P. MOULIN1 1 Aix Marseille Univ, CNRS, Cent Marseille, M2P2, Marseille, France, UMR 7340, Equipe Procédés Membranaires (EPM), Europôle de l’Arbois, BP80, Pavillon Laennec, Hall C, 13545 Aix en Provence Cedex, France 2 Aix Marseille Univ, CNRS, Cent Marseille, Inst Fresnel, Marseille, France The presence and the increasing quantity of natural and synthetic NanoParticles (NP) in surface waters lead to a particular interest about NP separation process in drinking water production. Membrane processes present a great potential for NP retention and the behaviour of these nanomaterials in relation to the membrane filtration: their retention, their participation to fouling and their possible transfer into purified water are research axes which arouse a great interest. Filtration of ideal suspensions NP/ultrapure water has been carried out on multichannel hollow fiber membranes (Alteon I, Aquasource, France) having a 200kDa cut-off (nominal pore size of 20 nm). Nanoparticles used are silica NP of 30 nm and 100 nm, labelled with rhodamine, making them fluorescent (Micromod partikletechnologie GmbH, Germany). The filtration was conducted in dead-end mode under a constant pressure of 0.2 bar (Figure 8). At the end of the filtration, the membrane was recovered and analysed by microscopic techniques to proceed at a membrane autopsy in order to determine and visualize the NP deposition on membrane surface or in the membrane material.

Figure 1 - Dead-end ultrafiltration of NP suspension

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First of all, a macroscopic study was conducted during the filtration to evaluate the flux reduction generated by the NP retention. The flux decreases have been correlated to Hermia model laws to estimate the fouling model which reflects the better the fouling establishment operated during the filtration. Fouling models corresponding the better to the filtration of NP of 30 nm and 100 nm appears to be the cake filtration and the intermediate pore blocking which reflect a NP deposition on membrane surface. Each flux was analysed by Nanoparticle Tracking Analysis (NTA) (NanoSight NS300 – Malvern Instruments, UK) and Zetasizer (Zetasizer Nano S – Malvern Instruments, UK) to obtain the size distribution of NP used. Feed, retentate and permeate NP size distribution show no aggregation of particles during the filtration which could have been the source of a retention. The concentration of each fluxes were determined by fluorimetry and confirmed by NTA in order to obtain a concentration of NP. It was so possible to determine the number of particles filtered during the experiment and found in the permeate and the number of NP recovered in the retentate. By mass balance, the number of NP stayed blocked on membrane surface was estimated. The assumption of a homogeneous NP deposition in the different channels and all along the hollow fiber length on membrane surface was made to estimate a NP deposit thickness by calculation. This assumption is likely for NP of 30 nm and 100 nm because the diameter of NP is greater than the membrane pore size (20 nm). Membranes fouled by fluorescent NP were recovered, dried in a desiccator and hollow fibers were briefly frozen in liquid nitrogen and broken. Then, membrane sections were analyzed by CLSM (TCS SP5, Leica Microsystems CMS GmbH, Germany). CLSM has already been used in many studies to characterize the membrane morphology and structure1–6as well as for fouling characterization7–10. For each filtration experiment, membrane was analyzed at different lengths on its section. Two scans have been made in different conditions: in a visible scan (membrane) and in a fluorescence scan mode (NP). NP distribution profiles could be determined in different areas of interest of the membrane: the surface of the central channel, on the surface of an external channel inwardly and to the surface of an external channel outwards (respectively zones A, B and C in Figure 8). The great interest to analyze directly the membrane section against to scan according to depth9 is that the lateral resolution of CSLM is better than the axial one. Image analysis was performed using the software Image J 1.43 (National Institutes of Health, USA). Presence detection and distribution profiles of NP were exactly fixed at the same positions on the visible and fluorescent scan imaging in order to analyze the NP distribution profile relative to the membrane surface. The pixel size of the image with the microscope objective used is 538 nm. The imagery lets clearly identifies the membrane in red and the NP in green (arbitrarily assigned) (Figure 9- I)). The two scans have been decomposed in grayscale, as well, the presence profiles of NP in the membrane can be obtained. The membrane surface was

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defined like the maximum of the first pick obtain in the membrane profile acquired. NP distribution profile is obtained with respect to the surface of the membrane (Figure 9 – II)).

Figure 2 - I) CLSM imagery of a fouled membrane by 100 nm NP after filtration under 0.2bar II) 100nm NP distribution relative to the membrane surface (zone A)

For NP of 30 nm and 100 nm, no fluorescent signal was found inside the membrane structure. The NP deposit thickness on membrane surface was considered like peak width at half maximum of the fluorescent profile obtained. Thicknesses obtained were in agreement with results obtained by calculation. For NP of 100 nm, deposit thickness estimated by calculation is between 2 000 nm and 2 100 nm. With CLSM imaging and fluorescent NP profile analysis, a deposit thickness between 2 500 and 3 000 nm (± 500 nm) is found. Estimation of CSLM experimental error of ± 500 nm is the value of one pixel. Data obtained by the two methods present good agreement and conserve the same order of magnitude for the different size of NP. NP deposit was also visualized by Scanning Electron Microscopy (SEM) on membrane section and thicknesses found show good agreement with others techniques with a deposit thickness found between 2 000 nm and 2 600 nm (Figure 10).

Figure 3: SEM visualization of NP deposit on membrane surface for NP of 100 nm

This study allows to estimate the contribution of NP to process productivity decrease depending on the amount of NP retained and especially in function of their location on membrane surface or in membrane support. GOLD SPONSOR

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The highlight of this work is the accuracy obtained through the use of CLSM but also the cross-checking of the results obtained by the different analytical methods used. ACKNOWLEDGEMENTS:

“This work carried out in the framework of Labex MEC with the reference ANR-10LABX-0092 has received support of the State managed by the National Research Agency under the project Investments Future A * MIDEX with the reference No. ANR-11IDEX-0001-02 “. The authors are grateful to Aquasource for providing the new generation membranes used during this work. REFERENCES 1. Bonilla, G., Tsapatsis, M., Vlachos, D. G. & Xomeritakis, G. Fluorescence confocal optical microscopy imaging of the grain boundary structure of zeolite MFI membranes made by secondary (seeded) growth. J. Membr. Sci. 182, 103–109 (2001). 2. Charcosset, C., Cherfi, A. & Bernengo, J.-C. Characterization of microporous membrane morphology using confocal scanning laser microscopy. Chem. Eng. Sci. 55, 5351–5358 (2000). 3. Charcosset, C. & Bernengo, J.-C. Comparison of microporous membrane morphologies using confocal scanning laser microscopy. J. Membr. Sci. 168, 53–62 (2000). 4. Marroquin, M., Bruce, T., Pellegrino, J., Wickramasinghe, S. R. & Husson, S. M. Characterization of asymmetry in microporous membranes by cross-sectional confocal laser scanning microscopy. J. Membr. Sci. 379, 504–515 (2011). 5. Mulherkar, P. & van Reis, R. Flex test: a fluorescent dextran test for UF membrane characterization. J. Membr. Sci. 236, 171–182 (2004). 6. Yan, L., Hui, L., Xianda, S., Jianghong, L. & Shuili, Y. Confocal laser scanning microscope analysis of organic–inorganic microporous membranes. Desalination 217, 203–211 (2007). 7. Bjørkøy, A. & Fiksdal, L. Characterization of biofouling on hollow fiber membranes using confocal laser scanning microcscopy and image analysis. Desalination 245, 474–484 (2009). 8. Snyder, M. A., Vlachos, D. G. & Nikolakis, V. Quantitative analysis of membrane morphology, microstructure, and polycrystallinity via laser scanning confocal microscopy: Application to NaX zeolite membranes. J. Membr. Sci. 290, 1–18 (2007). 9. Wu, N., Wyart, Y., Siozade, L., Georges, G. & Moulin, P. Characterization of ultrafiltration membranes fouled by quantum dots by confocal laser scanning microscopy. J. Membr. Sci. 470, 40–51 (2014). 10. Zator, M., Ferrando, M., López, F. & Güell, C. Membrane fouling characterization by confocal microscopy during filtration of BSA/dextran mixtures. J. Membr. Sci. 301, 57–66 (2007).

LE HIR MORGANE Title: Ph.D student Aix Marseille University, France Phone: +644320869 E-mail: [email protected]

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THEME: MEMBRANE FOULING

W3.12 TAMAR JAMIESON COMMUNITY STRUCTURE AND IDENTIFICATION OF BIOFOULERS IN A SEAWATER REVERSE OSMOSIS DESALINATION PLANT

TAMAR JAMIESON1, SERGIO BALZANO1, AMANDA V. ELLIS2, SOPHIE C. LETERME1 1 School of Biological Sciences, Flinders University 2 Flinders Centre for Nanoscale Science and Technology, School of Chemistry and Physical Sciences, Flinders University The acceleration of climate change and the increasing population growth has placed additional stress on an already vulnerable global water supply. Seawater reverse osmosis (SWRO) is considered the simplest and most cost effective method of freshwater production to overcome this current problem. However, even after seawater pretreatment and cross flowing within the system, SWRO is often hindered by biofouling. The conditioning of the membrane and adhesion of microorganisms allow for the rapid growth of biofilms on the reverse osmosis (RO) membrane. Biofouling studies commonly focus on the role of bacteria in biofilm growth neglecting other potential biofouling organisms such as fungi and archaea. Microorganism composition, diversity and biofouling potential of the seawater supply is essential to improve pre-treatment systems, membrane coatings and the overall performance of the plant. The aim of this study was to identify the fraction of microbial community present in the seawater supply, which fouls membrane within a SWRO desalination plant using high throughput amplicon sequencing. Fragments of the ribosome small subunit-encoding gene (V1-V2 of the 16S rRNA and V4 of the 18S rRNA) were sequenced to identify the microbial communities in the seawater supply and in 2 - 4 years old biofilms on spiral bound reverse osmosis membranes. Our results suggest that the seawater supply supports a higher amount of diversity in comparison to the biofilms attached to the RO membrane. Prokaryotes, Actinobacteria, Alphaproteobacter and Thermoleophila and eukaryotes, Chromodorea, Cristidiscoidea, Trebouxiophyceae and Sordariomycetes dominated the biofilm. The microbial communities found in the seawater supply were dissimilar to the biofilm communities, which suggests that a sole survey of seawater cannot predict the biofouling potential of the community. This research provides first insights into the microbial communities in feed seawater and also in biofilms on RO membranes and their biofouling potential.

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TAMAR JAMIESON Title: Miss Flinders University, Australia Phone: +61 8 8201 2280 Fax: +61 8 8201 3015 E-mail: [email protected] edu.au 2010 - 2012

Bachelor of Medical Science

2013

Bachelor of (Honours)

Since 2014

Doctor of Philosophy

Research interests: Biofilms, Biofouling, Membranes

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

W3.13 YUNLONG LUO MEMBRANE PERFORMANCES IN MEMBRANE PHOTOBIOREACTORS (MPBRS): THE EFFECT OF HYDRAULIC RENTENTION TIME (HRT)

YUNLONG LUO,1,2 PIERRE LE-CLECH2 AND RITA K HENDERSON1,2 1 The bioMASS Lab, School of Chemical Engineering, UNSW Australia, Sydney 2 UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, UNSW Australia, Sydney The microalgae-based membrane photobioreactor (MPBR) is a newly established concept that combines photobioreactors (PBRs) and membrane filtration process for microalgae cultivation and wastewater treatment. Like MBRs, MPBR operation is exposed to membrane fouling which is still considered as an operational challenge. Membrane fouling in MPBRs develops as algae cells, organic matter derived from both algal cells and bacteria, (termed algal-derived organic matter (AOM), soluble microbial product (SMP) or transparent exopolymer particles (TEP)), and inorganic substances accumulate on the membrane surface and inside membrane pores. This study investigated the impact of an important operational parameter, hydraulic retention time (HRT), on membrane fouling in MPBRs growing Chlorella vulgaris fed with synthetic secondary effluent. Two HRTs (1 day and 4 days) were applied to two identical MPBR rigs (MPBR-1d and MPBR-4d) respectively. During this work, the biomass growth and characterisation were analysed through cell counting, measurement of mixed liquor suspended solids (MLSS), microscopic observation and flow cytometry.The membrane fouling was examined through two methods: long-term background membrane filtration at a low flux of 4 L/m2/h and batch membrane tests which involved short-term fluxstepping operation. During flux-stepping test, new batch membranes were added to the rigs, and increasing flux steps (5, 10, 15, 20 L/m2/h, …) were applied to the membrane with each step lasting for 30 minutes. The flux where rapid TMP occurred is referred to as critical flux. AOM characterisation was regularly performed via TOC measurement and liquid chromatography-organic carbon detection (LC-OCD) analysis. The results showed that operating the MPBR-1d achieved a higher biomass concentration, while applying longer HRT of 4 days resulted in a more heterogeneous system with increased bacterial counts, as demonstrated by flow cytometry analysis. The TOC data suggested that the longer HRT caused the formation of more AOM (19.1 ± 2.6 mg/L) in the rig as compared to the shorter HRT (3.5 ± 0.4 mg/L), which could be a consequence of cell lysis due to the much lower nutrient loading rate. The LC-OCD results obtained after 54-day operation confirmed that the concentration of biopolymers in the MPBR-4d (7.7 mg/L) was much higher than that in MPBR-1d (0.6 mg/L). The short-term batch membrane tests showed that MPBR-4d experienced more rapid fouling, probably due to the higher level of AOM produced during long HRT operation. However, the long-term background membrane filtration demonstrated an apparent different trend. The TMP of MPBR-1d reached over 35 kPa after GOLD SPONSOR

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55 days of operation at 4 L/m2/h , while MPBR-4d exhibited much less variation in TMP (<8 kPa) at the same flux. The higher membrane fouling propensity of background membrane in MPBR-1d could be explained by thicker cake formed on the membrane surface due to the higher biomass concentration in the rig. This work indicates that applying shorter HRTs in a microalgae-based MPBR is beneficial for microalgal biomass productivity but may be detrimental to membrane performances. Table 1. Organic fractionation of AOM

Organic fraction

Day 7

Day 28

Day 54

MPBR-1d

MPBR-4d

MPBR-1d

MPBR-4d

MPBR-1d

MPBR-4d

DOC (mg/L)

8.0

17.5

4.6

15.4

3.5

19.1

Biopolymer (mg/L)

1.9

7.9

0.8

5.9

0.6

7.7

% Protein in biopolymer

31

24

42

63

76

42

Humics (mg/L)

0.5

2.7

1.0

3.1

1.2

2.8

Building blocks (mg/L)

0.4

1.8

1.0

1.6

1.0

2.8

LMW neutrals (mg/L)

4.1

5.0

1.7

3.6

0.9

4.0

YUNLONG LUO Title: Mr. UNSW, Australia Phone: +61 466307962 E-mail: [email protected] 2012-2015

Master by Research at UTS

Since 2016

PhD at UNSW

Research interests: wastewater treatment, microalgae, membrane photobioreactor

400

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

W3.14 CORNELISSEN, E.R RO FOULING CONTROL BY OPTIMIZING PRE-TREATMENT, MEMBRANE FLUX AND AIR/WATER CLEANING

CORNELISSEN, E.R. 1,2, BLANKERT, B.3, HARMSEN, D.J.H. 1, WESSELS, L.P.4, VAN DER MEER, W.G.J. 3,5 1 KWR Watercycle Research Institute, Nieuwegein, the Netherlands 2 Singapore Membrane Technology Centre, Singapore, Singapore 3 Oasen Drinking Water Company, Gouda, the Netherlands 4 WE Consult Vianen B.V., Vianen, the Netherlands 5 Technical University of Delft, Delft, the Netherlands BACKGROUND

Multi-source 1-step full stream reverse osmosis (RO) is the working title of a conceptual innovation in water treatment for drinking water production which is based on a full stream membrane treatment with minimal pre-treatment. The main technical features of this concept are: (i) an extensive and robust removal of insoluble and soluble components from water, (ii) the production of demineralized water which is to be re-mineralized afterwards, (iii) a flexible use of locally available water sources (e.g. fresh and brackish ground and surface water, bank filtrate, rain water, (pre-treated) wastewater and seawater) and (iv) a decentral, local and relatively small production unit for drinking water supply. The application of the Multi-source 1-step full stream RO concept should therefore lead to a number of unique performance indicators, such as (i) the production of a safe and secure supply of drinking water of impeccable quality, (ii) an optimal and robust preparation on future threats (climate change, salinization, supplier demands, changing quality and quantity of available sources), (iii) high sustainability (lower energy and chemical use, less waste streams, less fouling of distribution network and drinking water installations) and (iv) a lower overall cost. AIM

The overall aim is a proof of concept of the multi-source 1-step full stream RO concept using minimal pre- and posttreatment using different water sources resulting in an impeccable water quality. This paper aims at the stable operation of RO using minimal pre-treatment processes using surface water. EXPERIMENTAL ISSUES

Locally available surface water (DOC = 6.1 mg C/L, biopolymers = 0.7 mg C/L, Calcium = 100 mg/L) was used to feed six parallel 2,5-inch RO membrane elements (Hydraunatics ESPA2) during 35 days (Fig 1). Water was pre-treated using a 250 mm coarse screen GOLD SPONSOR

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followed by (i) a 25 mm fine screen feeding four RO membrane elements and (ii) an ultrafiltration unit (Fig 2) (two Pentair X-flow XIGA 46 elements operated at 25 L/m2h using regular hydraulic and chemical backwashes) feeding two RO membrane elements. The purpose was to investigate the effect of different pre-treatment on RO operation. Half of the RO membrane elements were periodical cleaned (once per day during 5 minutes) using a mixture of air (1400 NL/h) and water (350 L/h) to study the influence of periodic hydraulic cleaning on RO operation. Four RO membrane elements were operated at a flux of 25 L/m2h and two RO membrane elements were operated at a flux of 10 L/m2h to investigate the impact of a lower fouling load. The RO membrane elements were monitored on permeate flow, feed and concentrate pressure and samples were taken for water quality monitoring (only conductivity is reported here). From this data membrane permeability, normalized pressure drop and salt passage were calculated. Membrane autopsy was performed at the end of the run (results not reported here).

Figure 1. RO installation with six parallel 2.5-inch RO membrane elements

Figure 2. UF installation feeding two 2.5-inch RO membrane elements

RESULTS AND DISCUSSION

Permeability of the RO element (at 25 L/m2h and without air/water cleaning) after UF pre-treatment remained constant during the filtration run (Fig 3), while also the normalized pressure drop did not increase significantly (Fig 4). The permeability of the RO element (at 25 L/m2h and without air/water cleaning) after fine filtration of 25 mm decreased sharply reaching 30% of its initial value. Chemical cleaning using HCl (pH 2) and NaOH (pH 11.5 at 30ºC) at 8,000 L and 15,000 L filtered volume restored the permeability only temporarily (Fig 3). A permeability decrease is caused by membrane fouling, possibly through adsorption of biopolymers1,2. At the same time a sharp pressure drop increase was observed for the RO element (at 25 L/m2h and without air/water cleaning), which could not be restored permanently by chemical cleaning as well. Pressure drop increase is caused by clogging of the feed spacer channel.

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THEME: MEMBRANE FOULING

Figure 3. Permeability RO element after UF (blue) and fine filter (red) pre-treatment (flux at 25 L/ m2h & no air/water cleaning)

Figure 4. Normalized pressure drop RO element after UF (blue) and fine filter (orange) pretreatment (flux at 25 L/m2h & no air/water cleaning)

The permeability decrease at 10 L/m2h (Fig 5) is significantly lower compared with 25 L/m2h (Fig 3) at the same filtered volume. The flux appears to have a significant impact on membrane fouling in practice, as is also known from critical flux studies3. Chemical cleaning using HCl (pH 2) and NaOH (pH 12) at 8,000 L and 15,000 L filtered volume restored the permeability only temporarily (Fig 5). A difference in permeability does not impact clogging of the feed spacer channel (Fig 4 & Fig 6), and the two fouling mechanisms (membrane fouling and spacer clogging) seem to occur independent.

Figure 5. Permeability RO element with (red) and without (blue) air/water cleaning (25 mm pre-treatment & flux at 10 L/m2h)

Figure 6. Normalized pressure drop RO element with (orange) and without (blue) air/water cleaning (25 mm pre-treatment & flux at 10 L/ m2h)

Periodic air/water cleaning does not impact permeability decrease as a result of membrane fouling (biopolymer deposition or adsorption) (Fig 5). Periodic air/water cleaning, however, is effective in controlling the normalized pressure drop coupled to spacer clogging (Fig 6)4.

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CONCLUSION

Ultrafiltration as a pre-treatment did result in stable RO operation, preventing RO membrane fouling and feed spacer clogging. Fine filtration (25 mm) on the other hand as a pre-treatment for RO did not result in stable RO operation. Decreasing flux will decrease the fouling load towards the membrane resulting in a lower membrane fouling. Air/water cleaning is ineffective in controlling membrane fouling, but is effective in controlling feed spacer clogging. A combination of pre-treatment, flux control and periodic air/water cleaning can effectively control RO fouling (both membrane fouling and spacer clogging), which is a first step in developing the multi-source 1-step full stream RO concept. REFERENCES 1

Q. Li, Z. Xu, I. Pinnau, J. Membr. Sci. 2007, 290, 173-181

2

K. Kimura, N. Ando, Sep. Pur. Tech. 2016, 163, 8-14

3

C.Y. Tang, T.H. Chong, A.G. Fane, Adv. Coll. Int. Sci. 2011, 164 (1-2), 126-143

4

E.R. Cornelissen, J.S. Vrouwenvelder, S.G.J. Heijman, X.D. Viallefont, D. Van Der Kooij, L.P. Wessels, J. Membrane Sci. 2007, 287 (1), 94-101

EMILE CORNELISSEN Title: Dr.ir. KWR Watercycle Research Institute, The Netherlands Phone: +31 30 6069538 Fax: +31 30 6069501 E-mail: [email protected] kwrwater.nl 1992

He obtained his Chemical Engineering MSc degree at the University of Twente (the Netherlands).

1997

He obtained his Chemical Engineering PhD degree at the University of Twente (the Netherlands).

1997-2002

He worked as a Process Engineer at Seghers better technology for Water in Belgium and worked on membrane filtration in waste water treatment.

Since 2003

He is a Senior Scientific Researcher at KWR Watercycle Research Institute and his research topics include membrane fouling and cleaning, rejection of emerging contaminants by pressure driven membranes and developing innovative processes

Since 2014

He is a Visiting Scientist at the Singapore Membrane Technology Centre (SMTC) at the NTU in Singapore.

He published more than 81 papers in well-respected scientific journals (h-factor of 22), co-filed 3 patents and written three book chapters. He received several innovation awards in the field water treatment and membrane filtration.

404

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

W3.16 SHENG LI EVALUATION OF POTENTIAL PARTICULATE/COLLOIDAL TEP FOULANTS ON A PILOT SCALE SWRO DESALINATION STUDY

SHENG LI, SHAHNAWAZ SINHA, TOROVE LEIKNES, GARY L. AMY, NOREDDINE GHAFFOUR Water Desalination and Reuse Center (WDRC), Division of Biological and Environmental Science and Engineering (BESE), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia, Tel. +966128084919, Email: [email protected] Nowadays, about 63% of established desalination capacity around the world is using membrane technology, mainly reverse osmosis (RO). RO is good at removing the microorganisms, salts and organics from seawater, but membrane fouling issues are still a big obstacle in seawater reverse osmosis (SWRO) desalination. Transparent exopolymer particles (TEP) and TEP precursors have been reported as potential foulants in SWRO membrane filtration 1-3. It is possible that TEP/TEP precursors form a chemical conditioning layer on the membrane surface when they deposit on membranes. This chemical conditioning layer can be thickened by the accumulation of deposited TEP/TEP precursors. Moreover, bacteria may agglutinate and grow on this TEP conditioning layer. Consequently, a biofilm can be formed and enhanced with the growth of bacteria on the conditioning layer. However, there is limited research evaluating the variation of TEP/TEP precursors (potential foulants) along the treatment scheme, especially the variation of different fractions of TEP substances in the treatment scheme. Therefore, the variation of particulate and colloidal TEP concentration along a conventional SWRO treatment scheme was evaluated in this study. The objectives are to provide a comprehensive understanding on which fraction of TEP is more problematic in SWRO fouling, and which pretreatment can better reduce the concentration of TEP. Results showed that TEP deposited on the RO membranes, and the extent of RO fouling increased with the increase of TEP concentration in RO feed water. Chlorination was effective in reducing bacterial populations till before the cartridge filters, but more TEP was produced in water after chlorination, probably because of the breakdown of bacterial cells and thus the release of internal exopolymers. However, bacteria population and TEP concentration were increased after cartridge filters. That was probably because SBS was dosed to quench the residual chlorine before the cartridge filter, and thus deactivated bacteria by chlorination recovered their activity. Consequently, the recovered bacteria might utilize the cartridge filter as an incubator for its growth and release TEP substances. A higher coagulant dosage (1.0 mg/L as Fe+3) reduced more dissolved organic carbon than the low dosage (0.25 mg/L as Fe+3). However, the more residual iron at the high dosage (if not controllable, passing through DMF) might interact with the dissolved TEP precursors GOLD SPONSOR

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THEME: MEMBRANE FOULING

present in RO feed, which led to a more severe RO membrane fouling. The addition of phosphate based antiscalant may also contribute to the higher biofouling of RO membranes. This pilot study provided an opportunity to identify the TEP related issues under different operational conditions in RO desalination of Red Sea water. REFERENCES 1. Berman, T., Biofouling: TEP - a major challenge for water filtration. Filtration and Separation 2010, 47, (2), 20-22. 2. Berman, T.; Holenberg, M., Don’t fall foul of biofilm through high TEP levels. Filtration and Separation 2005, 42, (4), 30-32. 3. Berman, T.; Mizrahi, R.; Dosoretz, C. G., Transparent exopolymer particles (TEP): A critical factor in aquatic biofilm initiation and fouling on filtration membranes. Desalination 2011, 276, (1-3), 184-190.

SHENG LI Title: Dr King Abdullah University of Science and Technology (KAUST) Phone: +966 12 8084919 Fax: +xxx E-mail: [email protected] 1999-2003

Anhui University of Technology, China

2006-2011

Delft University of Technology, Netherlands

Since 2012 King Abdullah University of Science and Technology, Saudi Arabia Research interests: membrane fouling, desalination, wastewater reuse. Forward osmosis and membrane distillation.

406

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

W3.17 SOPHIE C. LETERME THE BIOFOULING ROLE OF MICROBES IN THE DESALINATION SYSTEM School of Biological Sciences, Flinders University, GPO BOX 2100, Adelaide SA 5001 Ecological, genomics, molecular and chemical expertise were combined to assess the role played by microbial communities in biofouling Seawater Reverse Osmosis (SWRO) desalination plants. These microbes (i) have a size ranging from 0.02 to 200 µm, (ii) possess the potential to secrete extracellular polymeric substances (EPS), and (iii) are suspected to be the main source of biofouling within desalination plants. First, microbial communities were identified along the desalination system of Penneshaw (South Australia) and compared to in-situ conditions as well as water quality. This highlighted the importance of the seasonal variability of the feedwater which is likely to affect the biofouling potential of seawater and impact the performance of desalination plants. This provided useful insights on desalination plant efficiency. Then, the biofouling precursors of raw and pre-treated seawater from a reverse osmosis (RO) feed tank were investigated using a lab-scale RO cross-flow system. Bacteria and diatoms were observed on all biofouled membranes and this, along with the observed TEP and nutrients, would have formed a microbiota which has been proven to contribute to biofilm formation and its regulation. Pseudomonas sp. was identified as the major species present in the biofilm and isolated for testing. The availability of nutrients was also shown to be a key driver in TEP production, particularly for the static experiments. This provided insights into the phenomenon of biofouling by assessing the production of biofouling precursors from one of the main genera of biofilm-forming bacteria, namely Pseudomonas sp.. Finally, biofilms formed on RO membranes collected at Penneshaw desalination plant were analysed using Amplicon sequencing of the V4 region of the 18S rDNA and the V3-V5 region of the 16S rDNA gene. This was compared to information on the communities present in the feedwater to design better solutions to inhibit biofouling formation. Ultimately, this project provided further understanding of the biofouling problem and will assist in the development of strategies for future prevention. SOPHIE LETERME Title: Dr Flinders University, Australia Phone: +61 8 8201 3774 Fax: +61 8 8201 3015 E-mail: [email protected] 2003

Master in Biological Oceanography, Universite Pierre & Marie Curie - Paris VI, France

2006

PhD in Marine Biology, University of Plymouth, UK

2008-2011

Lecturer in Biological Oceanography, Flinders University, Australia

Since 2011

Senior Lecturer in Biological Oceanography, Flinders University, Australia

Research interests: microbial ecology, biofilms, desalination, climate change GOLD SPONSOR

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THEME: MEMBRANE FOULING

W3.18 JAEHYUN JUNG RECOVERY PROPERTIES OF PERMEABILITY BY PHYSICAL CLEANING TO FO MEMBRANES FOULED BY HYDROPHILIC AND HYDROPHOBIC ORGANIC MATTER

JAEHYUN JUNG, JUNHEE RYU, AND JIHYANG KWEON Department of Environmental Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, Korea INTRODUCTION

In recent years, forward osmosis process is getting great attention to overcome disadvantages of RO process in desalination and wastewater treatment. The advantages of FO process are operation at low or no hydraulic pressure, high rejection of a wide range of contaminants, and lower irreversible fouling than pressure-driven membrane processes because of the lack of applied hydraulic pressure. (Lee, et al., 2010). However, at higher flux, the fouling cake deposed on the active layer creates additional hydraulic resistance to filtration and consequently significant flux decline is observed over time. Different physical cleaning methods for FO systems have been investigated. Cross flow velocity, air-blowing, osmotic backwashing and effect of a spacer were compared to determine the most effective cleaning method for FO. In this study, we analyzed recovery properties of permeability by physical cleaning of the forward osmosis process fouled by hydrophilic (sodium alginate) and hydrophobic (humic acid) organic matter. Results from this study will provide new insights into the fouling mechanisms in FO and strategies for fouling control. METHODS

Membrane used in this study were provided by Toray Chemical, Inc. (Seoul, Korea). The Toray membrane is polyamide based membranes. The membrane area was 21.06 cm2. Sodium alginate (Junsei, Japan) and humic acids (Sigma Aldrich, USA) were used as model organic foulants to represent common organic matter. Humic acid and sodium alginate stock solution were prepared by dissolving the particle in distilled water. From this stock solutions of 100, 300, 500mg/L of humic acid and sodium alginate was prepared. The draw solution was prepared based on NaCl 1M in DI water. For the FO tests, draw and feed solutions were circulated by two gear pumps. The cross flow velocity was 9.6 cm/s on both sides of the membrane. All experiments were initiated with 1L of feed and draw solutions. After 30% of the feed solution permeated to the draw side test was stopped. Then new feed and draw solutions were prepared for physical cleaning. Physical cleaning was carried out on the feed side using a higher flow (i.e. cross flow velocity of 14.4, 19.6cm/s) for 5, 15, 30 min with DI water in a single pass. After cleaning, the cross flow velocity was reduced to its initial level, and water flux recovery was determined to evaluate the fouling reversibility.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE FOULING

Fig 1. Water flux from FO membranes using humic acid vs alginate. RESULTS AND CONCLUSIONS

The effect of flux fouling on FO level is shown in Fig.1. Tests were performed in the active layer-facing-draw solution configuration with initial fluxes ranging from 23–40 L/m2 h. Significant flux reduction was observed with the experiment with alginate. The water flux was declined by forming a denser cake layer of hydrophobic organic molecules. Effects of physical cleaning for fouling by organic will be further investigated in the next experiments and presented during the conference. ACKNOWLEDGEMENT

This research was supported by a grant (code 16IFIP-B088091-03) from Industrial Facilities & Infrastructure Research Program funded by Ministry of Land, Infrastructure and Transport of Korean government. REFERENCES 1

Lee, S.Y, Boo, C.H, Elimelech, M., Hong, S.K. Comparison of Fouling Behavior in Forward Osmosis (FO) and Reverse Osmosis (RO), J. of Mem. Sci., 2010, 365, 34-39.

JAEHYUN JUNG Department of Environmental Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, Korea Phone: +82-2-454-4056 E-mail: [email protected] Mr. Jung is a Ph. D course student at department of environmental engineering of the Konkuk University. He have completed the Master degree in 2011. After worked as a research at Korea Institute of Science and Technology (KIST) for 2year. His currently involved a research on forward osmosis.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION W4.2 BART NELEMANS NOVEL MODULE DESIGN FOR MEMBRANE DISTILLATION

BART NELEMANS, NIELS BRAND 1 1 Aquastill,Nusterweg 69, 6136KT, Sittard, The Netherlands Aquastill is in the process of developing a number of membrane distillation technologies ranging for desalination of seawater and brines from applications in the chemical, petro-chemical, and food and beverage industry. This presentation outlines the progress made on the development of membrane distillation modules and the understanding of the quantitative aspects. Extensive research is done on lab scale modules with the main focus on qualitative aspects such as scaling, fouling, wetting. Also fluxes are widely documented under many different process conditions, however a good understanding of the relationships between flux, thermal energy demand and electrical energy needs is rarely found in literature. Reason for this lack of knowledge is the difficulty of producing leak tight larger scale modules. This work presents theoretical and operational results of module testing ranging from small scale (lab tests) up to full scale membrane distillation modules. The model describes relationships between input parameters such as material geometry and process conditions (temperature profiles, salt concentrations, salt composition and cross flow velocities) and important design parameters such as flux, thermal energy en electrical energy consumption. Experimental testing, based on a reliable flexible patented module concept, is used to validate a mathematical model. Furthermore the model is used to optimize material choices and module design by performing a sensitivity analyses on material geometry. Based on this research it is possible to develop and build optimized modules for different process conditions and illustrates the importance of flexibility in module design to introduce novel membrane distillation technologies. B. NELEMANS Managing director Aquastill, The Netherlands Phone: +31 46 4572 555 Fax +31 46 4572 555 Email: [email protected] 1997 MSc degree University of Eindhoven (The Netherlands) 1997-1999 Shutdown manager chemical installations 1999-2000 Researcher at national research institute TNO 2000-2007 managing director Water Technology Holland bv Since 2007 magaging director Aquastill bv

410

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.3 PO ZHANG REVERSE OSMOSIS BRINE WASTE MINIMIZATION BY MEMBRANE DISTILLATION PROCESS PO ZHANG 1, 2, PHILIPP KNÖETIG 1, ARMIN PABSTMANN 1, STEPHEN GRAY 1 AND MIKEL DUKE 1 1 Institute for Sustainability and Innovation, College of Engineering and Science, Victoria University, Melbourne 2 Osmoflo Water Management Pty Ltd The aim of this study was to investigate the application of membrane distillation (MD) to increase water recovery from reverse osmosis (RO) brine from seawater and coal seam gas (CSG) produced water, and thus reduce discharge volumes. The effect of MD membrane fouling/scaling and cleaning regime were investigated for a direct contact membrane distillation (DCMD) bench scale apparatus operated at feed and distillate temperature of 50 °C and 25 °C, respectively. A flat sheet polytetrafluoroethylene (PTFE) membrane was used in this study. Seawater RO brine (TDS of 70 g/L and conductivity of 90 mS/cm) was studied in MD application. The results showed that MD achieved distillate electrical conductivity (EC) of less than 5 μS/cm and good flux (above 20 L/m2/h) prior to rapid flux reduction at a brine feed EC of approximately 160 mS/cm. Analysis by inductively coupled plasma (ICP) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM–EDS) revealed that flux reduction was primarily caused by precipitation of CaCO3 and CaSO4. Titration results showed that brine feed water pH and distillate flux changes were linked to the concentrations of HCO3- and Ca2+, and further revealed the precipitation process of CaCO3. It was concluded that salt precipitation was predominately caused by the supersaturation of salts in the bulk feed solution. The concentration and temperature polarization influence at the membrane surface was negligible due to only 0.5% of the feed flow being transferred as flux through the membrane (single pass recovery). A commercial antiscalant (60% of ATMP trisodium salt) was used in a synthetic supersaturated seawater RO brine solution at TDS of 185 g/L. Results showed that antiscalant could dramatically extend the induction period for the nucleation of magnesium calcite and slowed the precipitation of crystals at antiscalant concentration of 10 mg/L. Implementation of a 0.45 μm cartridge filter at the brine feed inlet extended water recovery without membrane fouling from 45% to 60% due to the removal of precipitating salts. Demineralised water and raw RO brine solutions were used to clean the membrane at flux reduction of 50%, and both cleaning regimes initially restored MD initial flux to near 100%. Periodic raw RO brine flushing restored membrane initial flux to 84% over 133 h of operation with gradual decline of initial flux after each clean. Continuous operation of MD at constant recovery showed that possible organic fouling developed over long-term MD operation with constant feed EC of SWRO brine. GOLD SPONSOR

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION CSG produced water was collected from Gloucester gas field (New South Wales, Australia), and the produced water consisted of low hardness but high sodium and bicarbonate concentrations. Batch mode MD was operated for 150 h on 72L CSG RO brine (45% RO recovery) without antiscalant dosing until brine feed reached 85mS/cm, with brine recovery at 90% (overall recovery of 95%) and normalised flux at 84% of the initial flux. SEM–EDS analysis revealed that less than 5% of the membrane surface area was covered by amorphous deposits which contain Mg, Ca, Si and Na. Thermodynamic model Phreeqc-3 calculations showed that magnesium silicates were likely to form at 90% brine recovery. A series of synthetic CSG RO brines were studied to understand interactions of silica, Mg2+, Ca2+ and HCO32-/CO32- in DCMD process. The results revealed that kinetics of CaCO3 formation was fast in brine feed due to positive Stiff & Davis Stability Index (S&DSI), and CaCO3 was likely to deposit on heat exchanger tubes due to the highest temperature in the hot cycle and lowest solubility occurring inside the heat exchanger. ICP results of MD brine samples revealed that silica did not co-precipitate with CaCO3. A 72 h continuous mode MD experiment operated at 90% brine recovery showed no co-precipitation of Mg and silica, and both Mg and silica remained in dissolved form at concentrations of 35 mg/L and 220 mg/L, respectively. Increasing of initial Mg2+ concentration in synthetic CSG RO brine resulted in formation of magnesium silicates at Mg2+ concentration greater than 45 mg/L. It was speculated that the abundant Na+ competed with Mg2+ to react with SiO44- which resulted in products more soluble than magnesium silicates. The formation of magnesium silicates did not cause appreciable flux decline. Also, distillate EC throughout the experiment was less than 5µS/cm. The effect of silica polymerization was investigated with synthetic solutions that contained NaHCO3 and NaCl. The results showed that HCO3-/ CO32- had a greater ability to stabilize silica in dissolved form when compared with Cl-. Dissolved silica stabilized at 380 mg/L at 82% recovery in 0.2M NaHCO3 solution. It was observed that silica polymerization firstly occurred at the hot brine outlet (cold distillate inlet) where the maximum temperature difference existed across the membrane. Silica polymerization on membrane surface subsequently led to rapid flux decline and membrane wetting. MD has the ability to recover a significant amount of water from RO brines. In seawater RO brine application, periodic flushing is required to remove inorganic salt nuclei from the membrane surface to prevent rapid formation of salt crystallization under supersaturated environment. However, organic fouling could be a problem when operating at conditions that do not lead to salt precipitations. In CSG RO brine application, CaCO3 and magnesium silicate will form in MD process at higher recovery. Efforts need to be made to avoid the formation of polymerised silica as it will cause irreversible membrane wetting.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

PO ZHANG Process engineer at Osmoflo Water Management Pty Ltd, Adelaide, South Australia, Australia PhD candidate at Victoria University, Melbourne, Victoria, Austrlaia Phone: +61 8 8282 9700 E-mail: [email protected] 2009-present

Process engineer at Osmoflo

2007-2009 Project engineer at Grampians Wimmera Mallee Water (GWMWater) Research interests: membrane distillation, membrane desalination and brine minimization.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.4 DARRELL ALEC PATTERSON ZN(TBIP)-PDMS: A NOVEL MOF MIXED MATRIX MEMBRANE FOR ENHANCED SEPARATION OF BIOBUTANOL

MARIA WEBER1,2, CHRIS DAVEY1,3, TINA DÜREN1,3,4, ANDREW BURROWS1,2, DAVID LEAK1,5 AND DARRELL ALEC PATTERSON1,3,4 1 Centre for Sustainable Chemical Technologies, University of Bath, UK 2 Department of Chemistry, University of Bath, UK 3 Department of Chemical Engineering, University of Bath, UK 4 Centre for Advanced Separations Engineering, University of Bath, UK 5 Department of Biology & Biochemistry, University of Bath, UK

Figure 1. Generation of commodity chemicals from a renewable feedstock through fermentation processes (from 1).

A shortage of petrochemical resources is an increasingly pressing issue in today’s energy and synthetic product hungry world. Capturing waste gases, which are then transformed through microorganisms in fermentation broths into commodity chemicals is one possible, more environmentally sustainable route (Fig. 1). However, one of the current limitations to lowering the carbon footprint of these processes is that energy intensive distillations are used for the recovery of these commodity chemicals, including the molecule of interest in this work - butanol. Pervaporative membrane separations are a potential replacement or supplementary process which could help reduce energy use, with mixed matrix membranes (MMMs) leading the

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION development of more highly selective and lower energy intensive developments. In this work, novel MMMs combining Zn(tbip) (tbip = 5-tert-butyl isophthalic acid) at different loadings (0, 3.33, 6.66 and 10 wt%) into polydimethylsiloxane (PDMS) have for the first time been successfully synthesised and evaluated for butanol pervaporation. The component and combined materials were characterised using XRD (Fig. 2), SEM, FTIR, contact angle measurements and TGA. The materials characterisations of the MMMs showed that Zn(tbip) was incorporated well into the PDMS matrix, allowing sufficient dispersion throughout. The resulting MMMs were hydrophobic, indicating their suitability for the separation of dilute organics such as butanol from water.

Figure 2. XRD patterns confirming increased loading with wt% of Zn(tbip) in PDMS.

Swelling tests using both water and butanol were conducted to determine the preferential uptake of each molecule in the membranes, examining the effect of Zn(tbip) wt%. Results (Fig. 3) indicate that there is a high adsorption of butanol and negligible adsorption of water, with an optimal at 3.33 wt% Zn(tbip) loading. These results show that these membranes have the potential for separation of butanol and water. Therefore a water-butanol system was used as a model fermentation broth to obtain first insights into the performance of these materials. Compared to PDMS membranes, it was demonstrated that addition of Zn(tbip) increased butanol fluxes and separation factors. Within the different wt% studied, 3.33 wt% Zn(tbip)-PDMS had the highest butanol flux and separation factor of 0.025 kg/m2h and 38 respectively (Fig. 4), agreeing with the swelling test results. This optimal low MOF loading is thought to be due to a combination of increased MOF selectivity over PDMS, as well as favourable polymer chain packing and lower defects at this lower MOF loading.

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Figure 3. Degree of swelling with butanol and water showing the effect of increased

Figure 4. Average total flux and separation factor for the Zn(tbip)-PDMS membranes showing the effect of Zn(tbip) loading.

These results indicate that Zn(tbip)-PDMS MMMs are promising materials for organophilic (or hydrophobic) pervaporative separation of butanol which warrant further more detailed optimisation and characterisation in order to fully determine their applicability to biobutanol production.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION REFERENCES 1

C. Davey, D. Leak and D. Patterson, Membranes (Basel)., 2016, 6, 17.

DR DARRELL ALEC PATTERSON Title: Director of the Centre for Advanced Separations Engineering University of Bath, United Kingdom Phone: +44(0)1225284468 E-mail: [email protected] Since 2015

ERC Consolidator Fellow and Director of the Centre for Advanced Separations Engineering, University of Bath

2011-2015

Senior Lecturer in Chemical Engineering, University of Bath

2005-2011

Lecturer then Senior Lecturer, University of Auckland

2003-2005

Postdoctoral Research Associate, Imperial College London

2001-2003

Technology Development Consultant, Atkins Water, UK.

Research interests: Nanofiltration, pervaporation and mixed matrix membranes; catalytic membrane reactors; immortal membranes; externally electrically tuneable membranes; process intensification.

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W4.5 ABSTRACT TO COME

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.6 GUANGXI DONG OPEN-SOURCE PREDICTIVE SIMULATORS FOR SCALE-UP OF DIRECT CONTACT MEMBRANE DISTILLATION MODULES FOR SEAWATER DESALINATION

GUANGXI DONG1, 2, JEONG F. KIM2, ENRICO DRIOLI2,3, YOUNG MOO LEE2, VICKI CHEN1 1 UNESCO Centre for Membrane Science and Technology, the University of New South Wales, Sydney, Australia 2 Department of Energy Engineering, College of Engineering, Hanyang University, South Korea 3 Institute on Membrane Technology (ITM–CNR), University of Calabria, Cosenza, Italy For many years, university research activities have been criticised for lack of real understanding of industrial needs. This is no exception for membrane research. For instance, many industrial processes rely on the use of filter-like membranes to achieve separation. Response to this industry thirst for better membrane techniques, research efforts have been dedicated to material chemistry for developing highly permeable membranes, neglecting a simple fact that membrane separation processes rely on chemical potential gradient as the mass transfer driving force, which can quickly diminish for highly permeable membranes with large membrane area. Growing number of industrial data show that for certain membrane-related separation processes, no matter how permeable a “good” membrane can achieve in lab-scale (membrane area of few cm2) , when scaled-up to industrial-size, these supposedly “good” membranes exhibit performance only marginally better than conventional membranes. These industrial evidences clearly highlight the importance of an appropriate membrane scale-up strategies, which to a certain extent, may determine the fate of a newly developed membrane in industrial-scale implementation. In this study, two open-source simulators (flat sheet and hollow fibre membranes) were developed on Matlab GUI platform to aid direct contact membrane distillation (DCMD) module scale-up. A “black box” coupled with finite-difference method (FDM) was proposed not only to offer a reasonably accurate prediction, but also to reveal the profiles of key variables as a function of module length. Using laboratory-scale experimental results in one configuration as simulation input, the developed simulators were able to predict large-scale DCMD module performance in several commonly used configurations. These two Matlab-based simulators exhibited good accuracy, comparable with the computational fluid dynamic (CFD) simulation, but with lower computational demand. Design considerations for an appropriate module scale-up for DCMD process were demonstrated using these simulators, and key industrial-scale module design criteria were GOLD SPONSOR

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION identified and evaluated. The results presented in this study offered practical guidance for a proper module scale-up strategy to deliver optimal pure water productivity for industrialscale seawater desalination using DCMD process. More importantly, these simulators are open-source, so that membrane researchers can utilise them to develop specific scale-up strategies for their own DCMD membrane modules and therefore help them to move closer to commercialisation. Further, these simulators were built upon Matlab GUI platform to enable the generation of a user-friendly graphical interface (Figure 1), so that membrane researchers with no or limited programming knowledge can still easily use these simulators for their own research purposes without the need of learning Matlab programming knowledge.

Figure 1. Interface of the developed hollow fibre simulator for DCMD module scale-up

GUANGXI DONG Research Fellow UNESCO Centre for Membrane Science and Technology, the University of New South Wales, Sydney, Australia Phone: (+61 2) 9385 6092 Fax: (+61 2) 9385 5966 E-mail: [email protected] 2011-2014

Research associate, University of New South Wales, Sydney, Australia

2014-2016

Research fellow, Hanyang University, South Korea

Research interests: membrane gas separation, membrane module and process design, Matlab programming

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.7 JULIA PLATTNER TREATMENT OF BRACKISH GROUNDWATER CONTAINING FLUORIDE AND PESTICIDES WITH DIRECT CONTACT MEMBRANE DISTILLATION (DCMD)

JULIA PLATTNER1, DR. GAYATRHI NAIDU1, PROF. THOMAS WINTGENS2, DR. CHRISTIAN KAZNER2, PROF. SARAVANAMUTHU VIGNESWARAN1 1 University Of Technology Sydney 2 University of Applied Sciences and Arts Northwestern Switzerland, School of Life Sciences SUMMARY

Direct Contact Membrane Distillation (DCMD) is tested for off-grid drinking water production from brackish groundwater in the Indian context. This study investigates the fate and rejection of pesticides with high relevance regarding their application and public health as well as the scaling potential of fluoride in brackish groundwater. INTRODUCTION

The intensive use of pesticides has led to widespread contamination of water sources in India [1, 2]. Also fluoride, a geogenic contaminant in groundwater, is found in high concentrations in many parts of India [3]. Simultaneously many coastal aquifers and several inland groundwater bodies suffer from increasing salinity due to over-abstraction or saltwater intrusion. In rural and peri-urban areas where groundwater is the main source for drinking water production, these issues are of particular concern. Membrane Distillation (MD) is an emerging technology for desalination with advantages in off-grid application where low grade heat, e.g. from diesel generators, is available. While some studies have started to investigate the fate and rejection of trace organic compounds including some pesticides in MD [4, 5], the simultaneous removal of salt, fluoride and pesticides from brackish groundwater has not been studied so far. Also, the prominent pesticides applied in India have not been studied yet as well as the long-term behaviour of polar and nonpolar pesticides once the sorption equilibrium has been reached. Furthermore, in the presence of calcium and fluoride the formation of the scalant fluorite (CaF2) is expected due to low solubility (3.9 x 10-5 mol3/L3 at 25°C). Detailed scaling studies with regards to fluorite have not been reported so far. The present study aims to address these questions. MATERIAL AND METHODS

In this study a model brackish groundwater solution was used containing 5 mg/L fluoride, 3 g/L of NaCl, 150 mg/L Ca2+, 150 mg/L Mg2+, 100 mg/L SO42-, 10 mg/L humic acid resembling typical brackish groundwater composition in rural India. Pesticides were selected to cover a range of relevant chemical properties, e.g. GOLD SPONSOR

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION hydrophobicity (LogD) and vapour pressure alongside criteria such as occurrence, persistence and toxicity (Table 1). The model solutions were spiked with 200 µg/L of each pesticide for the fate experiments. Phorate, parathion methyl and dichlorvos are amongst the most frequently used pesticides in India [6]. Table 1 Physiochemical properties of the selected compounds (data from Scifinder)

LogD at pH 7

Vapour pressure at 25ºC [mmHg]

Water solubility at pH 7, 25ºC [mg/L]

Molecular weight [g/Mol]

Phorate

3.67

2.60 x 10-3

50

260.38

Parathion Methyl

2.82

2.4 x 10-4

37

263.21

Atrazine

2.64

1.27 x 10-5

69

215.68

Dichlorvos

1.07

1.45

57’000

220.98

Clofibric Acid

-1.06

1.03 x 10-4

100’000

214.65

The studies are conducted at bench-scale using a DCMD unit as described by Naidu et al. [7] using a hydrophobic PTFE flat sheet membrane (GE, US) with a feed temperature of 55 °C and a cooling temperature of 25 °C at a feed flow of 0.8 L/min and a volume concentration factor (VCF) of 4. Scaling was assessed by contact angle measurement and mass balance and supported by PHREEQC simulations using various temperatures and pH values. RESULTS AND CONCLUSION

Membrane Distillation proved to be well applicable for the treatment of the model brackish groundwater with minor to moderate scaling potential providing a high quality distillate compliant with the standards of the Indian Drinking Water Guidelines (BIS, 2012). Based on the results it can be concluded that the presence of NaCl is the dominant factor influencing the MD flux. At the applied operating conditions and low feed concentration levels, fluoride (5 mg/L) did not play a significant role in influencing the MD flux trend. The scaling potential of fluorite was simulated at different temperatures (Figure 1). A higher feed temperature (70°C), associated with a higher solubility of CaF2, did not show a significant change in the saturation index and therefore also to the scaling potential. At a feed temperature of 30°C, calcium fluoride would precipitate immediately. After 3 experiments up to VCF 4 the membrane hydrophobicity was slightly reduced to 86%, compared to the virgin membrane. The hydrophobicity could be restored to 90% by flushing with ultrapure water and to 92% by flushing with a 0.1 M NaOH solution.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

Figure 1 PHREEQC simulation of the SI of CaF2 in model groundwater (composition s.a.)

With regards to the pesticide rejection, it can be said that pesticides with low LogD are well retained at rates above 95% (Figure 2). Phorate representing a very hydrophobic substance was retained only at around 40%. Dichlorvos, which represented substances with high vapour pressure, had a lower rejection rate ranging from 0 to 67%.

Figure 2 Rejection of selected pesticides in different feed solutio

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION REFERENCES 1

Yadav, I. C., Devi, N. L., Syed, J. H., Cheng, Z., Li, J., Zhang, G., Jones, K. C., Sci. Tot. Env., 2015, 511: p.123-137

2

Skiwar, S., Kavitag, G., Kanchan, S., Kashyap., S. M., Shoeb, K., Neeta, T., J. of Env. Sci. Eng., 2014, 56 (2): p. 157-164

3

Jagtap, S., Yenkie, M. K., Labhsetwar, N., Rayalu, S., Chem. Rev., 2012, 112 (4), p: 2454-2466

4

Wijekoon, K. C., Hai, F., Kang, J., Price, W. E., Cath, T. Y., Nghiem, L. D, J. of Memb. Sci., 2014, 453: p 636-642

5

Wijekoon, K., C., Hai, F., Kang, J., Price, W. E., Guo, W., Ngo, H. H, Cath, T. Y., Nghiem, L. D, Biores. Tech., 2014, 159: p. 334-341

6

Bhushan, C. A., Bhardwaj, A., Misra, S. S., Publication of the Centre for Science and Environment, New Delhi, 2013

7

Naidu, G., Joeng, S., Kim, S. J., Kim, I. S., Vigneswaran, S., Desalination, 2014, 347: p. 230-239

JULIA PLATTNER Title: Master of Engineering (expected graduation December 2016) University of Applied Sciences and Arts Northwestern Switzerland Phone: +416114674769 E-mail: [email protected] Since 2015

Master Student at University of Technology Sydney

2012-2015

Research Assistant at University of Applied Sciences and Arts Northwestern

2012

BSc graduation

Research interests: Drinking water and waste water technologies, advanced treatment processes (Adsorption, Membrane processes, Oxidation) and natural water treatment (Managed Aquifer Recharge, River Bank Filtration and Soil Aquifer treatment).

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.8 ZONGLI XIE SCALE FORMATION OF CALCIUM PHOSPHATE IN DIRECT CONTACT MEMBRANE DISTILLATION

ZONGLI XIE1,*, WENLI QIN1,2, DERRICK NG1, JIANHUA ZHANG3, STEPHEN GRAY3, XIAOSHENG JI2, YING YE 2 1 CSIRO Manufacturing, private bag 10, Clayton South, VIC 3169, Australia 2 Institute of Marine Geology and Resource, Zhejiang University, Zhejiang 316021, China 3 Institute for Sustainability and Innovation, Victoria University, Melbourne, VIC 8001, Australia Membrane distillation (MD) is one of the emerging desalination technologies which based on thermally-driven transport of water molecules through microporous hydrophobic membranes. Long-term stable performance is an important aspect to consider for the industrial implementation of MD which is often affected by membrane fouling and wetting. Several factors such as poor long term hydrophobicity of thematerial, membrane damage and the presence of inorganic, colloidal and particulate matters, organic macromolecules and microorganisms in the feed water could lead to fouling deposition and pore wetting, which can lower the salt rejection and deter the MD performance 1,2. Among various inorganic foulants, calcium phosphate scaling is a common problem in wastewater treatment 3. Its potential to scale in MD could be possibly related to the use of phosphate antiscalants, wherein improper dosage of antiscalants at their hydrolysis condition could make them as foulants themselves. Despite many studies on MD fouling, there is no report on scaling by calcium phosphate. We examined the scaling of calcium phosphate in a direct contact MD system. The experiments were performed with PTFE flat sheet membranes with an average pore size of 0.45 µm. Membrane fouling profile was quantified by reduction in the water flux. The morphology and composition of the fouling layer were studied using Fourier transform infrared and scanning electron microscopy coupled with the energy dispersing spectrometry. Results indicate that calcium phosphate scaling is more likely to occur on the membrane surface. The scaling mechanism of calcium phosphate in MD has been discussed based on the surface heterogeneous and bulk homogeneous crystallization mechanisms. Effect of concentration, feed velocity, temperature and pH has also been studied. pH is an important parameter which affects the transformation of calcium phosphate from amorphous to crystalline form. Surface crystallisation is more dominant at higher temperature, as demonstrated by sharp decrease of water flux and increase of permeate conductivity (Fig. 1).

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Figure 1: Effect of temperature on the water flux and permeate conductivity. REFERENCES: 1 M. Gryta, Fouling in direct contact membrane distillation process, J. of Mem. Sci, 2008, 325, 383-394. 2 L.D. Tijing, Y.C. Woo, J.-S. Choi, S. Lee, S.-H. Kim, H.K. Shon, Fouling and its control in membrane distillation—A review, J. of Mem. Sci, 2015, 475, 215-244. 3 A. Antony, J.H. Low, S. Gray, A.E. Childress, P. Le-Clech, G. Leslie, Scale formation and control in high pressure membrane water treatment systems: A review, J. of Mem. Sci, 2011, 383, 1-16.

DR ZONGLI XIE Senior Research Scientist / Research Team Leader CSIRO Manufacturing, Australia Phone: +61 3 9545 2938 Fax: +61 39544 1128 E-mail: [email protected] Research interests: membrane distillation, pervaporation, hybrid organicinorganic membranes, environmental catalysis for industrial emission control.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.9 XIAO CHEN THIN FILM FORMATION FROM AEROSOL ASSISTED PLASMA DEPOSITION FOR SOLVENT SEPARATION APPLICATION

XIAO CHEN1*, ZHIQIANG CHEN1, CHIARA LO PORTO2, RICCARDO D’AGOSTINO3, KEVIN MAGNIEZ1, XIUJUAN J. DAI1, FABIO PALUMBO3, AND LUDOVIC F. DUMÉE1 1 Deakin University, Institute for Frontier Materials, Waurn Ponds 3216, VIC, Australia 2 Department of Chemistry, University of Bari, via E. Orabona 4, 70126 Bari, Italy 3 Institute of Nanotechnology, CNR, via E. Orabona 4, 70126 Bari, Italy Polyhedral oligomeric silsesquioxane (POSS) are silicon based materials nano-cages containing flexible functional groups which may be used to form highly crystalline, 3 – dimensional building blocks towards nano-composite materials design, including membrane materials1. The control of agglomeration and homogeneous incorporation across the matrixes of such nano-materials are however challenging, and novel strategies are required2. POSS composite membranes were shown to provide improved thermal and mechanical properties and offer increased free volume and degree of cross-linking by covalently bonding the POSS nano-cages with the matrix backbone3-6. These variations may be used to alter the performance of membranes and control both permeation and selectivity to the sub-nanoscale which towards the next generation of dense gas or vapour separation materials. Hence in this project, POSS nano-powders have been functionalized to alter the performance of hydrophobic membranes by modifying the matrix-particle interface. The solvent separation performance by pervaporation were investigated and related to the degree interactions and the overall free volume of the material. In order to achieve better incorporation of nano-particles and polymer matrix different from physical blending and solvent casting methods, plasma polymerization of the functionalized POSS nano-cages with a monomer may be used as a route to generate composite membranes in a single step. In order to produce such composite films aerosol assisted plasma deposition, developed by the University of Bari (Italy)7, 8, was used to deposit in atmospheric conditions a composite of POSS and a hexamethyldisiloxane (HMDSO) based matrix with He gas as carrier gas. This approach offers a great control over synergistic interactions between nano-particles and the reinforcing materials, while also allowing for the realization of ultra-thin materials. In this work, the incorporation of polymer matrix and POSS particle deposited from HMDSO monomer and octamethyl-POSS nano-powder aerosols was studied and the novel nano-composite films characterized. A poly(sulfone) (PSF) supporting membrane was used GOLD SPONSOR

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION to deposit the composite layers from a 0.01 vol.% aerosol. The micrographs shown in Fig. 1 demonstrates that the roughness of the PSF membrane support was reduced upon the thin film formation, and the uniform distribution of the POSS particle in the film on silicon wafer also has been presented. This approach affected the surfaces wettability as measured by the water contact angle by POSS addition. In particular, at low POSS concentration a small increase of water contact angle is found, with respect to plasma deposited HMDSO, but further addition of POSS results in a decrease of water contact angle. The interface between the nano-particles and the polymer matrix can be controlled to affect the free volume distribution between the macromolecular chains which can be characterized by PALS. FTIR and XPS results highlight that coatings containing POSS present similar bands and peaks feature the ones deposited from pure HMDSO, indicating that the bonding structure is not largely different upon POSS particle addition. Particularly, in this presentation, the influence of the aerosol concentration and resulting film thickness will be discussed in order to correlate to the performance of the TFC membranes for separation of ethanol-water mixtures by pervaporation. Hence, it is believed that plasma polymerization method for membrane fabrication provide an effective way to produce homogenous ultra-thin film in order to compete with separation performance of common membranes.

Figure 1. SEM images for the plasma deposited thin film on PSF membrane and silicon wafer. (a) untreated PSF membrane, (b) 0.01 vol.% POSS in HMDSO deposited thin film on PSF membrane, (c) 0.01 vol.% POSS in HMDSO deposited thin film on silicon wafer, (d) 0.01 vol.% POSS in HMDSO deposited thin film on silicon wafer with a higher magnification.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION REFERENCES 1 In Applications of Polyhedral Oligomeric Silsesquioxanes, ed. C. HartmannThompson, Springer, Dordrecht, 2011, vol. 3, pp. 1-420. 2 P. Shao and R. Y. M. Huang, J. Membr. Sci., 2007, 287, 162-179. 3 Y. Li and T. S. Chung, Int J Hydrogen Energy, 2010, 35, 10560-10568. 4 N. L. Le, Y. Wang and T. S. Chung, J. Membr. Sci., 2011, 379, 174-183. 5 R. Konietzny, T. Koschine, K. Rätzke and C. Staudt, Sep. Purif. Technol., 2014, 123, 172-183. 6 J. Duan, E. Litwiller and I. Pinnau, J. Membr. Sci., 2015, 473, 157-164. 7 F. Fanelli, A. M. Mastrangelo and F. Fracassi, Langmuir, 2014, 30, 857-865. 8 F. Palumbo, G. Camporeale, Y.-W. Yang, J.-S. Wu, E. Sardella, G. Dilecce, C. D. Calvano, L. Quintieri, L. Caputo, F. Baruzzi and P. Favia, Plasma Processes and Polymers, 2015, 12, 1302-1310.

XIAO CHEN Title: Mr Institute for Frontier Materials, Deakin University, Waurn Ponds 3216, VIC, Australia: Phone: +61430125137 E-mail: [email protected] Personal History: 2010-2013

Bachelor of Engineering, Monash University

Since 2014

PhD, Institute for Frontier Materials, Deakin University

Research interests: membrane fabrication, membrane characterization, membrane application, plasma technique

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.16 ALESSIO CARAVELLA MODELLING OF PERMEATION BLOCKING EFFECT BY ADSORBED GASES IN ZEOLITE MEMBRANES

ALESSIO CARAVELLA1, 2, PASQUALE F. ZITO1,2, ADELE BRUNETTI2, ENRICO DRIOLI1,2, GIUSEPPE BARBIERI2 1 University of Calabria, Department of Environmental and Chemical Engineering (DIATIC),Via P. Bucci, Cubo 44A, Rende (CS), 87036, ITALY 2 National Research Council of Italy, Institute on Membrane Technology (ITM-CNR),Via P. Bucci, Cubo 17C, Rende (CS), 87036, ITALY MAIN TOPIC

In this work, a novel modelling approach is used to describe the multicomponent permeation of gas mixture through zeolite membranes. More specifically, the novelty of this study consists in accounting for steric interactions between Knudsen and surface diffusion, which are the main mass transport mechanisms occurring in microporous media like zeolites. MOTIVATION

In the literature, Knudsen and surface diffusion are considered to occur fully in parallel with each other1, which implies no interactions between them. However, in microporous and nanoporous structures, the pore size is actually of the same order of magnitude as the molecule one and, thus, the molecules adsorbed on the pore walls act like obstacles and can even cause a complete obstruction impeding in fact the Knudsen diffusion. MODELLING APPROACH

To take into account such a blocking effect and perform this investigation, the nominal geometrical parameters determining the permeation process – i.e., pore diameter, porosity and tortuosity – are corrected by developing appropriate functions of both adsorption loading and molecules size2. The so-corrected geometrical parameters are here referred to as effective porosity, effective pore size and effective tortuosity to distinguish them from the zero-loading conditions (i.e., the nominal values). For this analysis, a multicomponent approach is used, in the sense that all the adsorbed species contribute with their own loading and volume to obstruct the Knudsen diffusion. The main hypothesis behind is that the surface diffusion affects the Knudsen one but is not affected by it. As for the surface diffusion modelling, the expressions developed by Krishna using a Maxwell-Stefan approach are used3. Our model is generally trained through some literature datasets in single-gas conditions to obtain the necessary parameters, whereas

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION the simulation results are validated in mixture conditions using other literature data expressed in terms of permeance obtained from a number of different sources. -6

Permeance, mol m-2 Pa-1 s-1

10

CO2

) Single gas

-7

)

Surface diffusion

Surface diffusion

10

CH4

Single gas

Effective Knudsen

Effective Knudsen

-8

10

200

300

400

Temperature, K

500

200

300

400

500

Temperature, K

Fig.1. Single-gas behaviour of methane and carbon dioxide including the blocking effect MAIN RESULTS AND DISCUSSION

Fig.1 shows an example of simulation performed in single gas conditions for both CH4 and CO2. The corresponding experimental data are taken from van den Broeke et al. (1999)4. To this regards, it must be underlined that, in this case, the comparison with experimental data represents a validation for our model, since the data used for model training are taken from a different source5. Considering the CH4 trend, adsorption is relatively stronger at low temperature and, thus, the surface diffusion is dominant over the Knudsen one. In fact, the large amount of adsorbed molecules causes a reduction of the available void space in the channel, obstructing the movement of the molecules in the bulk (i.e., the Knudsen diffusion). As a results, the surface diffusion is in practice the only diffusional mechanism up to around 350 K. Above this temperature, the species adsorption becomes relatively weak and, thus, the pore channel area is poorly occupied by molecules. As a result, the effective Knudsen mechanism starts being progressively more significant and the dependence of permeance on temperature becomes weaker and weaker. The same qualitative trend is found for CO2, with the difference that in this case the characteristic maximum in the surface diffusion curve is observed to be placed at higher temperature (around 300 K). This is caused by the fact that CO2 adsorbs more strongly on the pore surface, determining the surface diffusion to be dominant with a wider temperature range with respect to the one observed for methane. GOLD SPONSOR

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION The blocking effect can be directly visualised in the plot by looking at the difference between the surface diffusion trend (green dashed-lines) and the Knudsen diffusion one (black dashed-lines): the larger such a difference, the stronger the blocking effect, as observed for the drop of the Knudsen diffusion contribution at low temperature. In this sense, the present model is able to predict quantitatively the fractional contributions of the two diffusion mechanisms considered, preventing one from distinguishing arbitrarily those geometry zones of porous media controlled by the Knudsen diffusion from those ones controlled by the surface one. CONCLUSIONS

A novel modelling approach describing the multicomponent diffusion in microporous zeolite membranes was developed. In particular, both Knudsen and surface diffusion were considered to interact, with the former being partially or fully obstructed by the latter. It was demonstrated that such a model successfully reproduce the experimental trends considered for validation in a wide temperature range (200-450 K), representing an effective tool for engineers and material scientists to predict the zeolite membrane performance (permeability and selectivity) in real conditions of gas mixture. ACKNOWLEDGEMENTS

A. Caravella gratefully acknowledges the “Programma Per Giovani Ricercatori “Rita Levi Montalcini”” granted by the “Ministero dell’Istruzione, dell’Università e della Ricerca, MIUR” for funding this research. REFERENCES 1

D.D. Do, Adsorption Analysis: Equilibria and Kinetics, Imperial College Press, 1998.

2 A. Caravella et al., Micropor. Mesopor. Mat., 2016, submitted. 3 R. Krishna, Chem. Eng. Sci., 1990, 45, 1779-91. 4 L.J.P. van den Broeke et al., AIChE J., 1999, 45, 976-85. 5 C. Algieri et al., J. Membr. Sci., 2003, 222, 181-90.

ALESSIO CARAVELLA Title: Professor University of Calabria, Italy Phone: +39.0984.49.4481; Fax: +39.0984.49.6655 E-mail: [email protected] 2014-Present

Assistant Professor

2013-2014

Visiting Researcher

2009-2013

Post-doc Research Scientist / Fellow

2005-2009

Ph.D. Student, Junior Fellow

Research interests: Membrane Technology for Hydrogen Purification, Transport in Porous Media, Modelling and Simulation of Chemical Processes, Chemical Reactors Design and Development

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W4.17 HELEN JULIAN NUMERICAL STUDY ON THE TEMPERATURE POLARIZATION, CONCENTRATION POLARIZATION AND CACO3 FOULING RATE IN SUBMERGED VACUUM MEMBRANE DISTILLATION AND CRYSTALLIZATION (VMDC)

HELEN JULIAN1, BOYUE LIAN1, YUAN WANG1, GREG LESLIE1, VICKI CHEN 1 1 UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, University of New South Wales, Sydney NSW 2052, Australia The efficiency of membrane distillation (MD) is limited by temperature polarization and concentration polarization, which reduce temperature and increase concentration on feed surface, thus reducing vapour flux. In addition, temperature and concentration polarization may induce faster deposition of salts on the surface and within the pores of the membrane which reduces water vapor transport, and promotes wetting1. Minimizing temperature polarization and concentration in MD is the subject of much research and several studies have attempted to understand the relationship between operation parameters and module design on this phenomena2,3. In some studies, Computational Fluid Dynamic (CFD) has been used to describe local heat and mass transfer in membrane distillation. Simulations showed that the increase in feed velocity and reduction in feed temperature lead to less severe temperature polarization4,5, however, these studies ignored the influence of polarization on inorganic fouling on water vapor transport. Inorganic fouling by CaCO3 is of concern in the operation of both MD and heat exchangers. Due to the difficulty of direct measurement, most studies of heat exchangers assume that the CaCO3 concentration on the interface is equal to the bulk concentration6. However, when Pääkkönen and others integrated CFD modelling with the CaCO3 deposition rate calculation in heat exhanger, they found that the deposition rate estimated for CaCO3 bulk concentration was higher than experimental observation. When the interfacial CaCO3 concentration was adjusted for concentration polarization the model showed good agreement with the experimental results, especially at lower Reynold number7. The approach of Pääkkönen has been adapted in this study to predict the CaCO3 fouling mechanism on the membrane surface in vacuum membrane distillation process. In this study, membrane flux, temperature polarization, concentration polarization and CaCO3 deposition rate on the membrane surface were observed at various feed concentration and their effects on vacuum membrane distillation performance were examined. Submerged configuration, in which the membrane module is put inside the feed solution, was chosen to provide more uniform feed temperature and avoid heat loss due to feed recirculation in conventional configuration.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION Numerical simulations were conducted using ANSYS-FLUENT 16.2. For simplification, the simulations were performed at steady state and all fluids were assumed to be incompressible the. The geometry of one fiber submerged VMDC system was created in 2D to minimize simulation time due to the uniformity of temperature profile and mass flux in the radial direction of the fiber. Three surfaces are made to represent feed, membrane and permeate side. The geometry size of membrane side surface is 0.45 mm x 70 mm, feed side surface is 3 mm x 70 mm and permeate side surface is 0.9 x 70 mm. The width of membrane side surface is equal to membrane thickness. The feed solution was representative on reject from reverse osmosis systems operating on saline groundwater with a TDS of 10.93 g/L.Experimental validation of the CFD model was based on data from a submerged VMDC system operating without agitation. The details of system can be found elsewhere8. Simulated results were in good agreement with the experimental data with 4-11% deviation (Fig.1). Temperature polarization coefficient (TPC) was calculated based on the feed temperature data at membrane surface from the modelling and the values were approximately in the range of 0.34-0.38. The TPC for submerged VMDC was low compared to other MD configuration due to the lack of fluid movement, which results on relatively thick stagnant film at the membrane surface.

Figure 1. Flux comparison from experiments and simulations - validation

Using pure water as the feed solution, drastic temperature reduction was calculated at the feed solution adjacent to membrane surface; approximately 150 µm from the membrane surface (Fig.2(a)). The effect of varied vacuum pressure was also studied and the TPC decrease as the vacuum pressure decrease. Similar drastic reduction in temperature on feed-membrane interface was also observed as the vacuum pressure increase (Fig.2(b)).

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION (a)

(b)

Figure 2. Temperature profile of the feed solution adjacent to the membrane at (a) various feed temperature and (b) various vacuum pressure

With model inland brine (MIB) as the feed (TDS = 10.93 g/L), the flux was slightly decreased (by 0.6%) compared to the pure water feed due to concentration polarization. When the feed concentration was doubled and tripled, the flux only decreased by 2.9% and 5.3%, respectively. The TPC and concentration polarization coefficient (CPC) for CaCO3 were also showed similar trends without significant effect from the feed concentration. The result indicated the lesser effect of concentration polarization to the submerged VMDC compared to the temperature polarization. At varied MIB feed temperatures, the temperature profile was similar with pure water feed (Figure 1(a)), however, the temperature on the membrane wall was 3 oC higher when MIB was used as the feed. The CPC for CaCO3 at various feed temperature also increase as the feed position closer to the membrane wall due to the rapid water vapor loss. Future work will investigate the mechanism and rate of the CaCO3 fouling rate based on the CaCO3 concentration on the membrane surface.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION REFERENCES 1 M. Gryta, Separation science and technology.. 2002, 37(15), 3535-3558 2 L. Martinez-Diaz, M.I. Vazquez-Gonzalez, Journal of Membrane Science. 1999, 156(2), 265-273 3 J. Phattaranawik, R. Jiraratananon, A. Fane, Journal of Membrane Science. 2003, 217(1), 193-206 4 M. Shakaib, et al, Desalination. 2013, 51(16-18), 3662-3674 5 A.S. Alsaadi, et al, Journal of Membrane Science. 2014, 471, 138-148 6 M. Mwaba, M.R. Golriz, J. Gu, Applied thermal engineering. 2006, 26(4), 440-447 7 T. Pääkkönen, et al, International Journal of Heat and Mass Transfer. 2016, 97, 618-630 8 S. Meng, et al, Desalination, 2015, 361, 72-80

HELEN JULIAN Title: Miss Affiliation, Country: University of New South Wales, Australia Phone: + 61 456 172 171 E-mail: [email protected] 2010

B.Sc in Chemical Engineering, Institute of Technology Bandung, Indonesia

2012

M.Sc in Chemical Engineering, Institute of Technology Bandung, Indonesia

2013

PhD candidate University of New South Wales, Australia

Research interests: membrane contactor, membrane distillation and membrane for gas separation

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION

W4.18 HUNG C. DUONG OPTIMISING MEMBRANE DISTILLATION FOR SMALL-SCALE SEAWATER DESALINATION

HUNG C. DUONG AND LONG D. NGHIEM Strategic Water Infrastructure Laboratory, School of Civil, Mining and Environmental Engineering, University of Wollongong, Wollongong, Australia Membrane distillation (MD) embodies notable attributes that render it the most promising process for small-scale seawater desalination to augment fresh water supply in remote coastal areas. Using a microporous hydrophobic membrane as a barrier against the liquid water, and thus all dissolved salts and non-volatile substances, MD can produce ultrapure distillate directly from seawater. In addition, unlike other pressure-driven membrane filtration processes such as reverse osmosis (RO), MD utilises a water vapour pressure gradient induced by a temperature difference across the membrane as the driving force for water transfer. Therefore, water flux in MD is much less affected by the osmotic pressure and the concentration of its feed water. MD is also less susceptible to membrane fouling than RO. Thus, seawater MD desalination can be operated at higher process water recoveries while requiring significantly less feed water pre-treatment compared to RO. More importantly, given its low operating hydraulic pressure, MD systems can be made of inexpensive and noncorrosive plastic materials, leading to a remarkable reduction in investment and operation costs. Finally, the optimal operating temperature of MD processes is in the range from 40 to 80 °C; thus, low-grade primary energy sources such as waste heat and solar thermal energy can be utilised to meet MD energy demands. Key technical challenges that have restricted the full realisation of MD for small-scale seawater desalination applications are intensive energy consumption and membrane scaling. As a thermal distillation process, MD requires huge amounts of heating and cooling for liquid-vapour phase conversion. Thus, the energy consumption of MD processes reported in the literature is several orders of magnitudes higher than that of a state-of-theart RO for seawater desalination application. In addition, seawater MD desalination processes reportedly encounter membrane scaling caused by the precipitation of sparingly soluble minerals associated with the desire for a high process water recovery. The scale formation on the membrane aggravates temperature polarisation effects, reduces water vapour pressure at the membrane surface, and causes pore blockage and liquid intrusion to the pores. These negative consequences lead to a decline in water flux and distillate quality, and an inevitable increase in energy consumption of the MD process. Among four basic configurations of MD, direct contact membrane distillation (DCMD) exhibits the simplest process arrangement, and thus is deemed the best suited for smallscale seawater desalination. However, DCMD also demonstrates the lowest process thermal efficiency compared to other configurations due to its simple arrangement. In addition, our heat and mass transfer calculation shows that a single-pass DCMD process GOLD SPONSOR

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION operated at the temperatures shown in Fig. 1A cannot achieve a water recovery above 10% regardless the length of the membrane channel. Given its capability to process at high feed salinity, seawater MD is desired to be operated at water recoveries considerably higher than those of RO (i.e. 50%). Thus, we investigated a simple but effective method, termed as brine recycling, to increase both the water recovery and thermal efficiency of a seawater DCMD process1. The influence of operating conditions, including feed salinity, feed temperature, and water circulation rates, on water flux, thermal efficiency, and membrane scaling during the seawater DCMD process with brine recycling was systematically elucidated.

Fig. 1. (A) Heat and mass transfer during a single-pass DCMD process, and (B) Schematic diagram of a DCMD process with brine recycling.

With brine recycling, the DCMD process could be operated at any desired water recovery by simultaneously feeding seawater into and bleeding out the brine from the feed tank (Fig. 1B). More importantly, the sensible heat of the hot brine could be recovered to enhance thermal efficiency of the DCMD process. Our experimental results demonstrated that there was an optimal water recovery range (i.e. from 20% to 60%) with respects to water flux, thermal efficiency, and membrane scaling for the DCMD process with brine recycling (Fig. 2). The DCMD process at water recoveries within this range could achieve a reasonable water flux and a maximum thermal efficiency (i.e. lowest specific thermal energy consumption and highest gained output ratio), while membrane scaling caused by the precipitation of sparingly soluble salts could be avoided. Indeed, no indications of membrane scaling was observed during the extended seawater DCMD process at water recovery of 60% and 70% (Fig. 3). Over increasing water recovery not only reduced both water flux and thermal efficiency of the process (Fig. 2), but also increased the risk of membrane scaling - severe membrane scaling was observed during the seawater DCMD process at the water recovery of 80%.

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Fig. 2. Water flux, specific thermal energy consumption (STEC), and gained output ratio (GOR) as functions of water recovery during a seawater DCMD process with brine recycling.

Fig. 3. Stable water flux, and constant feed and distillate electrical conductivity achieved during the seawater DCMD process with brine recycling at water recovery of 60% and 70%, feed temperature of 50 °C.

The scaling behaviour during seawater MD processes at high water recoveries also depends on operating temperatures. Given the long membrane channels of pilot and small-scale MD modules, the temperature of process streams can significantly vary along the membrane channels2. The significant variation of process stream temperatures might affect the distribution of water flux, membrane scaling, and the efficiency of subsequent membrane cleaning during small-scale MD processes of seawater. Recently, we have demonstrated that water flux and membrane scaling were unevenly distributed along the membrane channel during the MD process of seawater due to the variation in feed/ coolant temperature along the membrane channel3. The membrane areas at high temperatures could obtain higher water flux; however, they also encountered more severe membrane scaling compared to the ones at low temperature. Operating temperatures also affected the efficiency of the scaled membrane cleaning. Membrane cleaning with fresh water and vinegar (which is a domestic chemical) was more efficient for the membrane scaled at lower feed/coolant temperatures. The results obtained from this study have crucial implications for membrane module design and process optimisation for small-scale seawater MD desalination systems.

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THEME: PERVAPORATION VOPOUR SEPARATION AND MEMBRANE DISTILLATION REFERENCES 1 H.C. Duong, P. Cooper, B. Nelemans, and L.D. Nghiem, Desalination 2015, 374, 1-9. 2 H.C. Duong, P. Cooper, B. Nelemans, T.Y. Cath, and L.D. Nghiem, Sep. Purif. Technol. 2016, 166, 55-62. 3 H.C. Duong, M. Duke, S. Gray, P. Cooper and L.D. Nghiem, Desalination 2016, 397, 92-100.

HUNG C. DUONG University of Wollongong (UOW), Australia Phone: 0415743544 E-mail: [email protected]

440

2000-2005

Bachelor of Chemical Engineering

2010-2011

Master of Chemical Engineering, University of Adelaide

Since 2013

PhD Candidate in Environmental Engineering, UOW

Since 2006

Lecturer, Le Quy Don Technical University (Vietnam)

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ELECTRICALLY ENHANCED MEMBRANE OPERATIONS

THEME: ELECTRICALLY ENHANCED MEMBRANE OPERATIONS W4.11 DR. IR. MARJOLEIN VANOPPEN A NEW MODE OF REVERSE ELECTRODIALYSIS OPERATION TO REDUCE SEAWATER RO ENERGY DEMAND

DR. IR. MARJOLEIN VANOPPEN1, MSC. GRIET WALPOT1, MSC. ELLA CRIEL1, PROF. DR. IR. ARNE VERLIEFDE1 1

Particle and Interfacial Technology group, Ghent University

Water and energy are two of the main challenges facing our modern world today. With water shortages and pollution reaching alarming levels, research is pushed to look for alternative water sources, such as (secondary treated) waste water and seawater. In the case of seawater, the main issue is the large amount of energy needed for its desalination, around 2-3 kWh/M³ at a recovery of 50% (35 g/l total dissolved solids) in the case of state-of-the-art reverse osmosis (RO). By coupling RO with reverse electrodialysis (RED), the energy demand can be decreased in two ways: (1) energy can be produced in RED by the salinity gradient between the seawter and for example impaired water and (2) the concentration of the seawater decreases in RED, entailing a lower energy demand in the RO step. This type of hybrid can theoretically decrease the energy demand of seawater desalination to the point of energy neutrality and can even be energy producing1,2. However, the viability of the process is limited by the slow desalination kinetics in RED, resulting in a high required membrane area and consequent high capital costs; The desalination rate in RED is mainly limited in the first stages of desalination, where the low salinity compartment causes a high resistance of both the solution itself and of the membrane. Indeed it was shown that the membrane resistance mainly depends on the low salinity solution it is in contact with3,4.

Figure 1. Envisioned hybrid (A)RED-RO process

To overcome this initially high resistance, a new mode of RED operation was developed: assisted RED or ARED. Here, instead of producing energy, a small potential difference is GOLD SPONSOR

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applied in the same direction as the natural salt transport to increase the desalination rate. ARED can be incorporated into the hybrid system as shown in Figure 1. This study is one of the first to explore the possibilities of ARED on lab-scale. MATERIALS AND METHODS

A 5 cell-pair RED set-up was used for the ARED tests. Fujifilm type I and type II membranes were used, with an active membrane area of 7.8x11.2 cm². Spacers with a thickness of 485 μm were used to create the low and high salinity compartments. A constant current density (0-136 A/m²) was applied and the resulting voltage was recorded to create current-voltage curves. Experiments were executed in once-through mode to keep the influent concentrations constant. RESULTS

To study the influence of the low salinity compartment (impaired water compartment), the seawater compartment concentration was kept constant, at 0.5M NaCl, while the impaired water compartment concentration was varied (0.01M, 0.1M and 0.25M NaCl). All obtained current-voltage curves at the lower concentrations (0.01 and 0.05M NACl) show a clear downward declination (shown in Figure 2 for the Fujifilm type I membranes), indicating a significant decrease in resistance at increasing currents. At lower flow rates, this decrease in resistance becomes more apparent, as the residence time in the system increases. At higher concentrations (0.1 and 0.25M NaCl), the relation is linear, as theoretically expected.

Figure 2. Influence of the low salinity compartment concentration on the current-voltage curves

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The observed decrease in system resistance is caused by an increase in concentration of the low salinity compartment due to the salt transport in the system. Galama et al. (2014) and Geise et al. (2014) showed that the low salinity compartment concentration determines the membrane resistance3,4 and that an increase in the concentration of this compartment thus leads to a decrease in the membrane resistance as well. The rapid decrease in resistance observed in ARED is its main advantage. Further characterisation and modelling of the system is under way to further assess its value in the hybrid RED-RO system. REFERENCES 1 W. Li, W.B. Krantz, E.R. Cornelissen, J.W. Post, A.R.D. Verliefde, C.Y. Tang, Appl. Energ. 2013, 104, 592-602 2 M. Vanoppen, G. Blandin, S. Derese, P. Le-Clech, J.W. Post, A.R.D. Verliefde, In: A. Cipollina, G. Micale, editors. Woodhead Publishing-Elsevier, 2016, 281-313. 3 a.H. Galama, D.a. Vermaas, J. Veerman, M. Saakes, H.H.M. Rijnaarts, J.W. Post, K. Nijmeijer, J. Membrane Sci. 2014, 467, 279-291 4 M. Geise, A.J. Curtis, M.C. Hatzell, M.A. Hickner, B.E. Logan, Environ. Sci. Technol. Lett. 2014, 1, 36-39

MARJOLEIN VANOPPEN Title: Senior researcher Ghent University, Belgium Phone: +32 (0)9 264 99 11 Fax: +32 (0)9 264 62 42 E-mail: [email protected] 2012

Graduation as a bioscience engineer in environmental technology

2012-2016

Received degree of PhD in applied biological sciences: environmental technology

Since 2016

Senior researcher at the Particle and Interfacial Technology Group (PaInT) at Ghent University

Research interests: Electrochemical membrane processes, industrial water treatment, sustainable membrane processes

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THEME: ELECTRICALLY ENHANCED MEMBRANE OPERATIONS

W4.12 RAMATO ASHU TUFA REVERSE ELECTRODIALYSIS DRIVEN WATER ELECTROLYSIS FOR HYDROGEN PRODUCTION

RAMATO ASHU TUFA1, DEBABRATA CHANDA2, JAROMIR HNAT2, JOOST VEERMAN3, WILLEM VAN BAAK4, ENRICO DRIOLI1,5, KAREL BOUZEK2, EFREM CURCIO1,5 1 Department of Environmental and Chemical Engineering, University of Calabria (DIATIC-UNICAL) via P. Bucci CUBO 45A, 87036 Rende (CS) Italy; email:[email protected] 2 Department of Inorganic Technology, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic 3 REDstack B.V., Pieter Zeemanstraat 6, 8606 JR Sneek, The Netherlands 4 Fujifilm Manufacturing Europe B.V., Oudenstaart 1, 5047 TK Tilburg, The Netherlands 5 Department of Institute on Membrane Technology of the National Research Council (ITM-CNR), c/o the University of Calabria, via P. Bucci, cubo 17/C, 87036 Rende, CS, Italy Hydrogen represents a clean, efficient and versatile energy carrier that can address issues of energy, environment, and sustainability. It can be produced by water electrolysis using electricity from renewable resources like wind and solar energy. However, such power sources are associated with reliability and efficiency issues due to intermittent nature. On the other hand, there exists a huge global potential for renewable energy (2000 TWh/year) generation from Salinity Gradient Power (SGP): a completely renewable and sustainable energy generated by mixing two solutions of different salinity. Among the emerging membrane-based technologies for exploitation of SGP is Revere Electrodialysis (RED)1,2. Recently, we have reported an innovative use of SGP as a renewable energy source for an indirect production of hydrogen3. In this work, a lab-scale RED unit, fed with NaCl solutions of varying concentrations (up to 5 M), was coupled to an APEWE cell. The SGP-RED unit, equipped with 27 cell-pairs and ion exchange membranes particularly tailored for operations in highly concentrated brine solutions, resulted in an open circuit voltage of 3.7 V and maximum gross power density of 3.2 Wm-2 MP (membrane pair) when operated with 0.1 M NaCl//5 M NaCl solutions. The single-cell APEWE unit membrane electrode assembly consisted of highly conductive anion selective membrane based on low-density polyethylene and water-soluble poly (ethylene glycol-ran-propylene glycol), non-Platinum catalysts (NiCo2O4 and NiFe2O4, loading: 10 mg cm-2) and PTFE polymer binder (loading: 15 %w/w) at both cathode and

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anode. The APEWE attained a current density of 120 mA cm-2 when operated at 1.8 V, 65 °C and 10% w/w KOH. The integrated RED-APEWE system reached a maximum hydrogen production rate of 44 cm3 h-1cm-2. Moreover, the potential of coupling RED with other types of water systems was explored for comparative assessment in terms of efficiency and cost. Finally, prospective research directions are outlined through identification of key process challenges. REFERENCES 1

B. E. Logan and M. Elimelech, Nature. 2012, 488, 313-319.

2

R. A. Tufa, E. Curcio, E. Brauns, W. van Baak, E. Fontananova and G. Di Profio, Journal of Membrane Science. 2015, 496, 325-333.

3

R. A. Tufa, E. Rugiero, D. Chanda, J. Hnàt, W. van Baak, J. Veerman, E. Fontananova, G. Di Profio, E. Drioli, K. Bouzek and E. Curcio, Journal of Membrane Science. 2016, 514, 155-164.

RAMATO ASHU TUFA Title: Dr. University of Calabria (DIATIC-UNICAL), Italy Phone: +39 3296566587 Fax: +39 0984496655 E-mail: [email protected] 2005

Bachelor of Science in Applied Chemistry, Hawassa University, Ethiopia

2008

Master of Science in Chemistry (Analytical), Addis Abeba University, Ethiopia

2011

European Master in Quality in Analytical Laboratories (EMQAL), University of Barcelona, Spain; Gdansk University of Technology, Poland

2012-2015

Erasmus Mundus Joint Doctorate in Membrane Engineering (EUDIME), University of Calabria, Italy; University of Twente, The Netherlands, University of Chemistry and Technology, Czech Republic.

Since 2016

Postdoctoral fellow at University of Calabria

Research interests: Membranes for energy applications, electrochemical energy systems, hydrogen production

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THEME: ELECTRICALLY ENHANCED MEMBRANE OPERATIONS

W4.13 SALMAN SHAHID IN-SITU FOULING CONTROL USING INTEGRALLY SKINNED FLAT SHEET HIGHLY CONDUCTIVE POLYANILINE ULTRAFILTRATION MEMBRANES WITH POLYMER DOPANTS

SALMAN SHAHID, LILI XU, AGNIESZKA KINGA HOLDA, DARRELL ALEC PATTERSON Centre for Advanced Separation Engineering and Department of Chemical Engineering, University of Bath, Claverton Down, Bath, United Kingdom Rising populations and source contamination have been exerting increased stress on fresh water supplies. Despite of intensive amount of work on developing high performance membranes, fouling remains an obstacle to wide-spread of membrane technology. In view of this, an in-situ method of fouling control is desperately needed. In this work, a simple, scalable method for fabricating electrically tuneable polyaniline (PANI) composite membranes with improved fouling-resistant is developed (Fig. 1).

Figure 1. Schematic of the desired effects of an electrically tuneable membrane: removal and control of fouling.

Composite membranes were prepared using a 10, 25 and 50 wt% loading of extended graphite (EG), blended in to a mixture of PANI and poly(2-acrylamido-2-methyl-1propanesulfonic-acid) or PAAMPSA. Polymer acids were used as dopants to produce more stable PANI membranes, since the conventional use of small mineral acids for doping PANI in order to make these polymers conductive is inappropriate in membrane applications since these small mineral acids (such as HCl) leach during filtration leading to dedoping and conductivity loss. Furthermore membranes doped by small acids are brittle and thus difficult to handle and use. Polymer acids such as PAAMPSA can act as plasticizers and their stronger molecular interactions with PANI should reduce leaching.

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The membranes of PANI-PAAMPA/EG were prepared via phase-inversion process. The performance properties of these membranes were investigated by using FTIR, dynamic contact angle measurements, SEM, dead-end filtration, light box and 4-point probe conductivity measurements. Fouling resistance was studied by evaluating their ability to remove bovine serum albumin (BSA) fouling layer using applied electrical potential. Both composite and pure membranes showed tuneable properties when tested in dynamic contact angle measurements under electric potential. These membranes showed an increase in permeability and MWCO under the applied potential in the PEG cross-flow filtrations, with the 50wt% membrane showing the greatest increase at 30 V. The composite membranes exhibited very high water permeance compared to pure PANI membranes but relatively lower rejection of PEG mixtures. Significant flux reduction with a simultaneous rise in the PEG rejection was observed as a result of fouling with BSA. The composite membranes successfully removed BSA fouling layer when voltage was applied to the fouled membranes. The images taken by confocal microscopy further confirm the fouling removal using applied electric potential (Fig. 2).

Unfouled membrane

Fouled membrane

After cleaning

Figure 2. Confocal Microscopy Images of the membranes before and after cleaning using electric potential

Extended cross-flow filtrations of these membranes have also shown that they are stable and robust, with minimal leaching and reduction of conductivity during use compared to small acid doped PANI membranes. This work therefore indicates that PANI-PAAMPA/EG are extremely promising candidate membranes for further development as a solution for the in-situ control of fouling control. These flat sheet membranes could be scaled up as spiral wound or flat and frame modules. Furthermore, this is an indication that stimuli-responsive membranes have strong potential for future applications in in-situ fouling control, drug delivery, and many other related technological processes. Key words: Polyaniline, stimuli-responsive, electrical-tuneability, fouling

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SALMAN SHAHID Title: Dr. Affiliation, Country: Centre of Advanced Separation Engineering and Department of Chemical Engineering, University of Bath, United Kingdom. Phone: +00447467910467 E-mail: [email protected] 2010

University of Catholique Louvain,Belgium

2011-2012

University of Twente, Natherlands

2012-2013

University of Montpellier-2, France

2013-2014

University of Leuven, Belgium

2014-2015

Technical university of Delft, Netherlands

Since Dec 2015 PDRA at University of Bath, UK Research interests: Membranes, Liquid separations, Gas separation, MOFs, Catalysis

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W4.14 FRANCOIS-MARIE ALLIOUX HYBRID HOLLOW-FIBER MEMBRANE ELECTRODES FOR THE REMOVAL OF TRACE ORGANIC POLLUTANTS IN MUNICIPAL WASTEWATER

FRANCOIS-MARIE ALLIOUX1, OANA DAVID2, MIREN ETXEBERRIA BENAVIDES2, DAVID ALFREDO PACHECO TANAKA2, PETER D. HODGSON1, LINGXUE KONG1, LUDOVIC F. DUMÉE1 1 Deakin University, Institute for Frontier Materials, Geelong, VIC 3216, Australia 2 TECNALIA, Energy and Environment Division, Mikeletegi Pasealekua 2, 20009, San Sebastian-Donostia, Spain Hollow-fiber (HF) membranes are widely used in filtration processes. Their enhanced surface to volume ratio and the absence of spacers in the membrane module result in a more cost-effective and efficient process compared to flat-sheet membrane systems. However, commercially available HF membranes are based on inert polymeric materials with no catalytic or ion-exchange capacity. The design of charged or ion-adsorbers HF materials are recent but remain based on polymeric systems which are intrinsically electrically resistant [1]. Porous metallic supports are emerging as a viable alternative to polymeric membranes, particularly in high pressure and temperature conditions as well as in corrosive environments. However, inorganic and metal substrates are most commonly found across flat-sheet configurations, which have the lowest surface to volume ratio and which require the largest module sizes. Porous and dense metal HF membranes such as stainless steel and titanium membranes [2, 3] have previously been successfully developed using dry-wet spinning processes. However, the development of novel HF materials combining high electrical conductivity, particularly resistant in harsh aqueous media and exhibiting catalytic activity are needed to enable large-scale electro-assisted wastewater treatment applications. Among the emerging wastewater treatment issues and challenges, the removal of pharmaceutical and other organic pollutants from the environment has become an increasing focus as they represent a novel source of pollution infiltrating surface and ground waters and are suspected to have adverse effect on living organisms including humans and animals [4]. Salicylic acid (SA) was chosen as a representative organic water pollutant due to its increased representation in wastewater and which can be easily detected and its concentration readily monitored using UV/Vis techniques [5]. SA is widely used across a range of applications, primarily for cosmetic and pharmaceutical purposes due to its exfoliating and antiseptic properties [4]. SA is also the primarily hydrolysate of aspirin (acetylsalicylic acid), a mild pain killer and one of the major pharmaceutical organic pollutants found in wastewater treatment plants [4]. A wide variety of electrode materials [6] have been investigated for the electro-chemical oxidation and detection of organic pollutant molecules including conventional metal and carbon materials [7, 8] and GOLD SPONSOR

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more recently carbon [9] and titanium nanotubes [10]. However, electro-oxidation of organic pollutants using electrodes requires additional treatment steps dedicated to the removal of the various oxidation products. In this work, stainless steel (SS) HFs were first fabricated using a dry-wet spinning process from a polymeric solution loaded with SS particles of various sizes (10, 20 and 44 μm) followed by a two steps thermal treatment in order to form metal HFs having small radial dimension (d ≤ 1 mm). The effects of the spinning and sintering conditions such as temperature, heating rate and sintering atmosphere on the final HF morphologies, porosity and pore size distribution were studied. The morphologies of the resulting fibers were characterized by scanning electron microscopy (SEM, Fig.1) and their mechanical and corrosion resistance properties were also assessed. Secondly, the sintered porous HF membranes were coated with an organic ion-exchange resin catalyst in strong acidic form and tested for their electro-catalytic properties. The organic catalyst coating was performed by paste method of a mixture containing an ion-exchange polymer and a backing polymer composed of poly(vinyl chloride) (PVC). The catalyst coating procedure consisted in the deposition of one or two layers in order to form a dense and ion permeable membranes. The electro-oxidation of SA by the novel hybrid HFs was then investigated using a synthetic municipal wastewater comprising of SA (0.04 M) and urea (0.006 M). Finally, the metal HFs were assembled in a module and tested for their capacity to degrade and remove the SA from the feed solution in order to develop an integrated solution to the electro-oxidation and removal of SA and other organic contaminants present in wastewater effluents. MEMBRANE DEVELOPMENT AND CHARACTERISATION SESSION

Figure 11 Morphology of the stainless steel HFs: a) green non-sintered HF; b) cross-section and c) surface of the sintered SS HFs at 1000°C for 90 min in N2:H2 mixture (95:5 v/v) atmosphere.

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REFERENCES 1. Avramescu, M.-E., Z. Borneman, and M. Wessling, Particle-loaded hollow-fiber membrane adsorbers for lysozyme separation. Journal of Membrane Science, 2008. 322(2): p. 306-313. 2. David, O., Y. Gendel, and M. Wessling, Tubular macro-porous titanium membranes. Journal of Membrane Science, 2014. 461: p. 139-145. 3. Schmeda-Lopez, D.R., et al., Stainless steel hollow fibres – Sintering, morphology and mechanical properties. Separation and Purification Technology, 2015. 147: p. 379-387. 4. Tewari, S., et al., Major pharmaceutical residues in wastewater treatment plants and receiving waters in Bangkok, Thailand, and associated ecological risks. Chemosphere, 2013. 91(5): p. 697-704. 5. Matyasovszky, N., M. Tian, and A. Chen, Kinetic study of the electrochemical oxidation of salicylic acid and salicylaldehyde using UV/vis spectroscopy and multivariate calibration. The Journal of Physical Chemistry A, 2009. 113(33): p. 9348-9353. 6. Patel, P.S., et al., Electro-catalytic Materials (Electrode Materials) in Electrochemical Wastewater Treatment. Procedia Engineering, 2013. 51: p. 430-435. 7. Vadivaambigai, A., et al., Graphene-Oxide-Based Electrochemical Sensor for Salicylic Acid. Nanoscience and Nanotechnology Letters, 2015. 7(2): p. 140-146. 8. Doulache, M. and A. Benchettara, Effect of the nature of conductive supported nickel electrocatalyst for salicylic acid oxidation in alkaline medium. Russian Journal of General Chemistry, 2014. 84(4): p. 775-781. 9. Zhang, W.-D., et al., Electrochemical oxidation of salicylic acid at well-aligned multiwalled carbon nanotube electrode and its detection. Journal of Solid State Electrochemistry, 2010. 14(9): p. 1713-1718. 10. Chang, X., S.S. Thind, and A. Chen, Electrocatalytic Enhancement of Salicylic Acid Oxidation at Electrochemically Reduced TiO2 Nanotubes. ACS Catalysis, 2014. 4(8): p. 2616-2622.

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THEME: ENGINEERED OSMOSIS TH2.2 HESAMODDIN RABIEE THERMORESPONSIVE ANIONIC COPOLYMER MICROGELS AS FORWARD OSMOSIS DRAW AGENTS

YUSAK HARTANTO, MASOUMEH ZARGAR, HESAMODDIN RABIEE, BO JIN, SHENG DAI School of Chemical Engineering, The University of Adelaide, SA 5005, Australia Thermoresponsive microgels with carboxylic acid functionalization have been recently introduced as an attractive draw agent for forward osmosis (FO) desalination, where the microgels showed promising water flux and water recovery performance1. In this study, various comonomers containing different carboxylic acid and sulfonic acid functional groups were copolymerized with N-isopropylacrylamide (NP) to yield a series of functionalized thermo-responsive microgels possessing different acidic groups and hydrophobicities. The purified microgels were examined as the draw agents for FO application, and the results show the response of water flux and water recovery was significantly affected by various acidic co-monomers as shown in Fig. 1. The thermoresponsive microgel with itaconic acid shows the best overall performance with an initial water flux of 44.8 LMH, water recovery up to 47.2 % and apparent water flux of 3.1 LMH. This study shows that the incorporation of hydrophilic dicarboxylic acid functional groups into MCG-NP microgels leads to the enhancement on water adsorption and overall performance. Our work elucidates in detail on the structure-property relationship of thermo-responsive microgels in their applications as FO draw agents and would be beneficial for future design and development of high performance FO desalination.

Figure 1. Initial water flux and water recovery for different thermoresponsive anionic microgels

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REFERENCES 1. Hartanto, Y.; Yun, S.; Jin, B.; Dai, S., Functionalized thermo-responsive microgels for high performance forward osmosis desalination. Water Research 2015, 70, 385-393

YUSAK HARTANTO Title: Mr. Affiliation, Country: School of Chemical Engineering, The University of Adelaide, SA 5005, Australia E-mail: [email protected] Personal History: 2012-2016

PhD Student

Research interests: Desalination, Stimuli-responsive polymers, Membrane technologies.

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TH2.3 GAETAN BLANDIN UP SCALING FORWARD OSMOSIS AND PRESSURE ASSISTED OSMOSIS TO COMBINE DESALINATION AND WATER REUSE: A PILOT SCALE STUDY ON 8´´ MODULES

GAETAN BLANDIN1, JUNGEUN KIM2, SHERUB PHUNTSHO2, ARNE VERLIEFDE3, HOKYONG SHON2,PIERRE LE-CLECH4 1 LEQUIA, Institute of the environment, University of Girona, Spain 2 School of Civil and Environmental Engineering, University of Technology, Sydney, Australia 3 Ghent University, Faculty of Bioscience Engineering, Department of Applied Analytical and Physical Chemistry, Particle and Interfacial Technology Group, Ghent, Belgium 4 UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering, The University of New South Wales, Sydney, Australia The forward osmosis (FO)-reverse osmosis (RO) hybrid process is a promising method to combine water reuse and desalination 1 (Figure 12), but its implementation requires significant water flux increase for more attractive economics 2. The development of novel FO membranes and the application of hydraulic pressure in FO under the form of pressure assisted osmosis (PAO) have both proven to be able to tackle current FO flux limitation 3,4. However, most PAO studies have been conducted on lab scale using a cross-flow cell, and very little is known about pilot scale operation of both FO and PAO, which is the necessary next step towards successful full-scale implementation. A better understanding of large spiral wound forward osmosis (SW FO) module operation is needed to provide practical insight for a full-scale FO desalination plant. In this study, we assessed the performance and practical limitations of two commercial 8’’ spiral wound FO modules (HTI CTA and Toray TFC) in terms of hydrodynamics, operating pressure, water and solute fluxes, fouling behaviour and cleaning strategy both in FO and PAO (up to 2.5 bar) operating modes using artificial seawater as draw solution (Figure 12).

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Figure 12: Schematic diagram of the pilot-scale FO experimental set up for the evaluation used for the evaluation of 8’’ (8040) FO modules:

Both the use of the novel TFC membrane and PAO confirmed to be successful strategies for water flux enhancement and reverse salt flux reduction. Typically, thanks to the combine use of TFC membrane and hydraulic pressure (2.5 bar), a water flux as high as 27 L.m-2.h-1 (Figure 1b) with very low reverse salt diffusion (Js/Jw < 0.1g.L-1) was reached (Figure 13). (a)

(b)

Figure 13: Water flux (Jw) and reverse salt diffusion (Js/Jw) in FO and PAO operation (0-2.5bar) for (a) HTI CTA and (b) Toray TFC membranes respectively

It was demonstrated that hydraulics in spiral wound module require special attention during full scale operation. Typically, operation with lower flowrate in the draw than in the feed channel was required to avoid pressure build-up. This was especially critical when operating the CTA module where permeate spacers are used, draw flow rate was of one order of magnitude lower than feed flowrate. Also, it was observed that the application of GOLD SPONSOR

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hydraulic pressure on the feed side led to significant draw channel pressurisation and impacted pressure balance within the modules. Fouling tests were conducted in FO mode with both modules, using model foulants mimicking wastewater (i.e. g.L-1 RSS, 0.22 g.L-1 CaCl2, 0.2 g.L-1 humic acid and 0.2 g.L-1 alginate) on the feed side and by operating three consecutive batches until reaching 80% feed recovery for each batch. It was observed first that due to lower initial flux and higher flux decrease during the operation, the time to reach 80% recovery was much longer for the CTA than for the TFC module (i.e.60 vs. 3.5 hours). During fouling tests, for both modules, increase of feed inlet pressure was observed but the water permeation flux did not decreased significantly. As such it confirms that foulant occurs but most likely in the feed channel rather than on the membrane surface. Osmotic backwash combined with physical cleaning was tested as cleaning strategy and confirmed to be effective and adapted to large-scale FO module operation even on a module scale. REFERENCES 1

Cath, T. Y.; Hancock, N. T.; Lundin, C. D.; Hoppe-Jones, C.; Drewes, J. E. Journal of Membrane Science 2010, 362, 417.

2

Blandin, G.; Verliefde, A. R. D.; Tang, C. Y.; Le-Clech, P. Desalination 2015, 363, 26.

3

Blandin, G.; Verliefde, A. D.; Tang, C. Y. Y.; Childress, A. E.; Le-Clech, P. Journal of Membrane Science 2013, 447, 1.

4

Sahebi, S.; Phuntsho, S.; Eun Kim, J.; Hong, S.; Kyong Shon, H. Journal of Membrane Science 2015, 481, 63.

BLANDIN GAETAN Title: Marie Curie and TECNIOspring Postdoctoral fellow LEQUIA, Institute of the environment, University of Girona, Spain Phone: +34 618 804 214 E-mail: [email protected] 2007-2012 R&D engineer for water and sludge treatment applications at Lhois R&D (Belgium) 2012-2015 Joint PhD at UNSW, Australia and Ghent university, Belgium (Assisted forward osmosis for energy savings in seawater desalination) Since Oct 2015 Marie Curie and TECNIOspring Postdoctoral fellow (OMBReuse: Osmotic membrane bioreactor for water reuse) Research interests: forward osmosis, membrane separation, water reuse, desalination

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ENGINEERED OSMOSIS

TH2.4 CORNELISSEN, E.R ORGANIC MICRO-POLLUTANTS (OMP) REJECTION IN CLOSED-LOOP FO/ RO: A PILOT PLANT STUDY

ORTEGA-BRAVO, J.C.1, HARMSEN, D.J.H.2, VERLIEFDE A.R.D.3, D’HAESE, A.3, JEISON, D.1, CORNELISSEN, E.R.2,4 1 Universidad de La Frontera, Chemical Engineering Department, Temuco, Chile 2 KWR Watercycle Research Institute, Nieuwegein, the Netherlands 3 Ghent University, Particle and Interfacial Technology Group, Ghent, Belgium 4 Singapore Membrane Technology Centre, Singapore, Singapore BACKGROUND

As a result of the increase in worldwide fresh water demand, FO applications involving water recovery from wastewater has received a considerable amount of attention. In high quality water recovery from wastewater by membrane processes, the rejection of organic micro-pollutants (OMP) is an issue of great concern. It was found that many OMP resist removal through conventional water-treatment processes1, and the human risks associated with exposure to MPs in drinking water from reuse water can be severe2. A closed-loop forward-reverse osmosis (FO/RO) may present an alternative to overcome this problem3,4. FO/RO process involves arguably a multi-barrier protection, leading to high quality (drinking) water and low RO membrane fouling3,5. However, a challenge in FO/RO closed-loop operation is OMP transport from feed to draw solution (DS) which can potentially result in an accumulation of OMPs in the DS loop3,5. AIM

This study focuses on the fate of OMPs in closed-loop FO/RO operation on pilot plant scale using 27 OMP in drinking water, using commercially available FO and RO elements. An assessment was made on (i) OMP rejection in function of OMP properties (size, polarity, charge), (ii) occurrence and effects of OMP accumulation in the DS loop and (iii) influence of the DS type of OMP rejection. EXPERIMENTAL ISSUES

Four spiral wound FO cellulose triacetate membrane elements with a membrane area of 14.4 m2 per element, were acquired from Hydration Technology Innovations (Albany, OR), and one spiral wound RO NanoH2O Quantum flux Qfx SW75ES element of 7.0 m2 was acquired from NanoH2O Inc. An integrated closed-loop FO/RO pilot was constructed (Fig 1 & 2). The FO elements were connected in series for the feed flow, while the draw flow was connected in parallel. The draw solution was re-concentrated by RO and permeate water was recirculated to the feed tank to maintain a constant feed volume. All samples GOLD SPONSOR

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were taken from the sample points P1, P2, P3 and P4; two samples were taken per day during 7 days of operation (for each draw solution run).

Figure 1. RO installation with six parallel 2.5-inch RO membrane elements

Figure 2. UF installation feeding two 2.5-inch RO membrane elements

The draw solution used in FO experiments were sodium chloride (NaCl) (Akzo Nobel, Netherlands) and magnesium chloride (MgCl2) (Nedmag Industries Mining & Manufacturing B.V., Veendam, Netherlands) in the different experiments. For both experiments the DS concentration was kept constant at approximately 0.1 M, which is relatively low as a result of pressure limitations in the RO set-up. The feed solution was locally available tap water supplemented with a mixture of 27 OMP, consisting of 10 negatively charged compounds (bezafibrate, clofibric acid, diclofenac, dinoseb, gemfibrozil, ibuprofen, ketoprofen, salicylic acid, sulfamethoxazole and triclopyr), 12 neutral compounds (atrazine, caffeine, chloridazon, diglyme, dimethoate, diuron, hydrochlorothiazide, paracetamol, pentoxifyline, phenazone, pirimicarb and simazine) and 5 positively charged compounds (atenolol, lincomycin, propranolol, ranitidine and terbutaline). All OMP were obtained from Sigma Aldrich at purity of 98% or above. OMP concentrations were determined using solid phase extraction (SPE) on Oasis HLB cartridges (Waters, USA), followed by UPLC-triple quad MS. The initial dosing concentration was 5-10 µg/L for each OMP. RESULTS AND DISCUSSION

The OMP rejection strongly depends on the OMP properties both for FO and RO membranes. FO rejection is assessed from the ratio between the OMP concentrations in sample points P1 and P2 (Fig 3-5). On the first day, neutral OMP displayed the lowest FO rejection range, from 16-61% (16% is for the smallest neutral compound diglyme), while positively charged and negatively charged OMP displayed higher rejection ranges, respectively 50-78% and 67-81%. RO rejection is very high (>95%) for all OMP.

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Figure 3. Concentrations of neutral OMP in time for sample points P1-P4 (DS: NaCl)

Figure 4. Concentrations of negatively charged OMP in time for sample points P1-P4 (DS: NaCl)

OMP transport occurred from the feed solution towards the draw solution because the OMP FO rejection is <100%,. Since the OMP were highly rejected by the RO membrane, accumulation of all OMP occurred in the DS loop. The rate of accumulation depends on the actual rejection value, and is a function of the OMP properties (size, hydrophobicityand charge), as can be observed from the OMP concentration increase in time in sample points P2 and P3 (Fig 3-6).

Figure 5. Concentrations of positively charged OMP in time for sample points P1-P4 (DS: NaCl)

Figure 6. Concentrations of positively charged OMP for sample points P1-P4 (DS: MgCl2)

Interestingly, clear differences can be observed in OMP transport through the FO membrane when different draw solutions are used. For example, rantidine transports faster to the NaCl DS loop side compared to the MgCl2 DS loop side. CONCLUSION

• OMP rejection of FO and RO membranes depend on the OMP properties in closedloop FO/RO • Accumulation of OMP occurs in the DS loop, and its rate depends on OMP properties • The DS type will affect the FO and RO rejection behavior in closed-loop FO/RO

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REFERENCES 1

(3) B.D. Coday, B.G..M. Yaffe, P. Xu, T.Y. Cath, T.Y. EST 2014 48(7), 3612-3624.

2

(5) A. D’Haese, P. Le-Clech, S. Van Nevel, K. Verbeken, E.R. Cornelissen, S.J. Khan, A.R.D. Verliefde, Wat. Res. 2013 47(14), 5232-5244

3

(2) O.A. Jones, J.N. Lester, N. Voulvoulis, Biotechn. 2005, 23(4), 163-167.

4

(4) K. Lutchmiah, A.R.D. Verliefde, K. Roest, L.C. Rietveld, E.R. Cornelissen, Wat. Res. 2014, 58, 179-197.

5

(1) P.E. Stackelberg, E.T. Furlong, M.T. Meyer, S.D Zaugg, A.K. Henderson, D.B. Reissman, Sc.Tot.Env. 2004, 329(1–3), 99-113.

EMILE CORNELISSEN Title: Dr.ir. KWR Watercycle Research Institute, The Netherlands Phone: +31 30 6069538 Fax: +31 30 6069501 E-mail: [email protected] kwrwater.nl 1992

He obtained his Chemical Engineering MSc degree at the University of Twente (the Netherlands).

1997

He obtained his Chemical Engineering PhD degree at the University of Twente (the Netherlands).

1997-2002

He worked as a Process Engineer at Seghers better technology for Water in Belgium and worked on membrane filtration in waste water treatment.

Since 2003

He is a Senior Scientific Researcher at KWR Watercycle Research Institute and his research topics include membrane fouling and cleaning, rejection of emerging contaminants by pressure driven membranes and developing innovative processes

Since 2014

He is a Visiting Scientist at the Singapore Membrane Technology Centre (SMTC) at the NTU in Singapore.

He published more than 81 papers in well-respected scientific journals (h-factor of 22), co-filed 3 patents and written three book chapters. He received several innovation awards in the field water treatment and membrane filtration.

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TH2.5 ASHLEY J. ANSARI INTEGRATING FORWARD OSMOSIS WITH ANAEROBIC TREATMENT FOR SIMULTANEOUS WASTEWATER TREATMENT AND RESOURCE RECOVERY – PROCESS PERFORMANCE AND CHALLENGES

ASHLEY J. ANSARI1, 2, FAISAL I. HAI1, WILLIAM E. PRICE2, AND LONG D. NGHIEM1 1 Strategic Water Infrastructure Laboratory, School of Civil, Mining and Environmental Engineering, University of Wollongong, Wollongong, NSW 2522, Australia. 2 Strategic Water Infrastructure Laboratory, School of Chemistry University of Wollongong, Wollongong, NSW 2522, Australia. The key advantages of forward osmosis (FO) can be strategically utilised to provide a revolutionary pathway to renew our wastewater treatment infrastructure. These key advantages include low fouling propensity and easy cleaning, low hydraulic pressure operation, and high rejection of a broad range of contaminants. Thus, FO can be integrated with membrane distillation (MD) to directly extract clean water from raw wastewater, while simultaneously concentrating wastewater to the level suitable for anaerobic treatment. Anaerobically digesting FO pre-concentrated wastewater via an anaerobic membrane bioreactor (An-MBR) can product biogas, which can then be used by a combined heat and power engine to produce electricity and thermal energy. While surplus electricity can be supplied to the grid, the thermal energy produced can be used to power MD and the anaerobic process itself. The anaerobic process also converts biologically bound phosphorus into a soluble form, thus allowing phosphorus recovery as struvite (MgNH4PO4·6H2O) or hydroxyapatite (Ca10(PO4)6(OH)2). The new clean water paradigm calls for significant improvement in system efficiency and innovative treatment technologies. An effective approach to improve efficiency is to replace electricity consumption (which is a secondary form of energy) by a primary energy source (e.g. thermal energy). Significant reduction in energy consumption can also be gained by replacing the conventional aerated activated sludge process by anaerobic treatment. Thus, the combination of FO, MD, and AnMBR is an excellent platform for a wastewater treatment plant of the future (Fig. 1).

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Figure 1. FO-based wastewater treatment plant where clean water is reclaimed, phosphorus and biosolids are recovered for agricultural purposes, and surplus electricity is produced.

The successful integration of FO with anaerobic treatment remains a prominent challenge that must be addressed for this application. Our recent research has focussed on the issues associated with the compatibility of FO pre-concentrated wastewater with An-MBR. These include the impact of reverse draw solute flux and salinity accumulation on methane production, as well as FO treatment efficiency and resource recovery potential. Reverse solute flux is a major drawback of FO and the migration of some draw solutes to the FO pre-concentrated wastewater can be detrimental to subsequent biological treatment, particularly the anaerobic process. We have developed a protocol using biomethane potential (BMP) evaluation to examine the impact of reverse draw solute flux on anaerobic treatment18. Our results (Fig. 2) show that at 90% clean water recovery, when using NaCl or MgSO4 as the draw solute, the transport of these salts to the preconcentrated wastewater results in less methane production compared to the reference substrate (without any draw solute addition). One promising approach to alleviate this adverse impact of reverse salt flux on anaerobic performance involves using organicbased draw solutes. Rather than inhibiting methane production, the presence of organicbased draw solutes improved methane production. Specifically, EDTA-2Na presented the lowest reverse solute flux and has proved to be highly effective at mitigating salinity build-up during wastewater pre-concentrationi and in aerobic osmotic membrane bioreactors19 (Fig. 3). Salinity mitigation is a key milestone for successfully integrating FO with anaerobic treatment. While there are a number of remaining challenges, we promote the advantages of organic-based draw solutes for FO applications integrated with anaerobic treatment.

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500

0

Reference Glycine (3.46 g/L) Glucose (1.48 g/L) Sodium acetate (2.41 g/L) Magnesium acetate (1.65 g/L)

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EDTA-2Na (1.52 g/L) Sodium chloride (5.78 g/L) Sodium formate (5.45 g/L) Magnesium sulfate (1.06 g/L)

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20 1500

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Figure 2. Impact of the presence of different draw solutes in wastewater substrate on methane production using BMP analysis.

Figure 3. Mitigation of salinity using ionic organic draw solutes during (a) wastewater preconcentration and in (b) an aerobic osmotic membrane bioreactor.

We have also developed a novel FO-MD hybrid system for sewer mining, in which clean water is directly extracted from wastewater for reuse. The FO membrane acts as a pre-treatment barrier to protect the MD process from membrane fouling while simultaneously concentrating the carbon content of the remaining wastewater for subsequent biogas production via AnMBR. Our work has demonstrated that FO can extract 90% clean water while simultaneously pre-concentrating wastewater chemical oxygen demand (COD) by approximately eightfolds1. To illustrate, low strength wastewater could be concentrated up to 3,000 mg COD/L, making it suitable for anaerobic treatment. Our research presents novel approaches to improve the sustainability of wastewater treatment practices by utilising alternative energy sources and promoting resource recovery. ASHLEY J. ANSARI University of Wollongong (UOW), Australia Phone: 0423240084 E-mail: [email protected] 2010-2013

Bachelor of Engineering (Environmental), UOW

Since 2012

Environmental Engineer, Shoalhaven Water

Since 2014

PhD Candidate in Environmental Engineering, UOW

GOLD SPONSOR

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THEME: ENGINEERED OSMOSIS

TH2.6 D’HAESE ARNOUT TRANSPORT OF OMPS THROUGH FO MEMBRANES: INFLUENCE OF OMP AND DRAW SOLUTE PROPERTIES

D’HAESE ARNOUT1, VAN KERREBROEK TIM1, SCHOUTTETEN KLAAS1, VANDEN BUSSCHE JULIE2, VANHAECKE LYNN2, VERLIEFDE ARNE1 1 Ghent University, Faculty of Bioscience Engineering, Department of Applied Analytical and Physical Chemistry, Particle and Interfacial Technology Group (PaInT), Coupure Links 653, B-9000 Gent, Belgium 2 Ghent University, Faculty of Veterinary Medicine, Department of Veterinary Public Health and Food Safety, Laboratory of Chemical Analysis, Salisburylaan 133, B-9820 Merelbeke, Belgium In this study, the transport of Organic Micro Pollutants (OMPs) through Forward Osmosis (FO) membranes is investigated. FO has been researched as a membrane process capable of treating highly polluted feed streams1, streams which could contain OMPs. It is therefore important to study the fate of OMPs in FO systems as well2. In this work, the rejection of 27 OMPs with different physico-chemical properties was studied. The FO membranes of cellulose triacetate (CTA) were operated in AL-FS (FO) mode. 4 draw solutes (NaCl, MgCl2, Na2SO4 and MgSO4) were tested at 5 concentrations, as well as simple diffusion (no salts present). In a separate set of experiments, the flux behaviour of the draw solutes was evaluated as well. It was found that the draw solute influences OMP rejection through charge effects: uncharged and anionic OMPs were better rejected by sulfate draw solutes, while cationic OMPs were better rejected by chloride draw solutes. Other draw solute effects were noted as well. For uncharged OMPs, the membrane permeability during diffusion was as high as during FO operation with chloride draw solutes, but was reduced when sulfate draw solutes were used. No relation was found between the draw solute permeabilities and OMP permeabilities. The draw solute permeability decreased in the following order: NaCl > MgCl2 > Na2SO4 > MgSO4. The hypothesis that a higher draw solute permeability hinders OMP transport is thus not supported by this study3.

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Certain OMPs showed a different permeability depending on the draw solute (fig.1), but this was not the case for every OMP (fig.2). Those OMPs whose membrane permeability were influenced by the draw solute, were predominantly smaller compounds in terms of molecular weight and surface area, showing an overall lower rejection. Susceptible compounds had an average molecular weight and surface area of 201 g/mol and 291 Å2 resp., compared to the average of 248 g/mol and 353 Å2 for all OMPs. It is therefore hypothesized that adsorption of certain draw solutes causes subtle structural changes in the membrane active layer. The permeability of relatively large compounds would not be impacted to a large extend, as transport through the membrane active layer of these 9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ENGINEERED OSMOSIS

compounds is strongly hindered in any case. The influence of structural changes would be larger on smaller compounds, with a size closer to the pores of the active layer.

Illustration 1: Rejection of Diuron in function of water flux and draw solute

Illustration 2: Rejection of Sulfamethoxazole in function of water flux and draw solute

OMP sterical parameters were modeled using MarvinBeans (ChemAxon). OMP permeability of uncharged compounds was strongly correlated to the OMPs’ minimal projected surface area (fig. 4) and molecular surface area (fig. 3), but not to the maximal projected surface area. This indicates that solutes are oriented in the most favourable position during membrane passage. This correlation was only valid for the uncharged OMPs. GOLD SPONSOR

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Illustration 3: Spearman correlation between uncharged OMP membrane permeability and OMP molecular surface area (Å2) for MgSO4 draw solution tests

Illustration 4: Spearman correlation between uncharged OMP membrane permeability and OMP minimal projected area (Å2) for diffusion tests in MilliQ water.

Surface energy determination of membrane samples soaked in draw solution also revealed a correlation between OMP-membrane interaction energy and measured OMP membrane permeability. This correlation was stronger for uncharged OMPs. For charged OMPs, charge effects probably dominate. ARNOUT D’HAESE Title: Transport of OMPs through FO membranes: influence of OMP and draw solute properties Affiliation, Country: Ghent University, Belgium Phone: +32 9 264 99 10 E-mail: [email protected] Research interests: Forward Osmosis, organic micropollutants, modeling, membrane transport

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TH2.7 AGATA ZAREBSKA INFLUENCE OF MECHANICAL WASTEWATER PRETREATMENT ON MEMBRANE FOULING DURING MUNICIPAL WASTEWATER TREATMENT BY FORWARD OSMOSIS

AGATA ZAREBSKA1, IRENA PETRINIC2, JASMINA KORENAK2, HERMINA BUKSEK 2, ANNA CISZEWSKA-KALUZKA1, CLAUS HELIXNIELSEN1,2 1 Department of Environmental Engineering, Technical University of Denmark, Bygningstorvet, Building: 115, 139, 2800 Kgs. Lyngby, Denmark 2 Faculty of Chemistry and Chemical Engineering, University of Maribor, Smetanova ulica 17, 2000 Maribor, Slovenia BACKGROUND

Recent development in the membrane technology indicates that forward osmosis (FO) has a high potential for wastewater treatment, producing high quality water1. Compared to other pressure driven membrane processes, FO membranes may suffer less severe fouling due to the lack of hydraulic pressure2. However, the extent of fouling is highly dependent on feed characteristics. Municipal wastewater management via conventional mechanical pretreatment though affects the effluents characteristic, and hence severity of fouling. Furthermore, the mechanical feed pretreatment might alleviate fouling due to the removal of suspended solids, microorganisms, extracellular polymeric substances (EPS), soluble macro/micro organics and inorganics. AIM

Due to the different types of fouling, which can occur during FO membrane operation, characterizing fouling is a complex issue. As biological, organic, and inorganic types of fouling3,4 can contribute to a water flux or product (permeate) quality decrease, one of the major challenges is to characterize and distinguish between the various phenomena underlying the observed performance decline. The objective of this work is to add knowledge on how FO membrane fouling is affected by different mechanical pretreatment techniques such as microsieving and microfiltration and to determine which pre-treatment method is the most feasible. METHODS

Membrane autopsies were performed on fouled membranes to characterize major foulants present on the membrane as a basis for optimizing pre-treatment methods. Fouled FO membranes came from experiments performed using Aquaporin Inside TM (AIM) membranes for recovery of water from the Källby municipal wastewater treatment plant in Lund, Sweden5. Membrane fouling was characterized using Scanning Electron Microscopy (SEM) coupled with X-ray Energy Dispersive Spectroscopy (EDS), Fourier Transform Infrared GOLD SPONSOR

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THEME: ENGINEERED OSMOSIS

Spectrometry (ATR-FTIR), Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES), Ion chromatography (IC), Streaming current measurements and adenosine triphosphate (ATP) measurements. RESULTS AND CONCLUSION

SEM analysis demonstrated that the surfaces of FO membranes during municipal wastewater treatment were covered with uneven deposits irrespective of the kind of applied pre-treatment. For membranes exposed to microfiltrated pretreated (MFP) wastewater, no microorganisms were observed by SEM in contrast to membranes exposed to raw (R) or microsieved wastewater (MSF). This is consistent with the EDS analysis revealing the presence of N and P on the fouled membranes (MSF and R), indicating biofouling and extracellular polymeric substances (EPS). Using ATP analysis, we detected more bacteria on the membrane after exposure to MSF wastewater (36 ngATP/cm2) compared to membranes exposed to raw wastewater (3 ngATP/cm2). This is likely caused by microorganism growth on/in the microsieve. EDS and ICP-OES analysis revealed presence of Fe and Ca on membrane after adsorptive fouling with raw wastewater, whereas Si and Al was found on membrane exposed to MFP. Also C and O were detected, reflecting the membrane fabric elements. This may explain why membrane becomes positively charged with raw wastewater as depicted in Fig. 1. Naturally occurring cations in the wastewater such as Fe or Ca are attracted to the negatively charged carboxylic group of the thin film composite (TFC) layer, being an integral part of the Aquaporin Inside TM (AIM) membrane. On the contrary membrane exposed to MFP wastewater becomes more negatively charged compared to clean membranes (Fig. 1) likely due to silica deposition in agreement with previous reports6,7. This presence might enhance organic fouling, since the space inside the polymerized silica clusters could be favourable sites for the accumulation and adhesion of biopolymers. The ATR-FTIR spectra (Fig. 2) of the fouled membrane (R and MSF) exhibited bands at 3295 cm-1, 2921 cm-1, 2851 cm-1, which are characteristic for polysachrides8 and at 1641 cm-1, 1576 cm-1, which are unique for protein secondary structure features (amide I and amide II)9. This indicates that the fouling is mainly of organic origin due to adsorption and deposition of proteins and carbohydrates in agreement with earlier observations10,11. After exposure to MFP treated wastewater, the bands characteristic for proteins and polysaccharides were significantly reduced compared to raw wastewater and MSF (Fig.2), meaning that less membrane and cleaning would be required. In conclusion our results suggest that microfiltration is a suitable pre-treatment method for municipal wastewater treatment for subsequent treatment by forward osmosis.

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Figure. 1 Zeta potential as a function of pH of clean Inside TM (AIM) membrane (black), fouled membrane with raw wastewater (red), fouled membrane with microsieve filtrate (MSF, green), fouled membrane with microfiltration permeate (MFP, blue).

Figure. 2 FTIR spectra of clean Inside TM (AIM) membrane (black), membrane after baseline experiment with tapwater (red), fouled membrane with raw wastewater (blue), fouled membrane with microsieve filtrate (MSF, pink), fouled membrane with microfiltration permeate (MFP, green). For transmittance band assignments, see text.

REFERENCES 1 K. Lutchmiah, A.R.D. Verliefde, K. Roest , L.C. Rietveld, E.R. Cornelissen. Forward osmosis for application in wastewater treatment: A review. Water Res. 2014, 58, 179-197. 2 S. Lee, C. Boo, M. Elimelech, S. Hong. Comparison of fouling behavior in forward osmosis (FO) and reverse osmosis (RO). J. Membrane Sci. 2010, 365, 34-39. 3 B. Mi, M. Elimelech. Organic fouling of forward osmosis membranes: Fouling reversibility and cleaning without chemical reagents. J. Membrane Sci. 2010, 348 (1-2), 337-45. 4 B. Mi, M. Elimelech. Gypsum Scaling and Cleaning in Forward Osmosis: Measurements and Mechanisms. Env Sci Tec, 2010, 44(6), 2022-8. 5 T. Hey, A. Zarebska, J. Vogel, C. Helix-Nielsen, J. Jansen, K. Jonsson. Influences of mechanical pre-treatment on the non-biological treatment of municipal wastewater by forward osmosis. Submitted to Water Res. 2016. 6 C. Boo, S. Lee, M. Elimelech, Z. Meng, S. Hong. Colloidal fouling in forward osmosis: Role of reverse salt diffusion. J. Membrane Sci. 2012, 390, 277-84. 7 B. Mi, M. Elimelech. Silica scaling and scaling reversibility in forward osmosis. Desalination. 2013, 312, 75-81. 8 P. Xu, JE. Drewes, T-U Kim, C. Bellona, G. Amy. Effect of membrane fouling on transport of organic contaminants in NF/RO membrane applications. J Membrane Sci. 2006, 279 (1-2), 165-75. 9 T. Maruyama, S. Katoh, M. Nakajima, H. Nabetani, TP Abbott, A. Shono, K. Satoh. FT-IR analysis of BSA fouled on ultrafiltration and microfiltration membranes. J. Membrane Sci. 2001, 192(1-2), 201-7. 10 X. Wang, B. Yuan, Y. Chen, X. Li, Y. Ren. Integration of micro-filtration into osmotic membrane bioreactors to prevent salinity build-up. Bioresour Technol. 2014, 167, 116-23. 11 J. Zhang, WLC. Loong, S. Chou, C. Tang, R. Wang, AG. Fane. Membrane biofouling and scaling in forward osmosis membrane bioreactor. J. Membrane Sci. 2012, 403, 8-14. GOLD SPONSOR

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AGATA ZAREBSKA Title: Postdoc Affiliation, Country: Technical University of Denmark, Denmark Phone: +45 52631110 E-mail:[email protected] 2010-2013

PhD fellow, University of Southern Denmark

2015

Postdoc, Technical University of Denmark

Research interests: forward osmosis, membrane distillation, fouling characterization

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ENGINEERED OSMOSIS

TH2.8 MASAFUMI SHIBUYA UP-CONCENTRATION OF SUGAR SOLUTION BY USING FORWARD OSMOSIS FOR BIOETHANOL PRODUCTION PROCESS

MASAFUMI SHIBUYA1, MASAHIRO YASUKAWA1, KENGO SASAKI2, YASUHIRO TANAKA1, TOMOKI TAKAHASHI1, AKIHIKO KONDO2, HIDETO MATSUYAMA1 1 Center for Membrane and Film Technology, Department of Chemical Science and Engineering,Kobe University 2 Graduate School of Science, Technology and Innovation, Kobe University In the bio-ethanol production process, it consists mainly the following step: the pretreatment of lignocellulosic biomass, hydrolysis, sugar fermentation, recovery and purification of ethanol. For commercializing cellulosic ethanol production, increasing the ethanol concentration after fermentation in order to decrease energy consumption in post-stage purification processes is required. To approach for this issue, a high concentration in culture broth is needed before the ethanol fermentation step. However, sugars derived from hemi-cellulose are at low concentration in the liquid fraction after the pretreatment 1. Previous studies, the pressure-driven membrane process have been used to remove fermentation inhibitors and / or concentrate sugars in the liquid fraction of pretreated lignocellulosic biomass 2. In these systems, limitation of sugar concentration is occurred due to the technical limitation of applied pressure. Recently, forward osmosis (FO) process has attracted as one of the water treatment system. The water permeation of FO is occurred by osmotic pressure difference. Water molecules are transferred from a low-osmotic pressure to a high-osmotic pressure solution without applied pressure. Therefore, FO process has a large potential to decrease energy cost. Additionally, FO process is able to achieve higher concentration ratio than the pressure-driven membrane processes by using high osmotic pressure solution. In this study, we investigated that influence up-concentrated sugar solutions on the fermentation process. We use the actual sugar solution as FS that was originated from pretreated rice straw. Permeation test was carried out using a flat sheet membrane cell. Trimethylamine solution after CO2 bubbling at 48 h was used as DS. Fig. 1 shows water flux and FS concentration ratio as a function of operating time. Water flux (Jw) decreased and up-concentration ratio increased with increasing elapsed time due to decrease the osmotic pressure difference between DS and FS. Fig. 2 shows the result of ethanol fermentation test. The ethanol concentration after 24 h fermentation was 17.7 g/L, and ethanol yield (grams of ethanol produced per gram of total sugars consumed) was 17 %. Therefore, the sugar solution was concentrated by the FO process and ethanol fermentation was performed successfully as well as the pressure driven membrane process. GOLD SPONSOR

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THEME: ENGINEERED OSMOSIS

Fig. 1 Water flux and FS concentration ratio as a function of operating time.

Fig. 2 Ethanol fermentation by using the high concentration sugar solution (FS conc. ratio: 5.0).

MASAFUMI SHIBUYA Influence of up-concentrated sugar solution by using forward osmosis for bioethanol production process Center for Membrane and Film Technology, Department of Chemical Science and Engineering, Kobe University, Japan Phone: +81-78-803-6180 E-mail: [email protected] Present Kobe University, PhD student Research interests: Forward osmosis, Pressure retarded osmosis

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ENGINEERED OSMOSIS

TH2.9 MING XIE SILICA SCALING IN FORWARD OSMOSIS: FROM SOLUTION TO MEMBRANE INTERFACE

MING XIE1*, AND STEPHEN R. GRAY1 1 Institue for Sustanbility and Innovation, Victoria Univeristy, Melbourne, VIC, 3030. Membrane silica scaling hinders sustainable water production. In this study, we elucidated silica scaling mechanisms on an asymmetric cellulose triacetate (CTA) membrane and polyamide thin-film composite (TFC) membrane. Scaling filtration showed that TFC membrane was subjected to more severe water flux decline in comparison with the CTA membrane, together with different scaling layer morphology. To elucidate the silica scaling mechanisms, silica species in the aqueous solution were characterised by mass spectrometry as well as light scattering. Key thermodynamic parameters of silica surface nucleation on the CTA and TFC membranes were estimated to compare the surface nucleation energy barrier. In addition, high resolution X-ray photoelectron spectroscopy resolved the chemical origin of the silica-membrane interaction via identifying the specific silicon bonds. For CTA membrane, silica scaling was promoted by the aggregation of mono-silicic acid into large silica aggregates, followed by the deposition from bulk solution onto the membrane surface; by contrast, silica surface polymerisation on the TFC membrane was the dominant mechanism where the majority of mono-silicic acid interacted with TFC membrane surface, which was followed by polymerisation of silica on the membrane surface resulting in severe water flux reduction. This hypothesis was supported by monitoring of aqueous silica species with mass spectrometry (Fig. 1) and light scattering techniques; as well as confirmed by the estimation of key silica nucleation parameters and high-resolution XPS analysis of Si 2p binding energy on the CTA and TFC membrane. For the CTA membrane, the aggregation of monomer silicic acid proceed via formation of dimmer – linear trimer – cyclic trimer, which resulted in a continuous increase in hydrodynamic radii as well as the weight-average molecular weight. However, for the TFC membrane, the major species of silica oligomers in the solution remained as cyclic trimer after ten-hours of scaling experiment, which was compounded by a largely unchanged hydrodynamic radii and weight-average molecular weight. Estimation of thermodynamic parameters of silica surface nucleation demonstrated a significant reduction of surface nucleation energy (more than 50%) for the TFC membrane in comparison with the CTA (Fig. 2). In addition, the Si 2p binding energy suggested different silicon bonds for the CTA (Si=O) and TFC (Si-O) membranes (Fig. 3), which supported the proposed chemical origins of silica scaling on these two membranes.

GOLD SPONSOR

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THEME: ENGINEERED OSMOSIS

Figure 1: Mass spectra for (A) CTA and (B) TFC membranes during silica scaling. The feed solution was sampled at the specific time interval and was diluted with methanol. The mass spectrometry conditions were: The direct infusion flow of the analyte was 10 µL/min. Electrospray negative ionization was used with the detector voltage of 3 kV, desolvation temperature of 250 ºC, and heating block temperature of 200 ºC. High purity nitrogen was used as the nebulizing gas at a flowrate of 1 L/min.

Nucleation E ven, ln(Nn)

25 20

CTA membrane TFC membrane

15 10 5 0.0

0.5 1.0 1.5 2.0 2 Solution Saturation State, 1/d

Figure 2: Estimation of silica surface nuleation parameters on CTA and TFC membranes by plotting the nucleation events (SEM-identifiable crystal number) as a function of the inverse square of saturation index. The slope of the trend line yields B, which is directly proportional to the energy barrier of nucleus formation ΔG*.

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30000

TFC membrane

CTA membrane

103.8 eV, Si-O

Intensity

25000 20000 15000 105.2 eV, Si=O

10000 5000

0 100 101 102 103 104 105 106 107 108

Binding Energy (eV) Figure 3: High resolution Si 2p scan by X-ray photoelectron spectroscopy of CTA and TFC membranes at the conclusion of silica scaling. Binding energy of Si 2p of 103.8 and 105.2 eV was for Si-O and Si=O bond, respectively

NAME Title: Dr Victoria University, Australia Phone: +61 3 9919 8174 Fax: +61 3 9919 8174 E-mail: [email protected] 2011-2014

University of Wollongong

2014

Yale University

Since 2015

Victoria University

Research interests: forward osmosis, membrane distillation, trace organic contaminant, membrane fouling

GOLD SPONSOR

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THEME: MEMBRANE DISTILLATION

THEME: MEMBRANE DISTILLATION TH1.11 YUN CHUL WOO OMNIPHOBIC MEMBRANE TO TREAT REVERSE OSMOSIS BRINE FROM COAL SEAM GAS PRODUCED WATER BY MEMBRANE DISTILLATION

YUN CHUL WOO1, LEONARD D. TIJING1, MINWEI YAO1, JUNE-SEOK CHOI2, HO KYONG SHON1* 1 Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney (UTS) P. O. Box 123, 15 Broadway, NSW 2007, Australia 2 Environment and Plant Research Institute, Korea Institute of Civil Engineering and Building Technology (KICT), 283, Goyangdae-Ro, Ilsanseo-Gu, Goyang-Si, Gyeonggi-Do 411-712, Republic of Korea 1. INTRODUCTION

Membrane distillation (MD) is a thermally-driven separation process using a hydrophobic membrane.1 Currently, most membranes used in MD are microfiltration (MF) membranes. However, MF membranes are not ideally fabricated for MD application. Thus, a new design of membrane surface structure should be developed for MD. Phase inversion is a commonly-used technique in fabricating membranes.2 However, current phase inverted membranes still suffer from low hydrophobicity and porosity, which consequently affect the membrane permeability and rejection. Therefore, several membrane designs and surface modification techniques have been carried out to enhance the membrane properties, such as plasma treatment and incorporation of nanoparticles in the polymer solution. However, those techniques still have their drawbacks and therefore in this study, an omniphobic membrane surface modification (both of superhydrophobic and oleophobic) was developed. In general, omniphobic membranes have been achieved by coating methods, and they have much higher wetting resistance against not only water but also low surface tension liquid contaminants.3 In the present study, an omniphobic coating was used with incorporation of silica aerogel to increase the roughness. A layer-by-layer (LBL) technique involving the deposition of separate layers was used to ensure strong adhesion between the membrane and silica aerogel and good coverage of the functional layer at the air interface. 2. MATERIALS & METHODS

In order to prepare the polyvinylidene fluoride (PVDF) solution, a PVDF concentration of 12 wt% was first dispersed in a certain amount of N, N – dimethylformamide (DMF). After that, the solution was mixed with 3 wt% lithium chloride (LiCl) by stirring (200 rpm) at 80°C for 2 hours. Afterwards, the PVDF solutions were further stirred (120 rpm) at 30°C for at least 24 hours. To fabricate PVDF flat-sheet membrane, the PVDF solution was poured over a glass

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plate and was gently lathered by a casting knife at a gap of 250 µm. Then, the lathered film solution was immediately immersed into a coagulation bath (de-ionized water, DI water) for 1 h. After completing coagulation, the membrane was transferred and immersed into another coagulation bath (DI water) for 24 h to remove the residual solvents, and afterwards, it was rinsed with DI water, followed by drying in the air at room temperature until a dry flat-sheet membrane was obtained. The LBL surface modification took four steps: 1) 5 wt% poly(diallyldimethylammonium chloride) (PDDA) was mixed with DI water by stirring for 2 h. After that, the PDDA solution was poured on the PVDF membrane, and after 40 min, the PDDA coated PVDF was rinsed with DI water to remove PDDA solution and dried by nitrogen (N2) gas. 2) 5 wt% silica aerogel (SiA) was dispersed in DI water, the SiA solution was then poured on the PDDA coated PVDF membrane surface, after that the SiA coated PDDA-PVDF membrane was rinsed with DI water and dried by N2 gas. 3) This step is same with step 1. 4) 1 wt% 1H, 1H, 2H, 2H – Perfluorodecyltriethoxysilane (FTCS) solution was poured on the PDDA-SiA coated PVDF membrane, after that the FTCS coated PDDA-SiA-PVDF membrane was rinsed with DI water and dried by N2 gas. The LBL surface modification procedure is illustrated in Fig. 1.

Figure 1 Graphical illustration for the surface modification by layer-by-layer assembly technique 3. RESULTS AND DISCUSSION

Fig. 2 shows the contact angle (CA), XPS results and AFM images of the neat and modified phase inversion membranes. The neat membranes showed much lower CA than the modified membranes, and the droplets failed to slide down while the modified membrane had very low sliding angle (Fig. 2(a)). Fig. 2(d) shows that contact angles of the coated membranes were 174° and 162°, with water (surface tension, ɤ= 72.8 mN/m) and ethanol (ɤ = 22.1 mN/m) droplets placed on its surface respectively. This suggests both superhydrophobic and superoleophobic characteristics. This combination of superhydrophobicity and superoleophobicity is due to low surface free energy of fluoropolymer (CF2-CF2) and trifluoromethyl (-CF3) (Fig. 2(e)) and high roughness of GOLD SPONSOR

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membrane surface. It can be clearly observed that this surface shows a structure with ridges and valleys, which are attributed to the formation of micro-beads (Fig. 2(f)). The roughness of the membrane was increased as the coated membrane had asperities scattered on the membrane surface, leading to its achievement of superomniphobicity. Air gap MD (AGMD) was carried out to evaluate the performance of the neat and coated membranes using RO brine from coal seam gas (CSG) produced water as feed. The water vapor flux of the neat and coated membranes was 11.6 LMH and 10.8 LMH, respectively. However, the neat membrane suffered the wetting problem during AGMD operation, while the coated membrane did not.

(a)

(b)

(c)

-CF2-CH2-

C-H

C=C

-CF2-CF2-

Ra 20.30 ± 1.46

(d)

(f)

(e) C-F -CF2-CF2-

-CF3

C=O

Ra 67.55 ± 19.67

Figure 2 (a, d) Water and ethanol contact and sliding angles, (b, e) XPS patterns of C1s and (c, f) AFM images of the (a, b, c) neat 12 wt% PVDF membrane and (d, e, f) PDDA-SiA-FTCS coated PVDF membrane 4. CONCLUSIONS

In the present study, omniphobic coating was implemented using a LBL technique on the phase inverted membrane. The coated membrane consisted of high water and ethanol contact angles due to the surface structure with ridges and valleys and low surface free energy on the membrane surface, which leads to high salt rejection and water vapor flux in long-term AGMD operation. Even though the coated membrane had a relatively low flux compared with the neat membrane, it showed stable water vapor flux and salt rejection performances during AGMD operation. It can be concluded that the omniphobic membrane has strong potential in membrane distillation.

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REFERENCES 1 E. Drioli et al., Desalination 2015, 356, 56-84 2 J. A. Kharraz et al., J. Mem. Sci 2015, 495, 404-414 3 S. Lin et al., ES&T Letters 2014, 11, 443-447

YUN CHUL WOO Title: Mr University of Technology Sydney (UTS), Australia Phone: +61 432 239 507 E-mail: [email protected] 2011-2013

M.S. at Myongji University, Republic of Korea

Since 2014

Ph.D. student at University of Technology Sydney (UTS), Australia

Research interests: Membrane Distillation, Forward Osmosis, Electrospinning, Membrane fabrication, Membrane modification.

GOLD SPONSOR

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THEME: MEMBRANE DISTILLATION

TH1.12 MING XIE FOULANT – MEMBRANE INTERACTION DURING MEMBRANE DISTILLATION: INSIGHTS FROM SYNCHROTRON FOURIER TRANSFORM INFRARED SPECTROSCOPY

MING XIE1*, WENHAI LUO2 AND STEPHEN R. GRAY1 1 Institue for Sustainability and Innovation, Victoria Univeristy, Melbourne, VIC, 3030. 2 School of Civil, Mining and Environmental Engineering, University of Wollongong, NSW, 2522 We evaluated foulant-membrane interaction in MD fouling process using ultra-bright synchrotron infrared (IR) beamline. MD membrane was fouled by varying model foulants. Water flux decline as well as product water quality was used to describe MD fouling profile. Synchrotron IR mapped the cross-section of fouled MD membrane, revealing the location and spatial distribution of foulants (Fig. 1). The mapping also enabled identifying the chemical information of foulant-membrane interface, which was vital to the behavior and mechanisms of the MD fouling. The Synchrotron IR imaging was further corroborated by element mapping, thereby elucidating the MD fouling mechanisms. These findings also highlight the efficiency of Synchrotron IR technique in characterization foulant-membrane interface. Figure 1: Synchrotron IR mapping during membrane distillation fouling, using (a) alginate with colloidal silica; (b) BSA with colloidal silica, and (c) humic acid with colloidal silica.

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(a) Alginate with colloidal silica

(b) BSA with colloidal silica

(c) humic acid with colloidal silica GOLD SPONSOR

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MING XIE Title: Dr Victoria University, Australia Phone: +61 3 9919 8174 Fax: +61 3 9919 8174 E-mail: [email protected] 2011-2014

University of Wollongong

2014

Yale University

Since 2015

Victoria University

Research interests: forward osmosis, membrane distillation, trace organic contaminant, membrane fouling

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DISTILLATION

TH1.13 G. NAIDU MEMBRANE DISTILLATION FOR SEAWATER REVERSE OSMOSIS (SWRO) BRINE TREATMENT AND METAL RECOVERY

G. NAIDU1, S. JEONG1,2, S. VIGNESWARAN1 1 Centre for Technology in Water and Wastewater (CTWW), Faculty of Engineering and IT, University of Technology, Sydney, Broadway, NSW 2007 Australia, 2 King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia INTRODUCTION

SWRO desalination technology has a fundamental role in mitigating water scarcity in many countries1. One of the limitations of SWRO technology is the large brine volume produced, necessitating brine treatment, incurring addition cost to desalination plants. Membrane distillation (MD) is an alternative thermal membrane technology with the ability to desalinate saline solutions2. As a technology that is not significantly affected by salinity, MD could potentially reduce SWRO brine volume while producing additional water. Further, valuable metals could be extracted from a supersaturated MD-SWRO brine solution, specifically rubidium (Rb). Rb, present at a concentration of 0.19 mg/L in SWRO brine, is a trace alkali metal with a high market price (€7856.64/kg), predominantly used in the field of laser technology and fiber optics3. The aim(s) of this study were to analyze the performance of MD for reducing SWRO brine volume and valuable Rb extraction.

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THEME: MEMBRANE DISTILLATION

Performance of a direct contact MD (DCMD) for SWRO brine volume reduction At a moderate temperature of 55°C, a DCMD operation achieved a stable initial permeate flux of 11 LMH with SWRO brine However, prevalent flux decline, membrane wetting and significant crystal deposition (SEM-EDS analysis) was observed (Fig. 1A). A simple approach of periodic membrane rinsing and batch crystallization was successful in reducing the crystal deposition on the MD membrane, enabling to concentrate SWRO brine by 4 times (Fig. 1B). Batch crystallization was carried out at low temperature (20 ºC) for 8h with slow stirring (50 rpm) inducing crystal formation that was filtered out (Fig. 1C). As a result, DCMD was able to achieve 70-75% recovery with SWRO brine.

. Fig. 1 DCMD flux pattern with SWRO brine (A) without membrane rinsing (B) with periodic membrane rinsing and (C) batch precipitation/crystallization

Extracting valuable Rb metal from MD concentrated SWRO brine A polymer (polyacrylonitrile, PAN) encapsulated potassium copper hexacyanoferrate (KCuFC) adsorbent, produced in the lab, showed selectivity to extract Rb from MD concentrated SWRO brine (Fig 2A). A high sorption of Rb was observed with KCuFC-PAN (maximum Langmuir 86.4 mg/g) with regenerative capacity (Fig. 2B). A 95% Rb desorption was achieved with 0.2 M KCl.

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THEME: MEMBRANE DISTILLATION

(A) (B) Fig. 2 Rb extraction by (A) lab produced polymer encapsulated KCuFC adsorbent (B) KCuFC in a fixed bed column (regenerative adsorption and desorption cycles). CONCLUSION

• DCMD was suitable to reduce SWRO brine volume (additional 70-75% recovery) when operated at moderate feed temperature of 55 °C, with periodic membrane rinsing, and batch precipitation/crystallization. At the same time, DCMD was able to concentrate Rb in SWRO brine. • A lab produced polymer encapsulated adsorbent, KCuFC-PAN was well suited for Rb sorption in fixed column mode (1.01 mmol/g) with regenerative capacity. REFERENCES 1

L.F. Greenlee, D.F. Freeman, B.D. Freeman, B. Marrot and P. Moulin, Water Res. 2009, 43, 2317-2348.

2

G. Naidu, S. Jeong, Y. Choi, E. Jang, T.M. Hwang, S. Vigneswaran, Desalination 2014, 345, 53-61.

3

G. Naidu, T. Nur, P. Loganathan, J. Kandasamy, S. Vigneswaran, Sep. Purif. Technol. 2016, 163,238246.

GAYATHRI NAIDU Title : Postdoctoral Research Fellow University of Technology Sydney, Australia Phone : +61-2-9514-2641 Fax: +61-2-9514-2633 E-mail : [email protected] Research interests: Membrane distillation, organic fouling and resource recovery

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THEME: MEMBRANE DISTILLATION

TH1.14 JIANFENG LI TREATMENT AND REUSE OF BIO-TREATED COKING WASTEWATER (BTCW) WITH MEMBRANE DISTILLATION: POSSIBILITIES AND CHALLENGES

JIANFENG LI, JING REN, CHEN ZHANG, FANGQIN CHENG Institute of Resources and Environmental Engineering, Shanxi University, PR China In China, pollution caused by coking wastewater remains a severe problem as China produces about 470 million tons of coke per year. Coking wastewater is often generated during high-temperature carbonation, coal gas purification, and chemical refining in coke plants. It is a typical toxic wastewater comprising hundreds of organic pollutants such as phenol, benzene, nitrogen heterocyclic compounds (e.g., quinoline, pyridine, and indole), and polycyclic aromatic hydrocarbons. Many of these compounds are refractory, toxic, mutative, and/or carcinogenic. Biological treatment is the widely used technology for BTCW prior to discharge to the receiving water bodies. Unfortunately, due to the presence of refractory and inhibitory contaminants, the effluents from these systems still contain a relatively high concentration of non-biodegradable organics. With more and more stringent regulations established or establishing in China and over the world, advanced treatment and zero discharge of the biologically treated coking wastewaters are becoming increasingly important. In the past decade, pressure driven membrane processes like UF, NF and or RO are often applied to treat and reuse this kind of wastewater. However, several pretreatment approaches like filtration, coagulation/ flocculation, and adsorption are required due to the membrane fouling problem. This makes the process very long and cause frequent failure due to the complexity of the system1. In this study, a direct contact membrane distillation (DCMD) system was developed for advanced treatment of BTCW, which has the potential to replace the current process, as is shown in Fig.1. The preliminary results are promising as the system can reject more than 97% of EfOM for 72hours without membrane wetting2, and flux decline was in an acceptable range (15-20%)(Fig.2). The effluent of organic matter (EfOM) at different operating times (0h, 24h, 48h and 72h) was characterized by GC-MS, 3D-EEM methods. It is interesting that the conductivity in the permeate increases at the first stage then decreases with the increase of time, which is corresponding to the release of EfOM3. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy demonstrated that the concentration of EfOM in distillate without pre-coagulation reached a peak in the second MD stage. While when MD was coupled with PACl/PAM, the EfOM peak was present earlier. GC/MS and 3D-EEM results suggested the EfOM remained in the permeate are low molecular weight (LMW) aromatics like benzene and it derives, and the interaction between coagulants and organics could influence the time of organics appeared in distillate (Fig.3). We suggest that the penetration of the LMW aromatics is likely due to fact that its vapor pressure difference across the membrane is greater than the membrane

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THEME: MEMBRANE DISTILLATION

resistance, as shown in Fig.4. Our work provides a novel convenient approach to treat and reuse biologically treated coking wastewater. An expanded study will involve exploring methods of exerting greater control over membrane fouling and energy utilization. REFERENCES 1

Jianfeng Li*, Jing Ren, Chen Zhang, Fangang Meng*, Fangqin Cheng*, Identifying the sources and fate of dissolved organic matter (DOM) in a large coking wastewater reclamation system, submitted to Water research.

2

Jianfeng Li, Jing Wu, Huifang Sun, Fangqin Cheng*, Yu Liu, Advanced treatment of biologically treated coking wastewater by membrane distillation coupled with pre-coagulation, Desalination 380 (2016) 43-51

3

Jing Ren, Chen Zhang, Jianfeng Li*, Fangqin Cheng*, Removal of dissolved organic matter (DOM) from bio-treated coking wastewater by membrane distillation, Oral presentation, The 5th IWA regional conference on Membrane Technology, Kunming, China Biological process

Advanced treatment

Raw

Anaerobic

Aerobic

Coagulation

MMF

UF

Adsorption

NF

RO

Figure 1. A typical coking wastewater treatment and reuse system (300m3/h) in Shanxi, China

BTCW PAC PAC/PAM Figure 2. The performance of DCMD system treating BTCW with and without coagulation/flocculation (a) conductivity and concentration factor (b) pictures before and after MD

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(a)

(b)

24h 48h 72h Figure 3. EfOM release during DCMD process (a) GC-MS results of EfOM in BTCW (b) 3D-EEM results of EfOM in the permeate of DCMD 4 50

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Figure 4. Possible mechanisms of EfOM release during DCMD of BTCW

JIANFENG LI Title: Associate Professor, PhD Shanxi University, PR China Phone: +86 13620612091 Fax: +86 351 7018553 E-mail: [email protected] 2003-2005

PhD candidate, Dalian Technological University, PR China

2005-2008

Joint PhD training program, Nanyang Technological University, Singapore

2008-2013

Research Fellow, Nanyang Technological University, Singapore

Since 2013

Associate professor, Shanxi University, PR China

Research interests: Membrane distillation, Membrane bioreactor, Wastewater reuse, Anti-fouling materials

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: MEMBRANE DISTILLATION

TH1.15 BERNA TOPUZ FABRICATION OF HIGH PERFORMANCE ZIF-8 MEMBRANES FOR GAS SEPARATION

BERNA TOPUZ1, MICHAEL TSAPATSIS2 1 Department of Chemical Engineering, Ankara University, Ankara 06100, Turkey 2 Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, MN, 55455, USA. High performance molecular sieving membranes have created interest as highperformance separation systems for production of petro-based and renewable fuels and chemicals. Compared to thermodynamically driven separation methods such as distillation, membrane-based processes can substantially reduce the energy and capital costs of separating molecules on a large scale. Separation based on the preferential adsorption and molecular sieving mechanisms can make the large-scale industrial deployment of membranes possible. The aim of this work is to fabricate ultra-thin MOFs (Metal Organic Frameworks) membranes by simple and low-cost method on ceramic supports for gas separation. MOFs consist of metal centers connected by coordination bonds to organic linker molecules. They have been used to grow crystalline molecular sieving membranes on disk and tubular substrates through techniques similar to those developed for zeolitic membranes. Due to their wide range of chemical composition, regular pore structure with high surface area and relatively high thermal and chemical stability they could find application as molecular sieving membranes, catalysis and gas storage materials. These materials can also grow as a membrane on polymeric support without any calcination process to activate the pores. Zeolitic imidazolate frameworks (ZIFs), as a subclass MOFs, have emerge excellent candidates for the fabrication of high-performance gas separation membranes due to their structural flexibility, which allows for rational design of pore sizes and surface properties. ZIF-8 with a sodalite (SOD) topology with a pore size of 0.34 nm, formed by bridging 2-methylimidazolate anions and zinc cations, is of particular interest for important separation such as H2 from hydrocarbons and propylene from propane. In the present work, gel-free method was introduced to fabricate thin ZIF-8 membranes on alumina support. For the application of this method, ZnO layer on porous alumina support was used for the ZIF-8 secondary growth. Following the vacuum coating of ZnO layer, the supports were subjected to impregnation of Hmim solution. The supports were then transferred to autoclave for the secondary growth at 120 oC for 24 h. A membrane thickness of less than 1 micron was obtained which resulted in a helium permeance of 1.6x10-6 molm-2s-1Pa-1 and a He/C3H8 separation factor (S.F.) of 25. This is the thinnest ceramic supported ZIF-8 membrane reported; though the S.F. is low. GOLD SPONSOR

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REFERENCES 1

K. Hartley, P. Lant, Biotechnol. Bioeng.2006, 95, 384-398

2

J. Cookney, E. Cartmell, B. Jefferson, E. J. McAdam, Water Sci. Technol. 2012, 65, 604-610

3

Y. Zhang, R. Wang, J. Membr. Sci. 2013, 443, 170-180

4

S. Wang, Y. Li, X. Fei, M. Sun, C. Zhang, Y. Li, Q. Yang, X. Hong, Journal of Colloid and Interface Science 2011, 359, 380-388

5

J. Xu, Y.B. Singh, G.L. Amy, N. Ghaffour, Journal of Membrane Science 2016, 512, 73-82

6

H.C. Yang, J.K. Pi, K.J. Liao, H. Huang, Q.Y. Wu, X.J. Huang, Z.K. Xu, Applied Materials & Interfaces 2014, 6, 12566-12572

7

K.M. Yeon, C.H. Lee, J.B. Kim, Environ. Sci. Technol., 2009, 43, 7403-7409

8

H.S. Oh, K.M. Yeon, C.S. Yang, S.R. Kim, C.H. Kim, S.Y. Park, J.Y. Han, J.K. Lee, Environ. Sci. Technol., 2012, 46, 4877-4984

9

S.K. Lee, S.K. Park, H.P. Kwon, S.H. Lee, C.H. Nahm, S.J. Jo, H.S. Oh, P.K. Park, K.H. Choo, C.H. Lee, T.W. Yi, Environ. Sci. Technol., 2016, 50, 1788-1795

10 M.S. Medina-Martinez, M. Uyttendaele, V. Demolder, J. Debevere, Food Microbiol., 2006, 23, 534-540 11 G. J. Millar et al., Renewable and Sustainable Energy Reviews 2016, 57, 669-691

2

3

L. D. Nghiem et al., Separation and Purification Technology 2015, 146, 94-100 H. C. Duong et al., Journal of Membrane Science 2015, 493, 673-682

12 K. Semenov et al., Progress in Solid State Chemistry. 2016, 44 (2), 59-74. 13 K. Otvagina et al., Membranes, 2016, 6(2), 31. 14 T. Sazanova et al., Petroleum Chemistry, 2016, 56(5), 427-435 15 A. J. Ansari, F. I. Hai, W. Gui, H. H. Ngo, W. E Price and L. D. Nghiem, Sci. Total Environ. 2016 566-567, 559-566. 16 M. Xie, L. D Nghiem, W. E. Price and M. Elimelech, Environ. Sci. Technol. Lett. 2014, 2, 191-195 17 A.J. Ansari, F. I. Hai, W. E. Price and L. D Nghiem, Sep. Purif. Technol. 2016, 163, 1-7. 18 A.J. Ansari, F. I. Hai, W. Guo, H. H. Ngo, W. E. Price and L. D. Nghiem, Bioresour. Technol. 2015, 191, 30-36. 19 W. Luo, F. I. Hai, W. E. Price, M. Elimelech and L. D. Nghiem, J. Membr. Sci. 2016, 514, 636-645.

This study was supported by The Scientific and Technological Research Council of Turkey (TUBITAK) within the context of 214M012 project. BERNA TOPUZ Title:.Assist. Prof. Dr. Affiliation, Country: Department of Chemical Engineering, Ankara University, Ankara 06100, Turkey. Phone: +90-532-5137502 E-mail:[email protected]

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ABSTRACTS

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THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION

THEME: ADVANCES IN MF AND UF MEMBRANES USE OF THE MICELLAR-ENHANCED ULTRAFILTRATION (MEUF) FOR FLUORIDE REMOVAL FROM AQUEOUS SOLUTIONS

MARTYNA GRZEGORZEK1, KATARZYNA MAJEWSKA-NOWAK1 1 Wrocław University of Science and Technology, Department of Environmental Engineering Wybrzeże Wyspiańskiego 27 50-370 Wrocław Poland Fluorine is a common chemical element with symbol F. It is freely soluble, for that reason in aqueous solutions fluorine only occurs as fluoride. According to World Health Organization standards, fluoride content in drinking water should not be higher than 1.5 mg F-/dm3. Fluorine can migrate to the environment from anthropogenic and natural sources. It is worth to know that the lack as well as the excess of fluorine can be harmful to human health. In small amounts fluorine is beneficial for health - it prevents against decay and osteoporosis. Fluorine excess leads to fluorosis, cancer or neurological problems. Elevated F- concentrations were monitored in many world regions, e.g. in China, India, Kenia, Ethiopia or Tanzania. Fluorine contamination became a global problem, for that reason new methods of fluoride removal should be developed. In this paper the experiments on fluoride removal with the use of micellar-enhanced ultrafiltration (MEUF) were described. MEUF is a process which combines conventional ultrafiltration (UF) and surfactant ability to form micelles (at a surfactant concentration greater than the critical micelle concentration CMC). The research were conducted with the use of UF cell (Amicon 8400) of volume equal to 350 cm3. Flat polymer membranes (Microdyn Nadir) made of polyethersulfone (PES4, cut-off 4 kDa) and cellulose (CEL5, cut-off 5 kDa) were applied in the experiments. Membrane diameter was equal to 76 mm. The MEUF process was carried out at a transmembrane pressure of 0.2 MPa. Fluoride concentration in model aqueous solutions amounted to 10 and 100 mgF-/dm3. The experimental solutions were made of NaF and cationic surfactants (octadecyloamine, ODA; cetylpyridinium chloride, CPC). Surfactant concentration was variable and amounted to 1, 2 and 3 CMC. Fluoride content was measured with use of colorimetric method with SPADNS reagent. It has been found, that application of CPC allowed to remove fluoride below permissible limit (< 1.5 mg F-/dm3). This satisfactory result was achieved at CPC concentration of 2 and 3 CMC for PES4 membrane and low initial fluoride concentration (10 mg F-/dm3). In the case of solutions containing 100 mg F-/dm3 the highest removal efficiency was equal to 51%. This result was obtained for ODA at 3CMC and PES4 membrane. Besides, it has been revealed that fluoride removal efficiency increased with increasing surfactant concentration. It has been also demonstrated that surfactants strongly influenced membrane permeabilty.

492

9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION MARTYNA GRZEGORZEK Title: M.Sc. Wrocław University of Science and Technology, Department of Environmental Engineering, Wybrzeże Wyspiańskiego27, 50-370 Wrocław, Poland Phone: +48713203639, E-mail: [email protected] 2013

B.Sc. in Environmental Protection, Wrocław University of Technology

2014

M.Sc. in Environmental Engineering, Wrocław University of Technology

Since 2014

Ph.D. student, Department of Environmental Engineering,



Wrocław University of Science and Technology

Research interests: membrane processes, water treatment, desalination

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493

THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION

GIL-SEON KANG EFFECT OF PA SYNTHESIS ACCORDING TO CHEMISTRY SURFACE OF AAO MEMBRANE

GIL-SEON KANG1, JI-BEOM YOO* 1 SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon, 440-746, Republic of Korea * School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon, 440-746, Republic of Korea Anodic Aluminum Oxide (AAO) membrane as support layer has ideal vertical structure, which is different from commercial polysulfone (PSf) membrane of Reverse Osmosis (RO) membrane. The surface property of AAO can also be changed from hydrophilicity to hydrophobicity by surface treatment. The different effects of AAO surface property could be compared by carbon-coated on AAO membrane using CVD without changing structure. Figure 1 shows the pore size evolution of water flux of variable pore size of hydrophilic and hydrophobic AAO membrane from 40 nm to 90 nm. The largest flux difference between hydrophobic and hydrophilic AAO exhibited at the pore size of 60 nm. Polyamide (PA) films were synthesized on AAO and C-AAO membrane by Interfacial Polymerization (IP) method during different time period. Different shapes of synthetic presented according to the surface chemistry property, as shown in the SEM images (figure 2, 3). In the case of hydrophobic surface AAO membrane, PA film synthesis rate was faster than hydrophilic surface, and formed upon the top of support layer unlike the synthesis of PA into the inner-pore of hydrophilic AAO membrane. For this reason, it is possible to research the effect of PA film as selective layer above the support layer. Accordingly, it could affect the permeability during the test of ion rejection

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Figure 1. Compare the water flux of the theoretical and experimental value. The theoretical water flux of each pore sizes along Hagen-Poiseuille eqn. The blue dot is water flux of hydrophilic surface (AAO membrane), and the red dot of hydrophobic surface (carbon-coated AAO membrane).

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

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Figure 2. PA synthesis on hydrophobic surface C-AAO membrane according to the time. At 5s, PA film wasn’t cover the surface of C-AAO membrane, but PA synthesis on top of C-AAO membrane after 10s.

Figure 3. PA synthesis on hydrophilic surface AAO membrane according to the time. PA synthesis on inner-pore of AAO membrane after 15s. And the PA film synthesis rate is slower than hydrophobic surface.

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THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION GIL-SEON KANG Title: Effect of PA synthesis according to chemeistry surface of AAO membrane Sungkyunkwan University, Suwon: Phone: +82-10-7353-1324 E-mail: [email protected] 2008

Bachelor’s degree in Advanced Material Science and Engineering, Kyung-sung University, Busan, Republic of Korea.

2012

Master degree in Advanced Material Science and Engineering, Sungkyunkwan University, Suwon. Republic of Korea.

Since 2013

Doctor course in SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon, Republic of Korea

Research interests: RO or NF membrane, desalination

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION

SIYING LI ONE-STEP GRAPHENE-POLYSULFONE MEMBRANE WITH ION SELECTIVITY

SIYING LI1, JUNG-HUN LEE2 1 SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon 440-746, Korea 2 School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746, Korea Recently, graphene is suggested as a promising material in the field of water purification or ion separation.1-4 Due to its one atomic layer thickness, the resistance of the flow of fluid and solutes could be minimized. Instead of simulation study, graphene membrane was researched as nanofiltration5 and water desalination6 membrane experimentally. Here, we report a fabrication method of large area graphene with high ion selectivity. Oxygen (Fig. 1) and Hydrogen plasma etching process7 were adopted to control the pores density and size on graphene. And subsequently, supporting layer formed via phase inversion of polysulfone (PSf) directly on graphene (fig.2; processes see Scheme 1). Using this method, a large area graphene membrane (7 cm x 4.5 cm) was fabricated. PSf acted not only as supporting of graphene during Cu etching, but also as the graphene membrane substrate, thus free of polymer residues and less tears or cracks appearing with the traditional polymer transfer method. This simple and convenient method could set the stage for graphene membrane commercial production. The selectivity and permeability of different ions and molecules were measured during forward osmosis (FO) process.

Scheme 1

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THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION

Figure 1. (a) Raman spectra of O2 plasma treated for 2, 4, 6, and 10 seconds at 15W and 480mTorr. (b) and (c) Time evolution of ID/IG and defect density in the unit of μm-2 when O2 plasma treated for 2, 4, 6, and 10 seconds, calculated from , and for Raman razer wavelength of 532nm, C=100.

Figure 2. (a-c) SEM images for graphene side surface, cross section, and polysulfone side surface.

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9TH INTERNATIONAL MEMBRANE SCIENCE AND TECHNOLOGY CONFERENCE

THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION SIYING LI Title: Ms. Affiliation, Country: SKKU Advanced Institute of Nanotechnology, Sungkyunkwan University, Republic of Korea Phone: +82 010 4950 2272 E-mail: [email protected] [email protected] Personal History: 2014 Bachelor degree from College of Material Science and Technolory, Harbin Institute of Technology, China Since 2014 Graduate student of Master and Doctor course in SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Republic of Korea Research interests: graphene membrane, polysulfone, desalination, ion separation

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THEME: ADVANCES IN MF AND UF MEMBRANES POSTER SESSION

YAN LV MUSSUL-INSPIRED NANOCOMPOSITE MEMBRANES FOR ENHANCED MECHANICAL STRENGTH AND WATER PERMEABILITY DURING NANOFILTRATION

YAN LV,1,2 YONG DU,1,2 WEN-ZE QIU,1,2 ZHI-KANG XU*,1,2 1 MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China 2 Key Laboratory of Adsorption and Separation Materials & Technologies of Zhejiang Province, Hangzhou 310027, China It is well accepted that water crisis caused by population growth and industry blossom is threatening the survival and development of human society all over the world.1 How to get clean water with high quality has become the world matter of concern. Nanofiltration is drawing much attention in the fields of drinkable water production, seawater desalination and wastewater treatment due to its superiorities of high water permeability, suitable retention to multivalent ions or organic molecules (200 - 1000 Da), and low operation pressure.2 A defect-free and stable selective layer is of critical significance for thin film composite membrane with excellent separation performance and service durability. Thin film nanocomposite (TFN) membranes have been prepared by mixing inorganic nanomaterials into the selective layer to improve