Membrane Handbook

Membrane Handbook Edited by

W. s. Winston Ho, Ph.D. and

Kamalesh K. Sirkar, Ph.D.

~.

" SPRINGER SCIENCE+BUSINESS MEDIA, LLC

Library of Congress Cataloging-in-Publication

Membrane handbook/editors, W.S. Winston Ho and Kamalesh K. Sirkar. p. em.

Includes index. ISBN 978-1-4613-6575-4 ISBN 978-1-4615-3548-5 (eBook) DOI 10.1007/978-1-4615-3548-5 1. Membranes (Teehnology)--Handbooks, manuals, etc. 1. Ho, W.S. Winston 1943-

II. Sirkar, Kamalesh L., 1942-TP159.M4M4444 1992 660' .2842--dc20

Copyright © 1992 by Springer Science+Business Media New York Origina1ly published by Van Nostrand Reinhold in 1992 Softcover reprint of the hardcover 1 st edition 1992 This Printing 2001 by Kluwer Academic Publishers

This printing is a digital duplicat ion of the original edition.

91-43661 CIP

AII rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, mechanical, photo-copying, recording, or otherwise, without the prior written permission of the publisher, Springer Science+ Business Media, LLC

Printed an acid-free paper.

To Annie Ho and Keka Sirkar for their support and

To the scientists and engineers for advancing membrane science and technology

Applications of membrane processes are rapidly expanding in fields ranging from chemical engineering, environmental science, and water treatment to food science and electronic engineering. As a result, there is a critical need for a central resource on these processes that bridges the gap between fundamentals and everyday industrial uses. This new work answers that need by offering a comprehensive description of principles, membranes, membrane modules, process design, applications, cost estimates, and data for membrane processes.

The Membrane Handbook thoroughly examines today's commercialized membrane processes. It also details new membrane processes under development. Each process is described in significant detail, with coverage of theory, design considerations, and cost-effective operation.

The handbook first deals with commercialized but not always well-understood membrane processes: • gas permeation' pervaporation • dialysis' electrodialysis· reverse osmosis' ultrafiltration' microfiltration • emulsion liquid membranes.

It then examines new membrane processes under development, as well as membrane-based controlled release. You'll find information on: • membrane-based solvent extraction· hollow­fiber contained liquid membrane· membrane reactors· facilitated transport· electrostatic pseudo-liquid-membrane· membrane-based gas absorption and stripping· membrane distillation· perstraction • controlled release.

Enhanced by more than 400 illustrations, the handbook serves as an invaluable tool for scientists and engineers in the chemical, petroleum, petrochemical, paper, textile, pharmaceutical, and electronic industries. It offers sound practical guidance for food and medical technologists, as well as for engineers involved in pollution control, water treatment, biotechnology, and chemical processing. Moreover, this handbook provides a solid foundation for specialized graduate courses in separations, membrane processes, membrane reactors, controlled release using synthetic membranes, and diffusion in thin films.

About the Editors

W.S. Winston Ho, Ph.D., is a Senior Engineering Associate in Corporate Research of Exxon Research and Engineering Company in Annandale, New Jersey. He has written numerous papers and several book chapters on membranes and separation processes, including a chapter on membrane processes in Perry's Chemical Engineers' Handbook. A co-inventor of membrane solvent extraction and Exxon's FLEXSORS® gas treating technology and New Jersey Inventor of the Year of 1991, Dr. Ho holds about 30 U.S. patents in membranes and separation processes.

Kamalesh K. Sirkar, Ph.D., holds a Sponsored Chair in membrane separations and biotechnology and is a Professor of Chemical Engineering at New Jersey Institute of Technology in Newark, New Jersey. He was with Stevens Institute of Technology. He has authored many papers and several book chapters on membrane processes and jointly edited New Membrane Materials and Processes for Separation. He is on the editorial board of Journal of Membrane Science. Holder of several U.S. patents and a consultant to industry, Dr. Sirkar is the inventor of contained liquid membrane and solvent extraction technologies based on microporous membranes.

List of Contributors

Mauro A. Accomazzo, Ph.D., Vice President, Research & Development, IonPure Technologies Corporation, 10 Technology Drive, Lowell, MA 01851 (Part VIII, Microfiltration: Chapter 34, Deadend Microfiltration: Applications, Design, and Cost). Previous affiliation: Millipore Corporation.

Dibakar Bhattacharyya, Ph.D., Professor, Department of Chemical Engineering and Center of Membrane Scien­ces, University of Kentucky, Lexington, KY 40506 (Part VI, Reverse Osmosis: Chapters 21-24, Introduction and Definitions, Theory, Design, and Selected Applications)

Robert H. Davis, Ph.D., Associate Professor, Department of Chemical Engineering, University of Colorado, Boul­der, CO 80309-0424 (Part VIII, Microfiltration: Chapters 31-33, Definitions, Theory for Deadend Microfiltration, and Theory for Crossflow Microfiltration)

Anthony J. Dileo, Ph.D., Manager, Advanced Separations Group, Millipore Corporation, 80 Ashby Road, Bedford, MA 01730 (Part VIII, Microfiltration: Chapter 34, Dead­end Microfiltration: Applications, Design, and Cost)

Josef Draxler, Dr.-Ing., Assistant Professor, Institute for Chemical Engineering and Environmental Technologies, Technical University of Graz, Inffeldgasse 25, A-8010 Graz, Austria (Part IX, Emulsion Liquid Membranes: Chapters 39 and 40, Applications and Capital and Op­erating Costs)

Gregory K. Fleming, Ph.D., Research Engineer, E. I. Du Pont de Nemours & Company, Inc., Willow Bank Plant, 305 Water Street, Newport, DE 19804 (Part II, Gas Permeation: Chapters 2-6, Definitions, Theory, Design of Gas Permeation Systems, Applications, and Eco­nomics)

Hubert L. Fleming, Ph.D., Vice President, Marketing and Commercial Development, Zenon Environmental, Inc., 13 Estates Drive, Sussex, NJ 07461 (Part III, Pervapora­tion: Chapters 7-10, Definitions and Background, Theory, Design, and Applications and Economics)

Edward W. Funk, Ph.D., Manager of Process Technology, Engineered Products and Process Technology, Allied Signal, Inc .. 50 East Algonquin Road, Des Plaines. IL 60017 (part VII, Ultrafiltration: Chapters 26-30, In­troduction and Definitions, Theory and Mechanistic Con­cepts, Membranes, Module and Process Configuration, and Applications and Economics)

Vinay Goel, Ph.D., Vice President, Membrane Research. Millipore Corporation, 80 Ashby Road, Bedford, MA

01730 (Part VIII, Microfiltration: Chapters 34 and 35, Deadend Microfiltration: Applications, Design, and Cost and Crossflow Microfiltration: Applications, Design, and Cost)

Donald C. Grant, M.S., Research Manager, FSI In­ternational, 322 Lake H<\Zeltine Drive, Chaska, MN 55318 (part VIII, Microfiltration: Chapter 32, Theory for Deadend Microfiltration)

Zhongmao Gu, B.S., Separations Group Leader, China Institute of Atomic Energy, P.O. Box 275-93, Beijing 102413, China (Part IX, Emulsion Liquid Membranes: Chapter 38, Design Considerations; Part X, New Mem­brane Processes under Development: Chapter 45, Electrostatic Pseudo-Liquid-Membrane)

Scott M. Herbig, M.S., Director, Controlled Release Phar­maceuticals, Bend Research, Inc., 64550 Research Road, Bend, OR 97701 (Part XI, Chapter 47, Controlled Release)

W. S. Winston Ho, Ph.D., Senior Engineering Associate, Corporate Research, Exxon Research and Engineering Company, Route 22 East, Annandale, NJ 08801 (Part I, Chapter I, Overview: Part IX, Emulsion Liquid Mem­branes: Chapters 36-38, Definitions, Theory, and Design Considerations)

Robert Kaiser, Sc.D., President, ARGOS Associates, Inc., 12 Glengarry Road, Winchester, MA 01890 (Part VIII, Microfiltration: Chapters 34 and 35, Deadend Microfil­tration: Applications, Design, and Cost and Crossflow Microfiltration: Applications, Design, and Cost)

Stephen B. Kessler, M.Eng., Manager, Product Develop­ment, Sepracor Inc., 33 Locke Drive, Marlborough, MA 01752 (part IV, Dialysis: Chapters 11-15, Definitions, Theory, Design, Applications, and Cost Estimates)

Elias Klein, Ph.D., Professor, Kidney Disease Program, University of Louisville, Louisville, KY 40292 (Part IV, Dialysis: Chapters 11-15, Definitions, Theory, Design, Applications, and Cost Estimates)

Sudhir S. Kulkarni, Ph.D., Scientist, Chemical Engineer­ing Division, National Chemical Laboratory, Pune 411008, India (Part VII, Ultrafiltration: Chapters 26-30, Introduction and Definitions, Theory and Mechanistic Concepts, Membranes, Module and Process Configura­tion, and Applications and Economics)

Norman N. Li, Sc.D., Director, Engineered Products and Process Technology, Allied Signal, Inc., 50 East Algon­quin Road, Des Plaines, IL 600 17 (Part VII, Ultrafiltra-

vii

viii List of Contributors

tion: Chapters 2~30, Introduction and Definitions, Theory and Mechanistic Concepts, Membranes, Mod­ule and Process Configuration, and Applications and Economics; Part IX, Emulsion Liquid Membranes: Chapters 3~38, Definitions, Theory, and Design Con­siderations)

Sudipto Majumdar, Ph.D., Research Associate, Center for Membranes and Separation Technologies, Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Hoboken, NJ 07030 (Part X, New Mem­brane Processes under Development: Chapter 42, Hollow-Fiber Contained Liquid Membrane). Present ad­dress: Department of Chemical Engineering, Chemistry and Environmental Science, New Jersey Institute of Technology, University Heights, Newark, NJ 07102

Rolf J. Marr, Dr.-Ing., Professor, Institute for Chemical Engineering and Environmental Technologies, Tech­nical University of Graz, Inffeldgasse 25, A-8010 Graz, Austria (Part IX, Emulsion Liquid Membranes: Chap­ters 39 and 40, Applications and Capital and Operating Costs)

Stephen L. Matson, Ph.D., President, Arete Technologies, hic., 15 Withington Lane, Harvard, MA 01451 (Part X, New Membrane Processes under Development: Chapter 43, Membrane Reactors)

Scott B. McCray, Ph.D., Director of Membrane Develop­ment, Bend Research, Inc., 64550 Research Road, Bend, OR 97701 (Part VI, Reverse Osmosis: Chapters 23 and 24, Design and Selected Applications)

Peter M. Meier, Ph.D., U.S. Marketing Manager, Food and Beverage, Millipore Corporation, 80 Ashby Road, Bedford, MA 01730 (Part VIII, Microfiltration: Chapter 34, Deadend Microfiltration: Applications, Design, and Cost)

Stephen L. Michaels, M.S., Marketing Manager, Process Systems Division, Millipore Corporation, 80 Ashby Road, Bedford, MA 01730 (Part VIII, Microfiltration: Chapter 35, Crossflow Microfiltration: Applications, De­sign, and Cost)

Leon Mir, Ph.D., Vice President & General Manager, Process Systems Division, Millipore Corporation, 80 Ashby Road, Bedford, MA 01730 (Part VIII, Microfiltration: Chapter 35, Crossflow Microfiltration: Applications, Design, and Cost)

Richard D. Noble, Ph.D., Professor, Department of Chemi­cal Engineering, Center for Separations Using Thin Films, University of Colorado, Boulder, CO 80309-0424 (Part X, New Membrane Processes under Development: Chapter 44, Facilitated Transport)

Aldo Pitt, M.S., Consulting Scientist, Millipore Corpora­tion, 80 Ashby Road, Bedford, MA 01730 (Part VIII, Microfiltration: Chapter 34, Deadend Microfiltration: Applications, Design, and Cost)

Malcolm Pluskal, Ph.D., Consulting Scientist, Millipore Corporation, 80 Ashby Road, Bedford, MA 01730 (Part VIII, Microfiltration: Chapter 34, Deadend Microfiltra­tion: Applications, Design, and Cost)

Ravi Prasad, Ph.D., Senior Development Engineer, Sepa­rations Products Division, Hoechst Celanese Corpora­tion, Charlotte, NC 28273 (Part X, New Membrane Pro-

cesses under Development: Chapter 41, Membrane­Based Solvent Extraction)

John A. Quinn, Ph.D., Robert D. Bent Professor, Depart­ment of Chemical Engineering, University of Penn­sylvania, Philadelphia, PA 19104-6393 (Part X, New Membrane Processes under Development: Chapter 43, Membrane Reactors)

Roderick J. Ray, Ph.D., Vice President and Chief Operat­ing Officer, Bend Research, Inc., 64550 Research Road, Bend, OR 97701 (Part VI, Reverse Osmosis: Chapters 23-25, Design, Selected Applications, and Cost Es­timates)

Amitava Sengupta, Ph.D., Chemical Engineer, Chemical Engineering Laboratory, SRI International, 333 Ravens­wood Avenue, Menlo Park, CA 94025 (Part X, New Membrane Processes under Development: Chapter 42, Hollow-Fiber Contained Liquid Membrane)

Kamalesh K. Sirkar, Ph.D., Professor, Center for Mem­branes and Separation Technologies, Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Hoboken, NJ 07030 (Part I, Chapter I, Overview; Part X, New Membrane Processes under De­velopment: Chapters 41,42, and 46, Membrane-Based Solvent Extraction, Hollow-Fiber Contained Liquid Membrane, and Other New Membrane Processes). Present address: Department of Chemical Engineering, Chemistry and Environmental Science, New Jersey In­stitute of Technology, University Heights, Newark, NJ 07102

C. Stewart Slater, Ph.D., Associate Professor, Department of Chemical Engineering, Manhattan College, Manhattan College Parkway, Riverdale, NY 10471 (Part III, Per­vaporation: Chapters 7-10, Definitions and Background, Theory, DeSign, and Applications and Economics)

Kelly L. Smith, M.S., Director of Research, Controlled Release, Bend Research, Inc., 64550 Research Road, Bend, OR 97701 (Part XI, Chapter 47, Controlled Re­lease)

Heinrich Strathmann, Dr.-Ing., Professor, Institut fiir Chemische Verfahrenstechnik, Universitiit Stuttgart, Boblinger Strasse 72, 7000 Stuttgart 1, Germany (Part V, Electrodialysis: Chapters 1~20, Introduction and Defini­tions, Theory, Ion-Exchange Membranes, Design and Cost Estimates, and Applications)

J. Douglas Way, Ph.D., Assistant Professor, Department of Chemical Engineering, Oregon State University, Corval­lis, OR 97331-2702 (Part X, New Membrane Processes under Development: Chapter 44, Facilitated Transport)

Michael E. Williams, M.S., Ph.D. Student, Department of Chemical Engineering and Center of Membrane Sci­ences, University of Kentucky, Lexington, KY 40506 (Part VI, Reverse Osmosis: Chapters 21-24, Introduction and Definitions, Theory, Design, and Selected Appli­cations)

Raymond R. Zolandz, Ph.D., Senior Research Engineer, Polymer Products Department, E. I. Du Pont de Nemours & Company, Inc., Experimental Station, P.O. Box 80323, Wilmington, DE 19880-0323 (Part II, Gas Per­meation: Chapters 2-6, Definitions, Theory, Design of Gas Permeation Systems, Applications, and Economics)

Contents

Foreword xi Chapter 27. Theory and Mechanistic Preface xiii Concepts 398

Chapter 28. Membranes 408 Part 1. Overview I Chapter 29. Module and Process

Chapter I. Overview 3 Configuration 432 Chapter 30. Applications and Economics 446

Part II. Gas Permeation 17 Chapter 2. Definitions 19 Part VIII. Microfiltration 455 Chapter 3. Theory 25 Chapter 31. Definitions 457 Chapter 4. Design of Gas Permeation Chapter 32. Theory for Deadend

Systems 54 Microfiltration 461 Chapter 5. Applications 78 Chapter 33. Theory for Crossflow Chapter 6. Economics 95 Microfiltration 480

Chapter 34. Deadend Microfiltration: Part III. Pervaporation 103 Applications, Design, and

Chapter 7. Definitions and Background 105 Cost 506 Chapter 8. Theory 117 Chapter 35. Crossflow Microfiltration: Chapter 9. Design 123 Applications, Design, and Cost 571 Chapter 10. Applications and Economics 132

Part IX. Emulsion Liquid Membranes 595 Part IV. Dialysis 161 Chapter 36. Definitions 597

Chapter II. Definitions 163 Chapter 37. Theory 611 Chapter 12. Theory 167 Chapter 38. Design Considerations 656 Chapter 13. Design 186 Chapter 39. Applications 70\ Chapter 14. Applications 206 Chapter 40. Capital and Operating Costs 718 Chapter 15. Cost Estimates 212

Part X. New Membrane Processes under Part V. Electrodialysis 217 Development 725

Chapter 16. Introduction and Definitions 219 Chapter 41. Membrane-Based Solvent Chapter 17. Theory 223 Extraction 727 Chapter 18. Ion-Exchange Membranes 230 Chapter 42. Hollow-Fiber Contained Liquid Chapter 19. Design and Cost Estimates 246 Membrane 764 Chapter 20. Applications 255 Chapter 43. Membrane Reactors 809

Chapter 44. Facilitated Transport 833 Part VI. Reverse Osmosis 263 Chapter 45. Electrostatic

Chapter 21. Introduction and Definitions 265 Pseudo-Liquid-Membrane 867 Chapter 22. Theory 269 Chapter 46. Other New Membrane Chapter 23. Design 281 Processes 885 Chapter 24. Selected Applications 312 Chapter 25. Cost Estimates 355 Part XI. Controlled Release 913

Chapter 47. Controlled Release 915 Part VII. Ultrafiltration 391

Chapter 26. Introduction and Definitions 393 Index 936

ix

Foreword

Membrane processes have wide industrial ap­plications covering many existing and emerging uses in the chemical, petrochemical, petroleum, environmental, water treatment, pharmaceutic­al, medical, food, dairy, beverage, paper, tex­tile, and electronic industries. The existing ap­plications include: (1) dialysis for the purifica­tion of human blood (the artificial kidney), (2) electrodialysis for the desalination of brackish water to produce potable water, (3) reverse osmosis for the desalination of seawater, (4) ultrafiltration for the concentration of large pro­tein molecules from cheese, casein whey, and milk, and (5) microfiltration for the sterilization of pharmaceutical and medical products, beer, wine, and soft drinks. Since membrane pro­cesses generally have low capital investment, as well as low energy consumption and operat­ing cost, there are a number of emerging ap­plications, which include: (1) gas permeation for the removal of acid gases from natural gas, (2) pervaporation for the dehydration of alcohols and organics and the separation of organics, (3) emulsion liquid membranes for wastewater treatment, (4) novel con­tactors for gas absorption/stripping, and (5) membrane reactors which combine chemical reaction and separation.

Although there is a great body of literature covering various aspects of membrane science and technology, to date there has been no single handbook covering the entire field and the full range of applications. Such a source is wel­come.

This handbook reviews the published litera­ture, presents an in-depth description of com­mercialized membrane processes, and gives a state-of-the-art review of new membrane pro­cess concepts under development. It is intended to be a single source of underlying principles, membranes, membrane modules, process de­sign, applications, and cost estimates. It is also a first attempt to bridge the gap between the theory and practice.

There are several groups which may benefit from this handbook. It can be used as educa­tional material for industrial personnel engaged in membrane separations. For scientists and engineers active in research and development in synthetic membranes, it will serve as a single source of reference for the entire field. Engi­neers evaluating separation processes will find this handbook to be a guide to allow membrane approaches to be compared with other separa­tion processes. To students examining sep­aration processes, membrane separations, membrane reactors, membrane-based con­trolled release, and diffusion in thin films, it should be a valuable sourcebook.

Frank B. Sprow, Ph.D.

Vice President Corporate Research Exxon Research and Engineering Company Annandale, New Jersey

xi

Preface

This handbook deals with processes using syn­thetic membranes. It consists of eleven parts: overview, gas penneation, pervaporation, di­alysis, electrodialysis, reverse osmosis, ul­trafiltration, microfiltration, emulsion liquid membranes, new membrane processes under development, and controlled release. The mem­brane processes have been arranged in the following order: (I) commercialized membrane separation processes (Parts II-IX), (2) new membrane processes under development (Part X), and (3) controlled release (Part XI). Pro­cesses using biological membranes have not been included.

Part I, consisting of a chapter, provides an overview of this handbook. This overview gives a definition of a membrane and a mem­brane process, and it serves as an introduction to the remaining parts of this handbook. It dis­cusses the characteristics of eight com­mercialized membrane separation processes with respect to the following seven aspects: (1) separation goal, (2) nature of species retained (size of the species), (3) nature of species trans­ported through membrane, electrolytic or vola­tile, (4) minor or major species of feed solution transported through membrane, (5) driving force, (6) mechanism for transport/selectivity, and (7) phase of feed and penneate streams. It includes additional considerations required for the selection of a membrane process or a hybrid process. This chapter also discusses the charac­teristics of new membrane processes for separa­tion under development with respect to these seven aspects.

Parts II-IX treat the eight commercialized membrane separation processes in significant

detail with an individual part devoted to each process. Each part has a detailed description of the following five aspects of each process: (1) definitions, (2) theory, (3) design, (4) applica­tions, and (5) cost estimates. In each part, an individual chapter is devoted to each of these five aspects, with a few exceptions. The goal is to have a comprehensive coverage with respect to practical application and fundamental un­derstanding.

For the new membrane processes under development covered in Part X, an indivi­dual chapter is devoted to each of the fol­lowing processes: (1) Membrane-Based Solvent Extraction (Chapter 41), (2) Hollow­Fiber Contained Liquid Membrane (Chapter 42), (3) Membrane Reactors (Chapter 43), (4) Facilitated Transport (Chapter 44), and (5) Electrostatic Pseudo-Liquid-Membrane (Chap­ter 45). These have been followed by Chapter 46, Other New Membrane Processes, which includes: (1) membrane-based gas absorp­tion and stripping, (2) membrane distillation, and (3) perstraction. The five aspects men­tioned above for the commercialized pro­cesses have also been used to describe each of these new processes except for their cost infonnation which, however, is rarely avail­able.

The last part of this handbook consisting of a chapter describes controlled release processes using membranes. This chapter is structured after the pattern used for the other membrane processes. However, attention is given to the description of typical controlled release tech­nologies since these are commercialized pro­cesses.

xiii

xiv Preface

There is a wide variation in the nomenclature used in the literature of membrane science and technology. To avoid such a problem, a list of general notation used throughout this handbook has been provided in the very beginning. Spe­cialized notation, if needed, has been added to the end of particular chapters.

W. S. Winston Ho Annandale, New Jersey

Kamalesh K. Sirkar Newark, New Jersey

Acknow ledgments

We wish to thank the contributors for their efforts in the preparation of their chapters in this handbook and their willingness to share their expertise and insights with those involved with membranes through these chapters. We also wish to thank Ms. Marianne Kane for many hours of typing throughout the preparation of this handbook. Many thanks are also due to the reviewers, to whom the publisher sent the manuscripts of all chapters, for their invaluable comments and suggestions.

The following copyright owners are ac­knowledged for granting pennission for the use of their tables and figures: Academic Press (Figure 47-3), American Chemical Society (Figures 42-5,42-18, and 44-7), American In­stitute of Chemical Engineers (Figures 4-14, 29-6,29-8,30-3,37-6,37-7,41-4,41-6,41-8, 42-3, 42-4, 42-6, 42-7, 42-11, 42-13, 42-14, 42-16, and 42-17), American Journal of Medi­cine and ALZA Corporation (Figures 47-9 and 47-16), Bakish Materials Corporation (Figures 10-14, 10-15, 10-16, 10-17, and 10-23), Baxter Healthcare Corporation (Figures 13-3 and 13-4), Bend Research, Inc. and R. J. Ray (Tables 25-1 through 25-15,25-17, and 25-18, Figures 25-1 through 25-14, and Appendix Worksheets in Chapter 25), Business Communications Co., Inc. (Table 29-3), Canon Communications, Inc. (Figure 34-17), Chemical Industry Press (Table 45-3 and Figures 45-1,45-3,45-4,45-5, 45-6, and 45-7), Chemical Processing and Coors Brewing Company (Figure 30-2), Child­wall University Press Ltd. (Figure 38-2), China Institute of Atomic Energy (Table 45-1), China Ocean Press and Water Treatment (Table 45-4 and Figure 38-3), CRC Press, Inc. (Table 30-3), Marcel Dekker, Inc. (Table 30-2 and Fi­gures 38-7, 38-8, 38-9, 38-10, 38-11, and

39-12), E. I. Du Pont de Nemours & Co., Inc., and G. L. Poffenbarger (Tables 5-2, 5-4, and 5-5 and Figures 5-1, 6-1, and 6-2), Elsevier Science Publishers (Tables 3-3, 3-4, 38-1, and 45-2 and Figures 3-7, 3-8, 3-13, 3-14, 4-3, 38-1,41-12,41-14,42-9,42-10,42-12,44-3, 45-2, 45-8, 46-6, 47-11, and 47-15), GFT and H. L. Fleming (Table 10-3 and Figures 7-7, 9-11, 9-13, 10-6, 10-8, 10-10, 10-11, 10-18, 10-19, and 10-20), Hoechst Celanese Corpora­tion (Table 5-3 and Figures 10-32,41-7,41-10, and 42-15), International Scientific Com­munications, Inc. (Figure 34-23), Journal of Environmental Science (Figures 32-4, 32-7, 32-8,32-9, and 32-10), Koch Membrane Systems (Figures 29-1 and 29-2), McGraw-Hill, Inc. (Tables 35-1,35-3, and 35-4 and Figures 34-2, 35-1, 35-2, 35-6, and 44-2), Membrane Tech­nology and Research, Inc. (Figures 7-8, 10-25, 10-27, 10-28, 10-29, 10-30, and 10-33), Milli­pore Corporation (Table 29-2 and Figures 29-3, 30-1, 34-1, 34-3, 34-4, 34-7 through 34-10, 34-12 through 34-14,34-16,34-18 through 34-22,35-3,35-4,35-7, and 35-9 through 35-14), Millipore Corporation and G. Larrabee (Table 34-16), Millipore Corporation and Texas In­struments Corporation (Figure 34-11), Nadir Separations (Hoechst) (Tables 28-4 and 28-8), The New York Academy of Sciences (Figures 43-1,43-2,43-3,43-11,43-12,43-13,43-14, and 43-23), New York State Energy Research and Development Authority (Figure 42-19), Noyes Publications (Figure 34-15), Parenteral Drug Associates (Figures 34-5 and 34-6), PCI Membrane Systems (Table 28-5), Plenum Publishing Corporation (Figures 37-1, 37-2, 37-3, 37-4, 37-5, 38-5, 38-6, 44-6, and 47-5), Royal Society of Chemistry (Figures 5-6 and 5-7), W. B. Saunders Company (Figures 12-11

xv

xvi Acknowledgments

and 13-8), Sepracor Inc. (Figure 41-9), Solid State Technology (Figure 32-6), Swiss Con­tamination Control (Figures 32-15, 32-16, 32-17, and 32-18), Ube Industries (Table 4-2), U.S. Department of Energy (Figures 5-4 and 5-5), and John Wiley & Sons (Tables 3-2, 3-3, and 3-4 and Figures 3-1, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 12-2, 12-8, 12-12, and 13-9).

Finally, we wish to acknowledge support from the Management of Exxon Research and Engineering Company and the Administration of Stevens Institute of Technology and those of the contributors. The contributors and editors are solely responsible for the content of this handbook.

W. S. Winston Ho Kamalesh K. Sirkar

General Notation

Units are given in terms of physical quantities, length (L), mass (M), time (t), temperature (1), amount of substance (mol, mole), electric cur­rent (A, ampere), electric potential (V, volt), energy (E = ML 2It2), and pressure (p = MI Lt2). Special notation is also present in some chapters.

a activity, various units or dimensionless, or particle radius, L

A area, L2 A species A Ai plasticization coefficient for species i,

L3/mol or L3/M Aij interaction coefficient between species i

Da

and j, L3/mol or L3/M Db b channel height, L, or Langmuir affinity Deff

constant, Lt 21M or p-l, or the ratio of Di frictional force of solute to the bulk Dm solution, dimensionless Ds

B species B Bij interaction coefficient between species i DT

and j, dimensionless c concentration, mollL3 [or cm3 (STP)I E

cm3 polymer] or MIL3

c Ai concentration of species A at the inside radius of membrane, mollL3 [or cm3 t::.Ea (STP)/cm3 polymer] or MIL3 f

C Ao concentration of species A at the outside radius of membrane, mol/L3 [or cm3 j; (STP)/cm3 polymer] or MIL3 F

cA Langmuir sorption capacity, L3 (STP)I L3 polymer [cm3 (STP)/cm3 polymer]

C heat capacity, L 21t 2T or ElMT C. reflection constant, 1.14 for air, di­

mensionless d diameter, L

diameter of filter fibers, L

F

g

hydraulic diameter, L inside diameter, or molecular diameter of species i, L outside diameter, L pore diameter, or particle diameter, L stirrer or impeller diameter, L tube diameter, L diffusion coefficient, L 21t dimensionless diffusivity, TJDlr 2Two

infinite dilution diffusivity, or charac­teristic diffusivity, L 21t Darnkohler number, kfcn--lf2fD (n = order of reaction), dimensionless diffusion coefficient for solute-carrier complex, L 21t Brownian diffusion coefficient, L 2/t effective diffusion coefficient, L 21t diffusivity in the internal phase, L21t diffusivity in the membrane phase, L 21t shear-induced diffusion coefficient, L 21t thermodynamic diffusion coefficient, L 21t energy, ML21t 2 or E, or activation ener­gy, ML21t 2 mol or Elmol, or enhance­ment factor (F - 1), dimensionless activation energy, ML21t 2 mol or Elmol Fanning friction factor, or inertia lift function, dimensionless fugacity of component i, MILt2 or p facilitation factor (ratio of flux with car­rier present to flux without carrier), di­mensionless, or F = DHIDD , convenient dimensionless group in the dual-mode sorption model Faraday's constant (9.652 X 104 amp' s/g-equivalent), Atlg-equivalent gravitational acceleration, Llt 2

xvii

xviii General Notation

G GPU

H H

ilim

I j

1

(1s)

k;

K

gravitational conversion factor, di­mensionless [or ft . lb/(lb force . s2) in the fps system] Gibbs free energy, ML21t 2 or E gas permeation unit, 10-6 cm3 (STP)I (cm2 • s . cm Hg) enthalpy, ML21t 2 or E Henry's law constant (c = Hp), t 2 moll L2M [or cm3 (STP)/(cm3 polymer atm)], or t 21L 2

channel half height, L latent heat of vaporization (per unit mass), L21t 2 or ElM electric current density, AIL 2

limiting current density, AIL 2

electric current, A mass transfer or permeation rate, mollt (or kg-equivalent/s) mass transfer rate due to diffusional transport, mollt (or kg-equivalent/s) or Mit mass transfer rate due to breakage, mollt (or kg-equivalent/s) or Mit flux, mollL2t or MIL2t, or volumetric flux, Lit area-averaged volumetric flux, Lit flux of species i, mollL2t or MIL2t area-averaged volumetric flux from in­ertial lift model, Lit area-averaged volumetric flux from shear-induced diffusion model, Lit volumetric flux, Lit thermal conductivity, MLlt 3T or EILtT, or Boltzmann's constant [1.38 x 10-16

g . cm2/(s2 . OK)], ML 21t 2T or EIT, or mass transfer coefficient, Lit forward reaction rate constant, (moll L3)I-nlt, n = order of reaction, various units mass transfer coefficient for species i, Lit reverse reaction rate constant, (moll L 3) I-nit, n = order of reaction, various units distribution coefficient, or hydrodynam­ic constant, dimensionless, or K=CJbl H, convenient dimensionless group in the dual-mode sorption model cake permeability, L 2

K;

Ks

l L

LRV m

M M

N

N

IIp p p

Pe

q Q

diffusion constant relating diffusivity to concentration for species i, L 5/mol t or LSIMt equilibrium constant (for extraction reaction), dimensionless or various units distribution coefficient for species i, a/a:, dimensionless equilibrium constant for stripping or re­extraction reaction, dimensionless or various units solubility product, various units, or sorption coefficient, mollL3 or MIL3

tortuosity correction factor for bubble point, dimensionless membrane thickness, L membrane length, or height of a column extractor, L filter log reduction value, dimensionless molal concentration, mollM distribution coefficient for species i, a/a:, dimensionless mass, M molarity, mollL3 (g-mole/liter or kg­mole/m3 )

molecular weight, Mlmol number of moles number of pores per unit membrane area, L-2

number of hollow fibers, or number of emulsion globules normal (g-equivalent/liter or kg-equiva­lent/m3) Avogadro's number, 6.023 x 1023

molecules/mol pressure drop, MILt2 or p pressure or partial pressure, MILt 2 or p permeability coefficient, various units, or fractional penetration, dimensionless PecJet number, vdID, or veLlDLe, di­mensionless heat flux, Mlt 3 or ElL 2t flow rate or permeation rate, mollt or Mit, or volumetric flow rate, L31t volumetric flow rate of the external phase, L31t volumetric flow rate of the internal phase, L31t volumetric flow rate of the membrane phase, L31t

Q' excess particle flux in boundary layer, ti L21t

Q dimensionless excess particle flux T Qcr critical excess particle flux for cake Tb

formation, dimensionless Tc Qv volumetric flow rate, L31t Tg r radius, or radial coordinate, L U;

rd drum radius, L ri inside radius, L v ro outside radius, or emulsion globule Ve

radius, L VL

rp pore radius, L r t tube radius, L VL,O

R gas constant, ML 21t2T mol, or rejection of solute, or recycle ratio, dimension- Vs

less V Rc cake resistance, MIL2t (or ptlL) , or Ve

~I ~

Rc specific cake resistance per unit thick- V; ~~,0 ~

R~ specific cake resistance (mass basis), LI Vs M V;

Re electrical resistance, VIA Re Reynolds number, dvplT/, dimensionless w Rf reaction rate for extraction per in­

terfacial area, mollL2t (or kg-equivalentl Wi

m2s) Ri rejection of solute species i, or intercep- WI

tion parameter, dimensionless W Rm membrane resistance, MIL2t (or ptIL),

or L- I We Rrrif final membrane resistance, L-I

Rmi initial membrane resistance, L- I We Rr reaction rate for stripping per interfacial

area, mollL 2t (or kg-equivalentlm2s) Wi s cake compressibility factor, dimension-

less Xcr

S entropy, ML 21t 2T or EIT, or shape factor Xi

for flux correction in a cylindrical geometry, dimensionless y;

Sc specific surface area (pore surface area! solids volume) in cake, L-I z

Sc Schmidt number, T/lpD, dimensionless Sh Sherwood number, kiLlD, dimension- Zi

less

General Notation xix

transport number of ionic species i, di­mensionless temperature, T normal boiling point, T critical temperature, T glass transition temperature, T absolute mobility of species i, t mol/M or L2 mollEt velocity, Lit velocity of the external phase, Lit inertial lift velocity for constricted tube or channel, Lit

inertial lift velocity for unconstricted tube or channel, Lit superficial face velocity, Lit volume, L3 volume of the external phase, L3 fractional free volume, dimensionless total volume of the internal phase, C volume of the membrane phase, L3 suspension volume, L3 partial molar volume of species i, L31 mol cake mass per unit membrane area, MI L2

mass fraction of species i, dimension­less penetrant mass fraction, dimensionless channel width, or drum width, or width of membrane sheet, L total consumption amount of the reagent in the external phase, kg-equivalent Weber number, w2 d; Pel'Y, dimension­less total consumption amount of the reagent in the internal phase, kg-equivalent critical distance for cake formation, L mole fraction of species i, dimension­less mole fraction of species i in permeate, dimensionless valence, dimensionless, or Z coordinate, L valence of species i, dimensionless

specific surface area (pore surface area! solids volume) in membrane, L-1

Greek Letters

time, t half-life, t

a selectivity, or mobility ratio (D ABCTI

D AC AO) for facilitated transport, or

xx General Notation

flow distribution parameter, dimension- Of less

aij separation factor, (Y;"lyj~/(YVyj), Yi = A Ci, Pi, Wi, Xi, etc., dimensionless

L\a difference in polymer thermal expansion coefficients above and below glass tran- A sition, r-I (or OK-I) IL

f3 matrix model coefficient in diffusion ex­pression, L3 polymerlL3 (STP) [or cm3 v polymer/cm3 (STP)] Vi

L\f3 difference in polymer compressibility above and below glass transition, Lt 21M g or p-I (or atm- I )

surface or interfacial tension, Mlt 2 or ElL 2 , or plasticization parameter in the 7r

free-volume model, dimensionless p 'Yi activity coefficient of species i, dimen- Po

sionless Pe 'Y shear rate, rl Pm Yo shear rate at edge of boundary layer, t- I Ps r tubesheet length, L u r inlet ratio of the internal reagent equiv-

alents to the feed solute equivalents, di- Uc

mensionless r i ratio of the internal reagent equivalents

to the external phase solute equivalents Uo

for stage i, dimensionless polarization layer thickness, or stagnant film thickness, L, or solubility param-eter (with subscript), (EIL3)1I2 T

l)c cake thickness, L E porosity, or void fraction, or in-

homogeneity factor, dimensionless Tc

Es suspension porosity, dimensionless T m

E inverse Damkohler number, Da-I , di- Tw

mensionless 71 viscosity, MILt, or efficiency, dimen- TwO

sionless 710 pure fluid viscosity, MILt <P 71d single fiber efficiency due to diffusion,

dimensionless <P .. 71e viscosity of the external phase, MILt 71i single fiber efficiency due to intercep- <Pw

tion, dimensionless 71m viscosity of the membrane phase, MILt '" 71s solvent viscosity, MILt, or single col- I/J.f

lector efficiency, dimensionless o diffusion time lag, or time constant, r, W

or stage cut, or angle, dimensionless n

angle subtended by submerged drum, dimensionless ratio of species diameter to pore dia­meter, or parameter of the advancing front model, dimensionless reduced filter coefficient, dimensionless chemical potential, ML21t2 mol or EI mol kinematic viscosity, L 21t

number of ions per molecule of electro­lyte i current utilization, or flow redistribu­tion decrement parameter, dimension­less osmotic pressure, MILt2 or p density or mass concentration, MIL3

pure fluid density, MIC density of the external phase, MIL3

density of the membrane phase, MIL3

cake solids density, MIL3

reflection coefficient, or inhomogeneity factor, dimensionless matrix model coefficient in solubility expression, L3 polymerlL3 (STP) [cm3

polymer/cm3 (STP)] infinite dilution solubility coefficient in matrix model, L3 (STP)/(L3 polymer· MIL(2) (or cm3 (STP)/(cm3 polymer . atm)] tortuosity factor, or number of pore volumes of fluid passed through filter, dimensionless cake fouling time constant, t membrane fouling time constant, t wall shear stress for constricted tube or channel, MILt 2

wall shear stress for unconstricted tube or channel, MILt 2

volume fraction, or solids volume frac­tion, dimensionless suspension solids volume fraction, di­mensionless solids volume fraction at cake surface, dimensionless electric potential, V solvent association factor, dimension­less stirring rate or impeller speed, rpm angular velocity, rl

Diacritical Marks

per mole per unit mass average value time rate of change

Superscripts

11

o

*

value in the feed stream, on the up­stream side or on the high-pressure side of the membrane, or value in the phase external to the membrane value in permeate, product or extract, or value on the downstream side or on the low-pressure side of the membrane value in the membrane indicated by ab­sence of superscript standard reference state ideal case

xxi

Subscripts

o initial value A, B particular species b bulk c cake f feed

10

int

general species index or solute species i inlet

j I 1m m out p

r s

interface species j liquid logarithmic mean membrane outlet product, permeate, permeant, or poly­mer retentate or reject solution or shell side

t tube or tube side T total v vapor w water or solvent x,y,z three coordinate directions