Table Of ContentMEMBRANE
SEPARATION
SYSTEMS
Recent Developments and
Future Directions
R.W. Baker, E.L. Cussler, W. Eykamp,
W.J. Koros, R.L. Riley, H. Strathmann
NOYES DATA CORPORATION
Park Ridge, New Jersey, U.S.A.
Copyright @ 1991 by Noyes Data Corporation
Library of Congress Catalog Card Number: 90.23675
ISBN: O-8155-1270-8
Printed in the United States
Published in the United States of America by
Noyes Data Corporation
Mill Road, Park Ridge, New Jersey 07656
10987654321
Library of Congress Cataloging-in-Publication Data
Membrane separation systems : recent developments and future
directions I by R.W. Baker . . . [et al.1 .
p. cm.
Includes bibliographical references and index.
ISBN O-8155-1270-8 :
1. Membrane separation. I. Baker, R.W. (Richard W.)
TP248.25.M46M456 1991
660’2842.-dc20 9923675
CIP
Acknowledgments
This report was prepared by the following group of experts:
Dr. Richard W. Baker (Membrane Technology & Research, Inc.)
Dr. Edward Cussler (University of Minnesota)
Dr. William Eykamp (University of California at Berkeley)
Dr. William J. Koros (University of Texas at Austin)
Mr. Robert L. Riley (Separation Systems Technology, Inc.)
Dr. Heiner Strathmann (Fraunhofer Institute, West Germany).
Mrs. Janet Farrant and Dr. Amulya Athayde edited the report, and also served as
project coordinators.
The following members of the Department of Energy (DOE) made valuable
contributions to the group meetings and expert workshops:
Dr. Richard Gordon (Office of Energy Research, Division of Chemical Sciences)
Dr. Gilbert Jackson (Office of Program Analysis)
Mr. Robert Rader (Office of Program Analysis)
Dr. William Sonnett (Office of Industrial Programs)
The following individuals, among others, contributed to the discussions and
recommendations at the expert workshops:
Dr. B. Bikson (Innovative Membrane Systems/Union Carbide Corp.)
Dr. L. Costa (Ionics, Inc.)
Dr. T. Davis (Graver Water, Inc.)
Dr. D. Elyanow (Ionics, Inc.)
Dr. H. L. Fleming (GFT, Inc.)
Dr. R. Goldsmith (CeraMem Corp.)
Dr. G. Jonsson (Technical University of Denmark)
Dr. K.-V. Peinemann (GKSS, West Germany)
Dr. R. Peterson (Filmtec Corp.)
Dr. G. P. Pez (Air Products & Chemicals, Inc.)
Dr. H. F. Ridgway (Orange County Water District)
Mr. J. Short (Koch Membrane Systems, Inc.)
Dr. K. Sims (Ionics, Inc.)
Dr. K. K. Sirkar (Stevens Institute of Technology)
Dr. J. D. Way (SRI International)
The following individuals served as peer reviewers of the final report:
Dr. J. L. Anderson (Carnegie Mellon University)
Dr. J. Henis (Monsanto)
Dr. J. L. Humphrey (J. L. Humphrey and Associates)
Dr. S.-T. Hwang (University of Cincinnati)
Dr. N.N. Li (Allied Signal)
Dr. S. L. Matson (Sepracor, Inc.)
Dr. R. D. Noble (University of Colorado)
Dr. M. C. Porter (M. C. Porter and Associates)
Dr. D. L. Roberts (SRI International)
Dr. S. A. Stern (Syracuse University)
2
Acknowledgments 3
Additional information on the current Federal Government support of membrane
research was provided by:
Dr. D. Barney
Dr. R. Bedick
Dr. R. Delafield
Dr. C. Drummond
Dr. R. Gajemki
Dr. L. Jarr
Dr. R. Cortesi
Dr. G. Ondich
PJational Once Foundation
Dr. D. Bruley
Dr. D. Greenberg
Foreword
This book discusses recent developments and future directions in the field of
membrane separation systems. It describes research needed to bring energy-sav-
ing membrane separation processes to technical and commercial readiness for
commercial acceptance within the next 5 to 20 years. The assessment was con-
ducted by a group of six internationally known membrane separations experts
who examined the worldwide status of research in the seven major membrane
areas. This encompassed four mature technology areas: reverse osmosis, micro-
filtration, ultrafiltration, and electrodialysis; two developing areas: gas separa-
tion and pervaporation; and one emerging technology: facilitated transport.
Membrane based separation technology, a relative newcomer on the separation
scene, has demonstrated the potential of saving enormous amounts of energy
in the processing industries if substituted for conventional separation systems.
It has been estimated that over 1 quad annually, out of 2.6, can possibly be
saved in liquid-to-gas separations, alone, if membrane separation systems gain
wider acceptance. In recent years great strides have been made in the field and
even greater future energy savings should be available when these systems are
substituted for such conventional separation techniques as distillation, evapora-
tion, filtration, sedimentation, and absorption.
The book pays particular attention to identifying currently emerging innova-
tive processes, and to further improvements which could gain even wider accep-
tance for the more mature membrane technologies. In all, 38 priority research
areas were selected and ranked in order of priority, according to their relevance,
likelihood of success, and overall impact. Rationale was presented for all the
final selections; and the study was peer reviewed by an additional ten experts.
The topics that were pointed out as having the greatest research emphasis are
pervaporation for organic-organic separations; gas separations; microfiltration;
an oxidant-resistant reverse osmosis membrane; and a fouling-resistant ultra-
filtration membrane.
V
vi Foreword
The information in the book is from Membrane Separation Systems, Volume I-
Executive Summary, and Volume II-Final Report, by the Department of
Energy Membrane Separation Systems Research Needs Assessment Group,
authored by R.W. Baker, E.L. Cussler, W. Eykamp, W.J. Koros, R.L. Riley, and
H. Strathmann. The report was prepared by Membrane Technology & Research,
Inc. of Menlo Park, California, for the U.S. Department of Energy Office of
Program Analysis, April 1990.
The table of contents is organized in such a way as to serve as a subject index
and provides easy access to the information contained in the book.
Advanced composition and production methods developed by
Noyes Data Corporation are employed to bring this durably
bound book to you in a minimum of time. Special techniques
are used to close the gap between “manuscript” and “completed
book.” In order to keep the price of the book to a reasonable
level, it has been partially reproduced by photo-offset directly
from the original report and the cost saving passed on to the
reader. Due to this method of publishing, certain portions of the
book may be less legible than desired.
NOTICE
The studies in this book were sponsored by the U.S.
Department of Energy. On this basis the Publisher
assumes no responsibility nor liability for errors or any
consequences arising from the use of the information
contained herein.
Mention of trade names, commercial products, and
suppliers does not constitute endorsement or recommen-
dation for use by the Agency or the Publisher. Final
determination of the suitability of any information or
product for use contemplated by any user, and the man-
ner of that use, is the sole responsibility of the user.
The book is intended for informational purposes only.
The reader is warned that caution must always be ex-
ercised when dealing with hazardous materials in mem-
brane separation systems, and expert advice should be
obtained before implementation is considered.
Contents and Subject Index
VOLUME I
1. EXECUTIVE SUMMARY. ................................ .4
References. ...................................... .8
2. ASSESSMENT METHODOLOGY ........................... .9
2.1 Authors. ........................................ .9
2.2 Outline and Model Chapter. .......................... .I2
2.3 First Group Meeting. ............................... .I2
2.4 Expert Workshops. ................................ .I2
2.5 Second Group Meeting. ............................. .17
2.6 Japan/Rest of the World Survey. ........................ 17
2.7 Prioritization of Research Needs. ........................ 17
2.8 Peer Review. .................................... .I7
References. ..................................... .I8
3. INTRODUCTION. .................................... .19
3.1 Membrane Processes. ............................... .I9
3.2 Historical Development ............................. .27
3.3 The Future. ..................................... .29
3.3.1 Selectivity ................................ .29
3.3.2 Productivity. .............................. .30
3.3.3 Operational Reliability. ....................... .31
References. ..................................... .33
4. GOVERNMENT SUPPORT OF MEMBRANE RESEARCH .......... .34
4.1 Overview ....................................... .34
4.2 U.S. Government Supported Membrane Research ............ .37
4.2.1 Department of Energy ........................ .37
vii
viii Contents and Subject Index
4.2.1.1 Office of Industrial Programs/Industrial
Energy Conservation Program ............. .37
4.2.1.2 Office of Energy Research/Division of
Chemical Sciences. .................... .39
4.2.1.3 Office of Energy Research/Division of
Advanced Energy Projects. ............... .40
4.2.1.4 Office of Fossil Energy. ................. .41
4.2.1.5 Small Business Innovative Research Program. ... .42
4.2.2 National Science Foundation. ................... .45
4.2.3 Environmental Protection Agency ................ .46
4.2.4 Department of Defense. ....................... .47
4.2.5 National Aeronautics and Space Administration ....... .48
4.3 Japanese Government Supported Membrane Research ......... .48
4.3.1 Ministry of Education ........................ .49
4.3.2 Ministry of International Trade and Industry (MITI) .... .49
4.3.2.1 Basic Industries Bureau. ................. .49
4.3.2.2 Agency of Industrial Science and Technology
(AIST) ............................ .50
4.3.2.3 Water Re-Use Promotion Center (WRPC) ...... .51
4.3.2.4 New Energy Development Organization
(NEDO). ........................... .52
4.3.3 Ministry of Agriculture, Forestry and Fisheries ........ .52
4.4 European Government Supported Membrane Research. ........ .52
4.4.1 European National Programs. ................... .53
4.4.2 EEC-Funded Membrane Research. ................ .54
4.5 The Rest of the World .............................. .55
5. ANALYSIS OF RESEARCH NEEDS ........................ .56
5.1 Priority Research Topics. ............................ .56
5.2 Research Topics by Technology Area .................... .65
5.2.1 Pervaporation .............................. .66
5.2.2 Gas Separation ............................. .68
5.2.3 Facilitated Transport. ........................ .70
5.2.4 Reverse Osmosis ............................ .72
5.2.5 Microfiltration ............................. .74
5.2.6 Ultrafiltration. ............................. .76
5.2.7 Electrodialysis ............................. .78
5.3 Comparison of Different Technology Areas ................ .79
5.4 General Conclusions. ............................... .81
References. ..................................... .84
APPENDIX A. PEER REVIEWERS’ COMMENTS ................. .86
A.1 General Comments ................................ .86
A.l.l The Report Is Biased Toward Engineering, or Toward
Basic Science .............................. .86
A.1.2 The Importance of Integrating Membrane Technology
Into Total Treatment Systems. .................. .87
A.1.3 The Ranking Scheme ......................... .88
Contents and Subject Index ix
A.1.4 Comparison with Japan ....................... .89
A.2 Specific Comments on Applications ..................... .90
A.2.1 Pervaporation .............................. .90
A.2.2 Gas Separation ............................. .91
A.2.3 Facilitated Transport. ........................ .91
A.2.4 Reverse Osmosis ............................ .92
A.2.5 Ultrafiltration. ............................. .92
A.2.6 Microfiltration ............................. .93
A.2.7 Electrodialysis ............................. .93
A.2.8 Miscellaneous Comments ...................... .93
VOLUME II
INTRODUCTION TO VOLUME II. ........................... .96
References. ..................................... .99
1. MEMBRANE AND MODULE PREPARATION. ................. 100
R.W. Baker
1 .I Symmetrical Membranes. ............................ 102
1.1.1 Dense Symmetrical Membranes .................. 102
1.1.1.1 Solution Casting. ..................... 102
1.1.1.2 Melt Pressing ........................ 102
1.1.2 Microporous Symmetrical Membranes. ............. 105
1.1.2.1 Irradiation .......................... 105
1.1.2.2 Stretching .......................... 105
1.1.2.3 Template Leaching .................... 109
1.2 Asymmetric Membranes ............................. 109
1.2.1 Phase Inversion (Solution-Precipitation) Membranes. .... 109
1.2.1 .I Polymer Precipitation by Thermal Gelation .... 110
1.2.1.2 Polymer Precipitation by Solvent Evaporation . 114
1.2.1.3 Polymer Precipitation by lmbibition of Water
Vapor ............................ .I14
1.2.1.4 Polymer Precipitation by Immersion in a
Nonsolvent Bath (Loeb-Sourirajan Process) .... 116
1.2.2 Interfacial Composite Membranes. ................ 118
1.2.3 Solution Cast Composite Membranes. .............. 121
1.2.4 Plasma Polymerization Membranes ................ 123
1.2.5 Dynamically Formed Membranes ................. 125
1.2.6 Reactive Surface Treatment. .................... 125
1.3 Ceramic and Metal Membranes. ........................ 126
1.3.1 Dense Metal Membranes ....................... 126
1 .3.2 Microporous Metal Membranes. .................. 126
1.3.3 Ceramic Membranes. ......................... 126
1.3.4 Molecular Sieve Membranes. .................... 127
1.4 Liquid Membranes. ................................ 131
1.5 Hollow-Fiber Membranes ............................ 132
1.5.1 Solution (Wet) Spinning. ...................... 134
1.5.2 Melt Spinning .............................. 134
x Contents and Subject Index
1.6 Membrane Modules ................................ 136
1.6.1 Spiral-Wound Modules ........................ 136
1.6.2 Hollow-Fiber Modules ........................ 140
1.6.3 Plate-and-Frame Modules ...................... 140
1.6.4 Tubular Systems. .......................... .I40
1.6.5 Module Selection. ........................... 140
1.7 Current Areas of Membrane and Module Research. ........... 144
References. ........................................ .I46
2. PERVAPORATION. .................................. .151
R. W. Baker
2.1 Process Overview. ................................. 151
2.1 .I Design Features. ............................ 154
2.1.2 Pervaporation Membranes. ..................... 156
2.1.3 Pervaporation Modules. ....................... 156
2.1.4 Historical Trends. ........................... 159
2.2 Current Applications, Energy Basics and Economics. .......... 160
2.2.1 Dehydration of Solvents. ...................... 161
2.2.2 Water Purification. .......................... 164
2.2.3 Pollution Control ........................... 169
2.2.4 Solvent Recovery ........................... 171
2.2.5 Organic-Organic Separations .................... 174
2.3 Industrial Suppliers ................................ 176
2.4 Sources of Innovation .............................. 180
2.5 Future Directions ................................. 182
2.5.1 Solvent Dehydration ......................... 182
2.5.2 Water Purification ........................... 184
2.5.3 Organic-Organic Separations .................... 184
2.6 DOE Research Opportunities. ......................... 185
2.6.1 Priority Ranking ............................ 186
2.6.1 .I Solvent Dehydration ................... 186
2.6.1.2 Water Purification. .................... 186
2.6.1.3 Organic-Organic Separations .............. 186
References. ..................................... 187
3. GAS SEPARATION. .................................. .I89
NJ. Koros
3.1 Introduction. .................................... 189
3.2 Fundamentals. .................................. .I91
3.3 Membrane System Properties. ......................... 193
3.4 Module and System Design Features ..................... 195
3.5 Historical Perspective. .............................. 199
3.6 Current Technical Trends in the Gas Separation Field. ......... 200
3.6.1 Polymeric Membrane Materials. .................. 200
3.6.2 Plasticization Effects ......................... 203
3.6.3 Nonstandard Membrane Materials. ................ 205
3.6.4 Advanced Membrane Structures. ................. 205
3.6.5 Surface Treatment to Increase Selectivity. ........... 205
