Membrane Technology in the Chemical Industry Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann Second, Revised and Extended Edition
Membrane Technology Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann
Related Titles Sammells, A. F., Mundschau, M. V. (eds.) Nonporous Inorganic Membranes for Chemical Processing approx. 380 pages with approx. 150 figures 2006 Hardcover ISBN 3-527-31342-7 Ohlrogge, K., Ebert, K. (eds.) Membranen Grundlagen, Verfahren und industrielle Anwendungen approx. 592 pages with approx. 270 figures 2006 Hardcover ISBN 3-527-30979-9
Membrane Technology in the Chemical Industry Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann Second, Revised and Extended Edition
The Editors Dr. Suzana Pereira Nunes GKSS Forschungszentrum Max-Planck-Str. 1 21502 Geesthacht Dr. Klaus-Viktor Peinemann GKSS Forschungszentrum Institut für Chemie Max-Planck-Str. 1 21502 Geesthacht n All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at <http://dnb.ddb.de> 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form by photoprinting, microfilm, or any other means nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Typesetting K+V Fotosatz GmbH, Beerfelden Printing betz-druck GmbH, Darmstadt Binding Litges & Dopf GmbH, Heppenheim Cover Design Grafik-Design Schulz, Fußgönheim Printed in the Federal Republic of Germany Printed on acid-free paper ISBN-13: 978-3-527-31316-7 ISBN-10: 3-527-31316-8
V Contents Part I Membrane Materials and Membrane Preparation S. P. Nunes and K.-V. Peinemann 1 Introduction 3 2 Membrane Market 5 3 Membrane Preparation 9 3.1 Phase Inversion 10 4 Presently Available Membranes for Liquid Separation 15 4.1 Membranes for Reverse Osmosis 15 4.2 Membranes for Nanofiltration 18 4.2.1 Solvent-resistant Membranes for Nanofiltration 20 4.2.2 NF Membranes Stable in Extreme ph Conditions 22 4.3 Membranes for Ultrafiltration 23 4.3.1 Polysulfone and Polyethersulfone 23 4.3.2 Poly(vinylidene fluoride) 26 4.3.3 Polyetherimide 28 4.3.4 Polyacrylonitrile 30 4.3.5 Cellulose 32 4.3.6 Solvent-resistant Membranes for Ultrafiltration 32 4.4 Membranes for Microfiltration 34 4.4.1 Polypropylene and Polyethylene 34 4.4.2 Poly(tetrafluorethylene) 36 4.4.3 Polycarbonate and Poly(ethylene terephthalate) 37 5 Surface Modification of Membranes 39 5.1 Chemical Oxidation 39 5.2 Plasma Treatment 40 5.3 Classical Organic Reactions 41 5.4 Polymer Grafting 41
VI Contents 6 Membranes for Fuel Cells 45 6.1 Perfluorinated Membranes 46 6.2 Nonfluorinated Membranes 48 6.3 Polymer Membranes for High Temperatures 51 6.4 Organic-Inorganic Membranes for Fuel Cells 52 7 Gas Separation with Membranes 53 7.1 Introduction 53 7.2 Materials and Transport Mechanisms 53 7.2.1 Organic Polymers 55 7.2.2 Background 55 7.2.3 Polymers for Commercial Gas-separation Membranes 57 7.2.4 Ultrahigh Free Volume Polymers 58 7.2.5 Inorganic Materials for Gas-separation Membranes 62 7.2.6 Carbon Membranes 62 7.2.7 Perovskite-type Oxide Membranes for Air Separation 64 7.2.8 Mixed-matrix Membranes 67 7.3 Basic Process Design 69 Acknowledgments 75 References 75 Part II Current Application and Perspectives 1 The Separation of Organic Vapors from Gas Streams by Means of Membranes 93 K. Ohlrogge and K. Stürken Summary 93 1.1 Introduction 94 1.2 Historical Background 94 1.3 Membranes for Organic Vapor Separation 96 1.3.1 Principles 96 1.3.2 Selectivity 96 1.3.3 Temperature and Pressure 97 1.3.4 Membrane Modules 98 1.4 Applications 100 1.4.1 Design Criteria 100 1.4.2 Off-gas and Process Gas Treatment 102 1.4.2.1 Gasoline Vapor Recovery 103 1.4.2.2 Polyolefin Production Processes 109 1.5 Applications at the Threshold of Commercialization 111 1.5.1 Emission Control at Petrol Stations 111 1.5.2 Natural Gas Treatment 113 1.5.3 Hydrogen/Hydrocarbon Separation 114 1.6 Conclusions and Outlook 116 References 116
Contents VII 2 Gas-separation Membrane Applications 119 D. J. Stookey 2.1 Introduction 119 2.2 Membrane Application Development 120 2.2.1 Membrane Selection 120 2.2.2 Membrane Form 123 2.2.3 Membrane Module Geometry 125 2.2.4 Compatible Sealing Materials 129 2.2.5 Module Manufacture 130 2.2.6 Pilot or Field Demonstration 130 2.2.7 Process Design 132 2.2.8 Membrane System 133 2.2.9 Beta Site 135 2.2.10 Cost/Performance 136 2.3 Commercial Gas-separation Membrane Applications 136 2.3.1 Hydrogen Separations 137 2.3.2 Helium Separations 140 2.3.3 Nitrogen Generation 140 2.3.4 Acid Gas-Separations 143 2.3.5 Gas Dehydration 144 2.4 Developing Membrane Applications 146 2.4.1 Oxygen and Oxygen-enriched Air 146 2.4.2 Nitrogen Rejection from Natural Gas 147 2.4.3 Nitrogen-enriched Air (NEA) 147 References 147 3 State-of-the-Art of Pervaporation Processes in the Chemical Industry 151 H.E. A. Brüschke 3.1 Introduction 151 3.2 Principles and Calculations 153 3.2.1 Definitions 153 3.2.2 Calculation 155 3.2.3 Permeate-side Conditions 163 3.2.4 Transport Resistances 166 3.2.5 Principles of Pervaporation 168 3.2.6 Principles of Vapor Permeation 171 3.3 Membranes 175 3.3.1 Characterization of Membranes 180 3.4 Modules 182 3.4.1 Plate Modules 183 3.4.2 Spiral-wound Modules 185 3.4.3 Cushion Module 185 3.4.4 Tubular Modules 186 3.4.5 Other Modules 187
VIII Contents 3.5 Applications 188 3.5.1 Organophilic Membranes 188 3.5.2 Hydrophilic Membranes 189 3.5.2.1 Pervaporation 189 3.5.2.2 Vapor Permeation 191 3.5.3 Removal of Water from Reaction Mixtures 194 3.5.4 Organic Organic Separation 197 3.6 Conclusion 200 References 200 4 Organic Solvent Nanofiltration 203 A.G. Livingston, L. G. Peeva and P. Silva Summary 203 4.1 Current Applications and Potential 203 4.2 Theoretical Background to Transport Processes 205 4.2.1 Pore-flow Model 205 4.2.2 Solution-Diffusion Model 206 4.2.3 Models Combining Membrane Transport with the Film Theory of Mass Transfer 207 4.3 Transport of Solvent Mixtures 210 4.3.1 Experimental 210 4.3.1.1 Filtration Equipment and Experimental Measurements 210 4.3.2 Results for Binary Solvent Fluxes 210 4.4 Concentration Polarization and Osmotic Pressure 213 4.4.1 Experimental 213 4.4.2 Results for Concentration Polarization and Osmotic Pressure 214 4.4.2.1 Parameter Estimation 214 4.4.2.2 Nanofiltration of Docosane-Toluene Solutions 216 4.4.2.3 Nanofiltration of TOABr-Toluene Solutions 219 4.5 Conclusions 224 Nomenclature 225 Greek letters 225 Subscripts 226 References 226 5 Industrial Membrane Reactors 229 M.F. Kemmere and J. T.F. Keurentjes 5.1 Introduction 229 5.2 Membrane Functions in Reactors 232 5.2.1 Controlled Introduction of Reactants 232 5.2.2 Separation of Products 238 5.2.3 Catalyst Retention 241 5.3 Applications 242 5.3.1 Pervaporation-assisted Esterification 242 5.3.2 Large-scale Dehydrogenations with Inorganic Membranes 248
Contents IX 5.3.3 OTM Syngas Process 250 5.3.4 Membrane Recycle Reactor for the Acylase Process 251 5.3.5 Membrane Extraction Integrated Systems 253 5.4 Concluding Remarks and Outlook to the Future 254 References 255 6 Electromembrane Processes 259 T.A. Davis, V.D. Grebenyuk and O. Grebenyuk 6.1 Ion-exchange Membranes 259 6.2 Ion-exchange Membrane Properties 262 6.2.1 Swelling 262 6.2.2 Electrical Conductivity 263 6.2.3 Electrochemical Performance 267 6.2.4 Diffusion Permeability 268 6.2.5 Hydraulic Permeability 269 6.2.6 Osmotic Permeability 269 6.2.7 Electroosmotic Permeability 270 6.2.8 Polarization 271 6.2.9 Chemical and Radiation Stability 273 6.3 Electromembrane Process Application 274 6.3.1 Electrodialysis 274 6.3.2 Electrodeionization 280 6.3.3 Electrochemical Regeneration of Ion-exchange Resin 282 6.3.4 Synthesis of New Substances without Electrode Reaction Participation: Bipolar-membrane Applications 283 6.3.5 Isolation of Chemical Substances from Dilute Solutions 285 6.3.6 Electrodialysis Applications for Chemical-solution Desalination 285 6.4 Electrochemical Processing with Membranes 286 6.4.1 Electrochemistry 286 6.4.2 Chlor-alkali Industry 291 6.4.3 Perfluorinated Membranes 291 6.4.4 Process Conditions 293 6.4.5 Zero-gap Electrode Configurations 294 6.4.6 Other Electrolytic Processes 295 6.4.7 Fuel Cells 297 6.4.8 Electroorganic Synthesis 299 6.4.9 Electrochemical Oxidation of Organic Wastes 300 Acknowledgments 300 List of Symbols 300 References 301
X Contents 7 Membrane Technology in the Chemical Industry: Future Directions 305 R. W. Baker 7.1 The Past: Basis for Current Membrane Technology 305 7.1.1 Ultrathin Membranes 305 7.1.2 Membrane Modules 306 7.1.3 Membrane Selectivity 308 7.2 The Present: Current Status and Potential of the Membrane Industry 309 7.2.1 Reverse Osmosis 309 7.2.2 Ultrafiltration 313 7.2.3 Microfiltration 314 7.2.4 Gas Separation 315 7.2.4.1 Refinery Hydrogen Applications 317 7.2.4.2 Nitrogen (and Oxygen) Separation from Air 319 7.2.4.3 Natural Gas Separations 323 7.2.4.4 Vapor/Gas, Vapor/Vapor Separations 326 7.2.5 Pervaporation 329 7.2.6 Ion-conducting Membranes 330 7.3 The Future: Predictions for 2020 332 References 333 Subject Index 337
XI Preface The idea of the first edition of Membrane Technology in the Chemical Industry was to review the available membranes for the broad variety of separation processes in the chemical sector. A further important decision was to invite wellknown membrane scientists with recognized experience in the chemical industry to supply a deep analysis of the main membrane applications in this field. After 5 years the use of membranes is even more widespread, new membranes have entered the market, some are no longer commercialized and some applications have become more relevant, justifying now the second edition of the book. In the first part of this new edition, market statistics have been reviewed, as well as the currently available membranes and membrane materials. A new chapter on Fuel Cells has been added, a field that has grown considerably in recent years. Also, the balance of applications connected to gas separation has been critically reanalyzed. Part II has been reviewed by the various authors. The future directions have been reanalyzed. The major change in Part II is the inclusion of a chapter on Organic Solvent Nanofiltration, written by Andrew Livingstone, Ludmila G. Peeva and Pedro Silva, which reflects the rapid development of this field in recent years. Suzana Pereira Nunes, Klaus-Viktor Peinemann March 2006
XIII List of Contributors R. Baker Membrane Technology & Research 1360 Willow Road Menlo Park, CA 94025 USA H.E. A. Brüschke Kurpfalzstraße 64 D-69226 Nußloch Germany T.A. Davis TAD Consulting 5 Davis Farm Road Annandale, NJ 08801 USA O. Grebenyuk Ionics 65 Grove Street Watertown, MA 02172 USA V. D. Grebenyuk Ionics 65 Grove Street Watertown, MA 02172 USA M. F. Kemmere NIZO Food Research B.V. P.O. Box 20 6710 BA Ede The Netherlands J. T. F. Keurentjes Eindhoven University of Technology P.O. Box 513 5600 MB Eindhoven The Netherlands A. Livingstone Department of Chemical Engineering Imperial College London Prince Consort Road South Kensington London, SW7 2AZ United Kingdom S.P. Nunes GKSS Forschungszentrum Max-Planck-Str. 1 D-21502 Geesthacht Germany K. Ohlrogge GKSS-Research Center Max-Planck-Str. 1 D-21502 Geesthacht Germany