Membrane Technology. in the Chemical Industry. Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann. Second, Revised and Extended Edition

Transcription

1 Membrane Technology in the Chemical Industry Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann Second, Revised and Extended Edition

2

3 Membrane Technology Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann

4 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 Ohlrogge, K., Ebert, K. (eds.) Membranen Grundlagen, Verfahren und industrielle Anwendungen approx. 592 pages with approx. 270 figures 2006 Hardcover ISBN

5 Membrane Technology in the Chemical Industry Edited by Suzana Pereira Nunes and Klaus-Viktor Peinemann Second, Revised and Extended Edition

6 The Editors Dr. Suzana Pereira Nunes GKSS Forschungszentrum Max-Planck-Str Geesthacht Dr. Klaus-Viktor Peinemann GKSS Forschungszentrum Institut für Chemie Max-Planck-Str 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 < 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: ISBN-10:

7 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 Phase Inversion 10 4 Presently Available Membranes for Liquid Separation Membranes for Reverse Osmosis Membranes for Nanofiltration Solvent-resistant Membranes for Nanofiltration NF Membranes Stable in Extreme ph Conditions Membranes for Ultrafiltration Polysulfone and Polyethersulfone Poly(vinylidene fluoride) Polyetherimide Polyacrylonitrile Cellulose Solvent-resistant Membranes for Ultrafiltration Membranes for Microfiltration Polypropylene and Polyethylene Poly(tetrafluorethylene) Polycarbonate and Poly(ethylene terephthalate) 37 5 Surface Modification of Membranes Chemical Oxidation Plasma Treatment Classical Organic Reactions Polymer Grafting 41

8 VI Contents 6 Membranes for Fuel Cells Perfluorinated Membranes Nonfluorinated Membranes Polymer Membranes for High Temperatures Organic-Inorganic Membranes for Fuel Cells 52 7 Gas Separation with Membranes Introduction Materials and Transport Mechanisms Organic Polymers Background Polymers for Commercial Gas-separation Membranes Ultrahigh Free Volume Polymers Inorganic Materials for Gas-separation Membranes Carbon Membranes Perovskite-type Oxide Membranes for Air Separation Mixed-matrix Membranes 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 Introduction Historical Background Membranes for Organic Vapor Separation Principles Selectivity Temperature and Pressure Membrane Modules Applications Design Criteria Off-gas and Process Gas Treatment Gasoline Vapor Recovery Polyolefin Production Processes Applications at the Threshold of Commercialization Emission Control at Petrol Stations Natural Gas Treatment Hydrogen/Hydrocarbon Separation Conclusions and Outlook 116 References 116

9 Contents VII 2 Gas-separation Membrane Applications 119 D. J. Stookey 2.1 Introduction Membrane Application Development Membrane Selection Membrane Form Membrane Module Geometry Compatible Sealing Materials Module Manufacture Pilot or Field Demonstration Process Design Membrane System Beta Site Cost/Performance Commercial Gas-separation Membrane Applications Hydrogen Separations Helium Separations Nitrogen Generation Acid Gas-Separations Gas Dehydration Developing Membrane Applications Oxygen and Oxygen-enriched Air Nitrogen Rejection from Natural Gas Nitrogen-enriched Air (NEA) 147 References State-of-the-Art of Pervaporation Processes in the Chemical Industry 151 H.E. A. Brüschke 3.1 Introduction Principles and Calculations Definitions Calculation Permeate-side Conditions Transport Resistances Principles of Pervaporation Principles of Vapor Permeation Membranes Characterization of Membranes Modules Plate Modules Spiral-wound Modules Cushion Module Tubular Modules Other Modules 187

10 VIII Contents 3.5 Applications Organophilic Membranes Hydrophilic Membranes Pervaporation Vapor Permeation Removal of Water from Reaction Mixtures Organic Organic Separation Conclusion 200 References Organic Solvent Nanofiltration 203 A.G. Livingston, L. G. Peeva and P. Silva Summary Current Applications and Potential Theoretical Background to Transport Processes Pore-flow Model Solution-Diffusion Model Models Combining Membrane Transport with the Film Theory of Mass Transfer Transport of Solvent Mixtures Experimental Filtration Equipment and Experimental Measurements Results for Binary Solvent Fluxes Concentration Polarization and Osmotic Pressure Experimental Results for Concentration Polarization and Osmotic Pressure Parameter Estimation Nanofiltration of Docosane-Toluene Solutions Nanofiltration of TOABr-Toluene Solutions Conclusions 224 Nomenclature 225 Greek letters 225 Subscripts 226 References Industrial Membrane Reactors 229 M.F. Kemmere and J. T.F. Keurentjes 5.1 Introduction Membrane Functions in Reactors Controlled Introduction of Reactants Separation of Products Catalyst Retention Applications Pervaporation-assisted Esterification Large-scale Dehydrogenations with Inorganic Membranes 248

11 Contents IX OTM Syngas Process Membrane Recycle Reactor for the Acylase Process Membrane Extraction Integrated Systems Concluding Remarks and Outlook to the Future 254 References Electromembrane Processes 259 T.A. Davis, V.D. Grebenyuk and O. Grebenyuk 6.1 Ion-exchange Membranes Ion-exchange Membrane Properties Swelling Electrical Conductivity Electrochemical Performance Diffusion Permeability Hydraulic Permeability Osmotic Permeability Electroosmotic Permeability Polarization Chemical and Radiation Stability Electromembrane Process Application Electrodialysis Electrodeionization Electrochemical Regeneration of Ion-exchange Resin Synthesis of New Substances without Electrode Reaction Participation: Bipolar-membrane Applications Isolation of Chemical Substances from Dilute Solutions Electrodialysis Applications for Chemical-solution Desalination Electrochemical Processing with Membranes Electrochemistry Chlor-alkali Industry Perfluorinated Membranes Process Conditions Zero-gap Electrode Configurations Other Electrolytic Processes Fuel Cells Electroorganic Synthesis Electrochemical Oxidation of Organic Wastes 300 Acknowledgments 300 List of Symbols 300 References 301

12 X Contents 7 Membrane Technology in the Chemical Industry: Future Directions 305 R. W. Baker 7.1 The Past: Basis for Current Membrane Technology Ultrathin Membranes Membrane Modules Membrane Selectivity The Present: Current Status and Potential of the Membrane Industry Reverse Osmosis Ultrafiltration Microfiltration Gas Separation Refinery Hydrogen Applications Nitrogen (and Oxygen) Separation from Air Natural Gas Separations Vapor/Gas, Vapor/Vapor Separations Pervaporation Ion-conducting Membranes The Future: Predictions for References 333 Subject Index 337

13 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

14

15 XIII List of Contributors R. Baker Membrane Technology & Research 1360 Willow Road Menlo Park, CA USA H.E. A. Brüschke Kurpfalzstraße 64 D Nußloch Germany T.A. Davis TAD Consulting 5 Davis Farm Road Annandale, NJ USA O. Grebenyuk Ionics 65 Grove Street Watertown, MA USA V. D. Grebenyuk Ionics 65 Grove Street Watertown, MA USA M. F. Kemmere NIZO Food Research B.V. P.O. Box BA Ede The Netherlands J. T. F. Keurentjes Eindhoven University of Technology P.O. Box 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 Geesthacht Germany K. Ohlrogge GKSS-Research Center Max-Planck-Str. 1 D Geesthacht Germany