advanced membrane technology

ADVANCED MEMBRANE
TECHNOLOGY AND
APPLICATIONS
ADVANCED MEMBRANE
TECHNOLOGY AND
APPLICATIONS
Edited By
Norman N. Li, Anthony G. Fane,
W. S. Winston Ho, and T. Matsuura
Copyright # 2008 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data:
Advanced membrane technology and applications/edited by Norman N. Li [et al.].
p. cm.
Includes index.
ISBN 978-0-471-73167-2 (cloth)
1. Membranes (Technology) 2. Six sigma (Quality control standard) 3. Membrane industry.
I. Li, Norman N.
TP159.M4A38 2008
660
0
.28424—dc22 2007041577
Printed in the United States of America
10987654321
&
CONTENTS
PREFACE xv
ABOUT THE EDITORS xvii
CONTRIBUTORS xix
PART I MEMBRANES AND APPLICATIONS IN WATER
AND WASTEWATER 1
1. Thin-Film Composite Membranes for Reverse Osmosis 3
Tadahiro Uemura and Masahiro Henmi
1.1 Introduction 3
1.2 Application of RO Membranes 3
1.3 Major Progress in RO Membranes 4
1.4 Trends in RO Membrane Technology 6
1.5 Reverse Osmosis/Biofouling Protection 13
1.6 Low-Fouling RO Membrane for Wastewater Reclamation 14
1.7 Chlorine Tolerance of Cross-Linked Aromatic Polyamide Membrane 17

References 18
2. Cellulose Triacetate Membranes for Reverse Osmosis 21
A. Kumano and N. Fujiwara
2.1 Introduction 21
2.2 History of Cellulose Acetate Membrane 21
2.3 Toyobo RO Module for Seawater Desalination 22
2.4 Actual Performance of Toyobo RO Module for Seawater Desalination 28
2.5 Most Recent RO Module of Cellulose Triacetate 35
2.6 Conclusion 43
References 45
3. Seawater Desalination 47
Nikolay Voutchkov and Raphael Semiat
3.1 Introduction 47
3.2 Seawater Desalination Plant Configuration 50
3.3 Water Production Costs 82
v
3.4 Future Trends 84
3.5 Conclusion 85
References 85
4. Seawater Desalination by Ultralow-Energy Reverse Osmosis 87
R. L. Truby
4.1 Introduction 87
4.2 SWRO Energy Reduction Using Energy Recovery Technology 88
4.3 SWRO Energy Optimization 95
4.4 Affordable Desalination Collaboration (ADC) 96
4.5 Conclusion 99
Acknowledgments 100
References 100
5. Microfiltration and Ultrafiltration 101
N. Kubota, T. Hashimoto, and Y. Mori

5.1 Introduction 101
5.2 Recent Trends and Progress in MF/UF Technology 104
5.3 Future Prospects 127
References 128
6. Water Treatment by Microfiltration and Ultrafiltration 131
M. D. Kennedy, J. Kamanyi, S. G. Salinas Rodrı
´
guez, N. H. Lee,
J. C. Schippers, and G. Amy
6.1 Introduction 131
6.2 Materials, Module Configurations, and Manufacturers 133
6.3 Microfiltration/Ultrafiltration Pretreatment 142
6.4 Membrane Applications 146
6.5 Membrane Fouling and Cleaning 149
6.6 Integrated Membrane Systems (MF or UF þ RO or NF) 160
6.7 Backwash Water Reuse, Treatment, and Disposal 164
References 165
7. Water Reclamation and Desalination by Membranes 171
Pierre Co
ˆ
te
´
, Mingang Liu, and Steven Siverns
7.1 Introduction 171
7.2 Water Reclamation and Seawater Desalination 172
7.3 Cost Estimation 173
7.4 Process Options for Water Reclamation 174
7.5 Cost of Water Reclamation 177
7.6 Process Options for Desalination 181
7.7 Cost of Desalination 181

vi CONTENTS
7.8 Water Reuse versus Desalination 185
7.9 Conclusions 186
References 186
8. Chitosan Membranes with Nanoparticles for Remediation
of Chlorinated Organics 189
Yit-Hong Tee and Dibakar Bhattacharyya
8.1 Introduction 189
8.2 Experimental Section 191
8.3 Results and Discussions 197
8.4 Conclusions 212
Acknowledgment 212
References 212
9. Membrane Bioreactors for Wastewater Treatment 217
P. Cornel and S. Krause
9.1 Introduction 217
9.2 Principle of the Membrane Bioreactor Process 217
9.3 MBR Design Considerations 230
9.4 Applications and Cost 233
9.5 Conclusions and Summary 235
References 237
10. Submerged Membranes 239
Anthony G. Fane
10.1 Introduction 239
10.2 Modes of Operation of Submerged Membranes 241
10.3 Submerged Membrane Module Geometries 246
10.4 Bubbling and Hydrodynamic Considerations 253
10.5 Practical Aspects 262
10.6 Applications 267
10.7 Conclusions 268

References 268
11. Nanofiltration 271
Bart Van der Bruggen and Jeroen Geens
11.1 Introduction 271
11.2 Process Principles 272
11.3 Application of Nanofiltration for Production of Drinking Water
and Process Water 276
11.4 Wastewater Polishing and Water Reuse 280
11.5 Other Applications 283
CONTENTS vii
11.6 Solvent-Resistant Nanofiltration 284
11.7 Conclusions 287
Acknowledgment 288
References 288
12. Membrane Distillation 297
Mohamed Khayet
12.1 Introduction to Membrane Distillation 297
12.2 Membrane Distillation Membranes and Modules 305
12.3 Membrane Distillation Membrane Characterization Techniques 320
12.4 Transport Mechanisms in MD: Temperature Polarization,
Concentration Polarization, and Theoretical Models 331
12.5 Membrane Distillation Applications 341
12.6 Long-Term MD Performance and Membrane Fouling in MD 355
12.7 Hybrid MD Systems 356
12.8 Concluding Remarks and Future Directions in MD 357
Acknowledgments 360
References 360
13. Ultrapure Water by Membranes 371
Avijit Dey
13.1 Introduction 371

13.2 Integrated Membrane Technology in UPW Systems 377
References 403
PART II MEMBRANES FOR BIOTECHNOLOGY AND
CHEMICAL/BIOMEDICAL APPLICATIONS 407
14. Tissue Engineering with Membranes 409
Zhanfeng Cui
14.1 Introduction 409
14.2 Hollow-Fiber Membrane Bioreactors for Three-Dimensional
Tissue Culture 412
14.3 Micromembrane Probes for Tissue Engineering Monitoring 420
14.4 Future Opportunities 427
14.5 Summary 429
Acknowledgments 429
References 429
15. Biopharmaceutical Separations by Ultrafiltration 435
Raja Ghosh
15.1 Introduction 435
15.2 Ultrafiltration: An Overview 436
viii CONTENTS
15.3 Basic Working Principles of Ultrafiltration 437
15.4 Ultrafiltration Membranes and Devices 438
15.5 Ultrafiltration Processes 446
15.6 Conclusion 449
References 450
16. Nanofiltration in Organic Solvents 451
P. Silva, L. G. Peeva, and A. G. Livingston
16.1 Organic Solvent Nanofiltration Membranes 451
16.2 OSN Transport Mechanisms—Theoretical Background 458
16.3 Applications of Organic Solvent Nanofiltration 461
References 465

17. Pervaporation 469
Fakhir U. Baig
17.1 Introduction 469
17.2 Applications of AZEO SEP and VOC SEP 471
17.3 Computer Simulation of Module Performance 475
17.4 Permeation and Separation Model in Hollow-Fiber
Membrane Module 481
17.5 Conclusion 487
References 488
18. Biomedical Applications of Membranes 489
G. Catapano and J. Vienken
18.1 Introduction 489
18.2 Membrane Therapeutic Treatments 490
18.3 Medical Membrane Properties 496
18.4 Medical Membrane Materials 501
18.5 Biocompatibility of Membrane-Based Therapeutic Treatments 508
18.6 Conclusions 511
References 513
19. Hemodialysis Membranes 519
Norma J. Ofsthun, Sujatha Karoor, and Mitsuru Suzuki
19.1 Introduction 519
19.2 Transport Requirements 521
19.3 Other Requirements 525
19.4 Membrane Materials, Spinning Technology, and Structure 527
19.5 Dialyzer Design and Performance 530
19.6 Current Market Trends 533
CONTENTS ix
19.7 Future Directions 533
19.8 Conclusions 536
References 536

20. Tangential-Flow Filtration for Virus Capture 541
S. Ranil Wickramasinghe
20.1 Introduction 541
20.2 Tangential-Flow Filtration 543
20.3 Tangential-Flow Filtration for Virus Capture 545
20.4 Tangential-Flow Filtration for Virus Clearance 550
20.5 Conclusions 552
Acknowledgments 553
References 553
PART III GAS SEPARATIONS 557
21. Vapor and Gas Separation by Membranes 559
Richard W. Baker
21.1 Introduction to Membranes and Modules 559
21.2 Membrane Process Design 563
21.3 Applications 567
21.4 Conclusions 577
21.5 Glossary 577
References 578
22. Gas Separation by Polyimide Membranes 581
Yoji Kase
22.1 Introduction 581
22.2 Permeability and Chemical Structure of Polyimides 582
22.3 Manufacture of Asymmetric Membrane 587
22.4 Membrane Module 588
22.5 Applications of Polyimide Gas Separation Membranes 589
References 597
23. Gas Separation by Carbon Membranes 599
P. Jason Williams and William J. Koros
23.1 Introduction 599
23.2 Structure of Carbon Membranes 599

23.3 Transport in Carbon Membranes 601
23.4 Formation of Carbon Membranes 604
23.5 Current Separation Performance 616
x CONTENTS
23.6 Production of CMS Modules 620
23.7 Challenges and Disadvantages of CMS Membranes 622
23.8 Direction of Carbon Membrane Development 626
Acknowledgments 627
References 627
24. Polymeric Membrane Materials and Potential Use in
Gas Separation 633
Ho Bum Park and Young Moo Lee
24.1 Introduction 633
24.2 Basic Principles of Gas Separation in Polymer Membranes 635
24.3 Limitations of Gas Separations Using Polymer Membranes 643
24.4 Polymer Membrane Materials 646
24.5 Membrane Gas Separation Applications and Conclusions 659
References 664
25. Hydrogen Separation Membranes 671
Yi Hua Ma
25.1 Introduction 671
25.2 Porous Nonmetallic Membranes for Hydrogen Separations 672
25.3 High-Temperature Hydrogen Separation Membranes 674
25.4 Concluding Remarks 680
References 681
PART IV MEMBRANE CONTACTORS AND REACTORS 685
26. Membrane Contactors 687
Kamalesh K. Sirkar
26.1 Introduction 687
26.2 Membrane-Based Contacting of Two Fluid Phases 690

26.3 Membrane-Based Solid–Fluid Contacting 696
26.4 Two Immobilized Phase Interfaces 697
26.5 Dispersive Contacting in a Membrane Contactor 699
26.6 Concluding Remarks 700
References 700
27. Membrane Reactors 703
Enrico Drioli and Enrica Fontananova
27.1 State-of-the-Art On Catalytic Membrane Reactors 703
27.2 Advanced Oxidation Processes for Wastewater Treatments 704
27.3 Selective Oxidations 710
CONTENTS xi
27.4 Biocatalytic Membrane Reactors 712
27.5 Catalytic Crystals 712
27.6 Inorganic Membrane Reactors 713
27.7 Microreactors 713
27.8 Conclusions 714
Acknowledgments 715
References 715
PART V ENVIRONMENTAL AND ENERGY APPLICATIONS 719
28. Facilitated Transport Membranes for Environmental, Energy,
and Biochemical Applications 721
Jian Zou, Jin Huang, and W. S. Winston Ho
28.1 Introduction 721
28.2 Supported Liquid Membranes with Strip Dispersion 729
28.3 Carbon-Dioxide-Selective Membranes 737
28.4 Conclusions 747
Acknowledgment 749
References 749
29. Fuel Cell Membranes 755
Peter N. Pintauro and Ryszard Wycisk

29.1 Introduction to Fuel Cells 755
29.2 Background on Fuel Cell Membranes 759
29.3 Recent Work on New Fuel Cell Membranes 764
29.4 Conclusions 779
References 779
PART VI MEMBRANE MATERIALS AND CHARACTERIZATION 787
30. Recent Progress in Mixed-Matrix Membranes 789
Chunqing Liu, Santi Kulprathipanja, Alexis M. W. Hillock,
Shabbir Husain, and William J. Koros
30.1 Introduction 789
30.2 Recent Progress in Mixed-Matrix Membranes 794
30.3 Summary and Future Opportunities 809
References 809
31. Fabrication of Hollow-Fiber Membranes by Phase Inversion 821
Tai-Shung Neal Chung
31.1 Introduction 821
31.2 Basic Understanding 822
xii CONTENTS
31.3 Recent Progresses on Single-Layer Asymmetric Hollow-Fiber
Membranes 825
31.4 Dual-Layer Hollow Fibers 831
31.5 Concluding Remarks 835
Acknowledgments 835
References 835
32. Membrane Surface Characterization 841
M. Kallioinen and M. Nystro
¨
m
32.1 Introduction 841
32.2 Characterization of the Chemical Structure of a Membrane 842

32.3 Characterization of Membrane Hydrophilicity 852
32.4 Characterization of Membrane Charge 855
32.5 Characterization of Membrane Morphology 859
32.6 Conclusions 867
Acknowledgment 869
References 869
33. Membrane Characterization by Ultrasonic
Time-Domain Reflectometry 879
William B. Krantz and Alan R. Greenberg
33.1 Introduction 879
33.2 Principle of UTDR Measurement 880
33.3 Characterization of Inorganic Membrane Fouling 882
33.4 Characterization of Membrane Biofouling 885
33.5 Characterization of Membrane Compaction 886
33.6 Characterization of Membrane Formation 889
33.7 Characterization of Membrane Morphology 891
33.8 Summary and Recommendations 894
Acknowledgments 896
References 896
34. Microstructural Optimization of Thin Supported Inorganic
Membranes for Gas and Water Purification 899
M. L. Mottern, J. Y. Shi, K. Shqau, D. Yu, and Henk Verweij
34.1 Introduction 899
34.2 Morphology, Porosity, and Defects 902
34.3 Optimization of Supported Membrane Structures 908
34.4 Synthesis and Manufacturing 917
34.5 Characterization 918
34.6 Conclusions 923
Acknowledgment 926
References 926

CONTENTS xiii
35. Structure/Property Characteristics of Polar Rubbery Membranes
for Carbon Dioxide Removal 929
Victor A. Kusuma, Benny D. Freeman, Miguel Jose-Yacaman, Haiqing Lin,
Sumod Kalakkunnath, and Douglass S. Kalika
35.1 Introduction and Background 929
35.2 Theory and Experiment 931
35.3 Results and Discussion 937
35.4 Conclusions 950
Acknowledgments 950
References 950
Index 955
xiv CONTENTS
&
PREFACE
Since the last membrane book I published with the New York Academy of Sciences, I have
attended several quite large membrane conferences including the one that I organized in
the beautiful city of Irsee, Germany. I was struck by the fact that there had been very
good progress made in the broad field of membranes science and technology. Also, mem-
branes seem to be coming to the center of the water treatment and desalination technologies.
Many parts of the world now are in critical need of clear water. Membrane technology is
gaining increasing importance in treating and reusing wastewater and in producing
potable water from seawater. It appears there is a timely need for a book that comprehen-
sively reviews the up-to-date membrane technology and its many applications.
To undertake the task of publishing this book, I invited three of my colleagues, Tony
Fan, Winston Ho, and Takeshi Matsuura to help, thus a team of four editors. Together
we invited 35 chapters to cover membrane applications from gas to water separations.
These chapters are now divided into six categories—membranes and applications in
water and wastewater, membranes and applications in biotechnology and biomedical
engineering, gas separations, membrane contactors and reactors, environmental and

energy applications, and membrane materials and characterization. These six categories
indeed cover a very broad field of applications.
I believe three somewhat unique features can be said about these chapters. One is that the
percentage of contributors from industry is high. This is, of course, a relative comparison, in
general, with the other published membrane books. As we know, most of the authors of the
chapters in a membrane book are from academia, whereas many of the contributors from
this book are from some of the major international membrane manufacturing companies.
The other feature is that the chapters, in general, are more into applications than theories.
The third feature is that a very strong coverage of water treatment and purification is
presented for the reason mentioned above.
We are truly gratified to the strong response to contributing chapters. As a matter of fact,
we still have quite many chapters that have been promised but have not been finished. This
prompted me to consider publishing a second book in the near future. Meanwhile, we are
indeed very pleased to have this book published and wish to thank all the reviewers and
chapter contributors.
N
ORMAN N. LI
NL Chemical Technology, Inc.
Mount Prospect, Illinois
xv
&
ABOUT THE EDITORS
Dr. Norman N. Li has about 40 years of working experience in the chemical and petroleum
industries. He was a senior scientist with Exxon Research and Engineering Co, Director of
Separation Science and Technology at UOP Co. and Director of Research and Technology
at AlliedSignal Co. (now part of Honeywell). Since 1995, he is the president of NL
Chemical Technology, Inc., which focuses on the development of membrane technologies.
Dr. Li has more than 100 technical publications, 44 U.S. patents, and 13 books edited, all
in the field of separation science and technology. He received the prestigious Award of
Separation Science and Technology from the American Chemical Society, the Founders

Award, Alpha Chi Sigma Award for Chemical Engineering Research, and the Award in
Chemical Engineering Practice from the American Institute of Chemical Engineers and
the Perkin Medal from the Society of Chemical Industry. The American Institute of
Chemical Engineers held special symposia on membranes in his honor at its national meet-
ings in 1995 and 2000. Dr. Li served as the president of the North American Membrane
Society and the chair of the International Congress on Membranes and Membrane
Processes (ICOM) in 1990. He is a member of the National Academy of Engineering,
United States.
Dr. Tony Fane is a chemical engineer with a Ph.D. from Imperial College, London. He has
been working on membranes since 1973 when he joined the University of New South
Wales, in Sydney, Australia. His current interests are in membranes applied to environ-
mental applications and the water cycle, with a focus on the sustainability aspects of mem-
brane technology. He is a former director of the UNESCO Centre for Membrane Science
and Technology at UNSW and recently Temasek Professor at Nanyang Technological
University, Singapore. He is currently director of the Singapore Membrane Technology
Centre at NTU. He is on the editorial board of the Journal of Membrane Science and
Desalination. He is a fellow of the Australian Academy of Technological Sciences and
Engineering, a recipient of the Centenary Medal in 2002 for services to Chemical
Engineering and the Environment, and an honorary life member of the European
Membrane Society.
Dr. W. S. Winston Ho is University Scholar Professor of Chemical and Materials Science
and Engineering at the Ohio State University since 2002. Previously, he was a professor of
chemical engineering at the University of Kentucky, after having more than 28 years of
industrial R&D experience with Allied Chemical, Xerox, and Exxon, and serving as
senior vice-president of technology at Commodore Separation Technologies. He was
elected a member of the National Academy of Engineering, United States, in 2002. A
New Jersey Inventor of the Year (1991), Dr. Ho holds more than 50 U.S. patents in
separation processes. He is co-editor of Membrane Handbook and the recipient of the
Professional and Scholarly Publishing Award for the most outstannding engineering
work in 1993. He received the 2006 Institute Award for Excellence in Industrial Gases

xvii
Technology and the 2007 Clarence G. Gerhold Award from AIChE. He obtained his B.S.
degree from National Taiwan University and his M.S. and Ph.D. degrees from the
University of Illinois at Urbana–Champaign, all in chemical engineering.
Dr. Takeshi Matsuura received his B.Sc. and M.Sc. degrees from the Department of
Applied Chemistry, University of Tokyo, and his doctoral degree from the Institute of
Chemical Technology of the Technical University of Berlin in 1965. After working at
the Department of Synthetic Chemisty of the University of Tokyo as a staff assistant and
at the Department of Chemical Engineering of the University of California as a postdoc,
he joined the National Research Council of Canada in 1969. He became a chair professor
at the University of Ottawa in 1992. He also served as the director of the Industrial
Membrane Research Institute until he retired in 2002. He is now a visiting professor
at the National University of Singapore and the University Technology Malaysia,
Skudai. Dr. Matsuura received the Research Award of International Desalination and
Environmental Association in 1983. A symposium of membrane gas separation was held
at the Eighth Annual Meeting of the North American Membrane Society, May 18–22,
1996, Ottawa, to honor him and Dr. S. Sourirajan. He received the George S. Links
Award for Excellence in Research from University of Ottawa in 1998. He has published
more than 300 articles in refereed journals, authored and co-authored 3 books, and
edited 4 books.
xviii ABOUT THE EDITORS
&
CONTRIBUTORS
Fakhir U. Baig, Petro Sep Membrane Technologies Inc., Oakville, Ontario, Canada
Richard W. Baker, Membrane Technology and Research, Inc., Menlo Park, California
94025
Dibakar Bhattacharyya, Department of Chemical and Materials Engineering, University
of Kentucky, Lexington, Kentucky 40506-0046
Bart Van Der Bruggen and Jeroen Geens, Department of Chemical Engineering,
Laboratory for Applied Physical Chemistry and Environmental Technology, University

of Leuven, Leuven, Belgium
G. Catapano, Department of Chemical Engineering and Materials, University of Calabria,
Rende (CS), Italy
Tai-Shung Neal Chung, Department of Chemical and Biomolecular Engineering,
National University of Singapore, Singapore 119260
P. Cornel, Technische Universita
¨
t Darmstadt, Department of Civil Engineering, Institute
WAR, Darmstadt, Germany
Pierre Co
ˆ
te
´
and Mingang Liu, GE Water and Process Technologies, ZENON Membrane
Solutions, Ontario, L6M 4B2, Can ada
Zhanfeng Cui, Department of Engineering Science, Oxford University, Oxford, United
Kingdom
Avijit Dey, Director – Application and Research, Omexell Inc., Stafford, Texas 77477
Enrico Drioli and Enrica Fontananova, Institute on Membrane Technology of the
National Council Research (ITM-CNR), and Department of Chemical Engineering and
Materials, University of Calabria, Rende (CS), Italy
Anthony G. Fane, UNESCO Centre for Membrane Science & Technology, University of
New South Wales, Australia 2052 and Singa pore Membrane Technology Centre,
Nanyang Technological University, Singapore
Raja Ghosh, Department of Chemical Engineering, McMaster University, Hamilton,
Ontario L8S 4L7, Canada
Alan R. Greenberg, Department of Mechanical Engineering, University of Colorado,
Boulder, Colorado 80309-0427
Alexis M. W. Hillock, Shabbir Husain, and William J. Koros, School of Chemical &
Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia, 30332

xix
Sumod Kalakkunnath, Department of Chemical and Materials Engineering and Center
for Manufacturing, University of Kentucky, Lexington, Kentucky 40506-0046
Douglass S. Kalika, Department of Chemical and Materials Engineering and Center for
Manufacturing, University of Kentucky, Lexington, Kentucky 40506-0046
M. Kallioinen and M. Nystro
¨
m, Laboratory of Membrane Technology and Technical
Polymer Chemistry, Department of Chemical Technology, Lappeenranta University of
Technology (LUT), Lappeenranta, Finland
Sujatha Karoor, Renal Division, Baxter Healthcare Corp., McGaw Park, Illinois,
Massachusetts
Yoji Kase, UBE Industries Ltd., Ichihara, Chiba 290-0045, Japan
M. D. Kennedy, J. Kamanyi, S. G. Salinas Rodrı
´
guez, N. H. Lee, J. C. Schippers, and
G. Amy, UNESCO–IHE Institute for Water Education, 2601 DA Delft, The
Netherlands
Mohamed Khayet, Department of Applied Physics I, Faculty of Physics, University
Complutense of Madrid, Madrid, Spain
William B. Krantz, Department of Chemical and Biomolecular Engineering, National
University of Singapore, The Republic of Singapore, 117576
S. Krause, Microdyn-Nadir GmbH, Wiesbaden, Germany
N. Kubota, T. Hashimoto, and Y. Mori, Microza Research & Development Department,
Specialty Products & Systems R&D Center, Asahi Kasei Chemicals Corporation, Fuji
City, Shizuoka, 416-8501 Japan
A. Kumano and N. Fujiwara, Desalination Membrane Operating Department, Toyobo
Co., Ltd., Osaka, Japan
Victor A. Kusuma, Benny D. Freeman, and Miguel Jose-YacamaN, Department of
Chemical Engineering, University of Texas at Austin, Austin, Texas 78712

Haiqing Lin, Membrane Technology and Research, Inc., Menlo Park, California 94025
Chunqing Liu and Santi Kulprathipanja, UOP LLC, 25 East Algonquin Road, Des
Plaines, Illinois, 60017
Yi Hua Ma, Center for Inorganic Membrane Studies, Department of Chemical
Engineering, Worcester Polytechnic Institute, Worcester, Massachusetts 01609
M. L. Mottern, J. Y. Shi, K. Shgau, D. Yu, and Henk Verweiji, Department of Materials
Science & Engineering, The Ohio State University, Columbus, Ohio 43210-1178
Norma J. Ofsthun, Clinical Science Department, Fresenius Medical Care, Lexington,
Massachusetts 02420
Ho Bum Park and Young Moo Lee, School of Chemical Engineering, Hanyang
University, Seoul, South Korea
Peter N. Pintauro and Ryszard Wycisk, Department of Chemical Engineering, Case
Western Reserve University, Cleveland, Ohio 44106-7217
xx CONTRIBUTORS
Raphael Semiat, Technion, Israel Institute of Technology, The Wolfson Chemical
Engineering Department, Technion City, Haifa, Israel
P. Silva, L. G. Peeva, and A. G. Livingston, Department of Chemical Engineering,
Imperial College, London SW7 2BY, United Kingdom
Kamalesh K. Sirkar, Otto H. York Department of Chemical Engineering, Center for
Membrane Technologies, New Jersey Institute of Technology, Newark, New Jersey
07102
Steven Siverns, EnviroTower, Toronto, Ontario, M5V 1R7 , Canada
Mitsuru Suzuki, Medical Membrane Department, Toyobo Corp., Osaka, Japan
Yit-Hong Tee, Department of Chemical and Materials Engineering, University of
Kentucky, Lexington, Kentucky 40506-0046
R. L. Truby, Toray Membranes, Escondido, California 92026
Tadahiro Uemura and Masahiro Henmi, Global Environment Research Laboratories,
Toray Industries Inc., Otsu Shiga, Japan
J. Vienken, Fresenius Medical Care, Bad Homburg, Germany
Nikolay Voutchkov, Poseidon Resources Corporation, Stamford, Connecticut

S. Ranil Wickramasinghe, Department of Chemical and Biological Engineering,
Colorado State University, Fort Collins, Colorado 80523-1370
P. Jason Williams and William J. Koros, School of Chemical and Biomolecular
Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332
Jian Zou, Jin Huang, and W. S. Winston Ho, Department of Chemical and
Biomolecular Engineering, Department of Materials Science and Engineering, The
Ohio State University, Columbus, Ohio 43210-1180
CONTRIBUTORS xxi
&
PART I
MEMBRANES AND APPLICATIONS IN
WATER AND WASTEWATER
&
CHAPTER 1
Thin-Film Composite Membranes for
Reverse Osmosis
TADAHIRO UEMURA and MASAHIRO HENMI
Global Environment Research Laboratories, Toray Industries Inc., Otsu Shiga, Japan
1.1 INTRODUCTION
Because of vastly expanding populations, increasing water demand, and the deterioration of
water resource quality and quantity, water is going to be the most precious resource in the
world. Thus, the 21st century is called the “water century.” In the 20th century, membrane
technologies made great progress, and commercial markets have been spreading very
rapidly and throughout the world. The key technologies fueling this progress are as follows:
1. Materials: Chemical design of high-performance materials suitable for each separ-
ation mode
2. Morphology: Morphological design of high-performance membranes
3. Element/Module: Element and module design for high-performance membranes
4. Membrane Process: Plant design and operation technology
In 21st century, to solve these water problems, membranes technology is going to be further

expanded and new technology—further improvements of membrane performance, develop-
ment of membrane systems, membranes stability such as antifouling membranes for
wastewater treatment, and other highly qualified membranes—will be needed.
Among desalination technologies available today, reverse osmosis (RO) is regarded as
the most economical desalination process. Therefore, RO membranes have played crucial
roles in obtaining fresh water from nonconventional water resources such as seawater
and wastewater.
1.2 APPLICATION OF RO MEMBRANES
Reverse osmosis membranes have been used widely for water treatment such as ultrapure
water makeup, pure boiler water makeup in industrial fields, seawater and brackish water
Advanced Membrane Technology and Applications. Edited by Norman N. Li, Anthony G. Fane,
W. S. Winston Ho, and T. Matsuura
Copyright # 2008 John Wiley & Sons, Inc.
3
desalination in drinking water production, and wastewater treatment and reuse in industrial,
agricultural, and indirect drinking water production as shown in Table 1.1.
The expansion of RO membrane applications promoted the redesign of suitable
membrane material to take into consideration chemical structure, membranes configuration,
chemical stability, and ease of fabrication. And along with the improvements of the
membranes, the applications are further developed.
1.3 MAJOR PROGRESS IN RO MEMBRANES
1.3.1 Cellulose Acetate Membrane
Reverse osmosis systems were originally presented by Reid in 1953. The first membrane,
which could be used at the industrial level in actual water production plants, was a
cellulose-acetate-based RO membrane invented by Loeb and Sourirajan in 1960. This
membrane has a so-called asymmetric or anisotropic membrane structure having a very
thin solute-rejecting active layer on a coarse supporting layer, as shown in Figure 1.1.
The membrane is made from only one polymeric material, such as cellulose acetate, and
made by the nonsolvent-induced phase separation method. After the invention by Loeb
and Sourirajan, spiral-wound membranes elements using the cellulose acetate asymmetric

flat-sheet membranes were developed and manufactured by several U.S. and Japanese
companies. RO technologies have been on the market since around 1964 (Kurihara et al.,
1987). They were widely used from the 1960s through the 1980s mainly for pure water
makeup for industrial processes and ultrapure water production in semiconductor industries;
and some are still used in some of these applications.
TABLE 1.1 Application of Reverse Osmosis Membrane Process
Industrial Use Drinking Water Wastewater Treatment and Reuse
Ultrapure water, boiler
water, process pure
water, daily
industries
Seawater desalination,
brackish water
desalination
Industrial water, agricultural
water, indirect drinking water
Figure 1.1 SEM photograph of CA asymmetric membrane.
Figure 1.2 Representative chemical structure of linear polyamide membrane (B-10).
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THIN-FILM COMPOSITE MEMBRANES FOR REV ERSE OSMOSIS
TABLE 1.2 Summary of Membrane Materials for RO
Membrane Material Membrane Morphology
Module
Configuration Examples of Membrane and Module, Membrane Suppliers
Cellulose acetate
Spiral 1. Toray, UOP, environgenics, Osmonics, Desalination, Ajax,
Hydranautics, Daiseru
4. Toray-Polyamidic acid, Du Pont-DP-1, Monsanto
6. Cellanese-Polybenzimidazole
9. UOP-CTA

10. North Star-NS-100, UOP-PA-300, -100, LP-300, RC-100
12. North Star-NS-200, Osmonics-NS-200 Environgenics-SPFA
(NS-200), Desalination-NS-200(?)
14. North Triangle Inst Plasma Polym. Toray-PEC-1000, Film
Tec-FT-30 Asahi Glass-MVP, Nihon Syokubai
Polyamide
Heterocyclic polymer
Cross-linked water-soluble
polymer
Hollow fiber 2. Dow, Monsanto, Toyobo
5. Du Pont
7. Cellanese-Polybensimidazole
13. FRL-NS-200, Gulf South Research Inst NS-100
Polymerizable monomer
(cross-linking)
Tubular 3. UOP, Environgenics, Universal Water Co. Raypak, Abcor,
PCI, Nitto, Daiseru
8. Teijin-PBIL
11. North Star-NS-100, Others Sumitomo-PAN-Composite
Memberane
5
1.3.2 Aromatic Polyamide Hollow Fiber Membrane
Since then, there has been intensive and continuous R&D efforts mainly around the United
States and Japan to meet the demands from commercial markets, and there exist many
inventions and breakthroughs in membrane materials and configurations to improve the
performances of membranes.
To overcome the problems of cellulose acetate membranes, many synthetic polymeric
materials for reverse osmosis were proposed, but except for one material, none of them
proved successful. The only one material, which could remain on the market, was the
linear aromatic polyamide with pendant sulfonic acid groups, as shown in Figure 1.2.

This material was proposed by DuPont, which fabricated very fine hollow fiber membranes;
the modules of this membrane were designated B-9 and B-10. They have a high rejection
performance, which can be used for single-stage seawater desalination. They were widely
used for mainly seawater or brackish water desalination and recovery of valuable materials
such as electric deposition paints, until DuPont withdrew them from the market in 2001.
1.3.3 Composite Membrane
Another approach to obtain a high-performance RO membrane was investigated by some
research institutes and companies in the 1970s. Many methods to prepare composite
membranes have been proposed, as shown in Table 1.2. In the early stage, very thin
films of a cellulose acetate (CA) polymer coating on a substrate, such as a porous cellulose
nitrate substrate, was tried. However, in spite of their efforts, this approach did not succeed
in industrial membranes manufacturing.
The next approach used the interfacial polycondensation reaction to form a very thin
polymeric layer onto a substrate. Morgan first proposed this approach (Morgan, 1965),
and then Scala et al. (1973) and Van Heuven (1976) actually applied this approach to
obtain an RO membrane. But it was Cadotte who invented the high-performance membrane
using the in situ interfacial condensation method (Cadotte, 1985). In his method, interfacial
condensation reactions between polymeric polyamine and monomeric polyfunctional acid
halides or isocyanates takes place on a substrate material to deposit a thin film barrier onto a
substrate. Some of the composite membranes were succeeded in industrial fabrication by
another method, which was designated as PA-300 or RC-100.
Another preparation method for composite membrane is an in situ monomer con-
densation method using the monomeric amine and monomeric acid halide, which was
also invented by Cadotte. Then, many companies succeeded in developing composite
membranes using this method, and the membrane performance has been drastically
improved up to now. Now, composite membrane of cross-linked fully aromatic polyamide
is regarded as the most popular and reliable material in the world. Permeate flow rate and its
quality have been improved 10 times greater than that of the beginning (Kurihara et al.,
1987, 1994b).
1.4 TRENDS IN RO MEMBRANE TECHNOLOGY

Figure 1.3 shows recent trends in RO membrane technology with two obvious tendencies.
One is a tendency toward low-pressure membranes for operating energy reduction in the
field of brackish water desalination. The other is a tendency toward high rejection with
high-pressure resistance in the large seawater desalination market.
6 THIN-FILM COMPOSITE MEMBRANES FOR REV ERSE OSMOSIS