Membranes in Bioprocessing: Theory and Applications PDF
Preview Membranes in Bioprocessing: Theory and Applications
MEMBRANES IN BIOPROCESSING: THEORY AND APPLICATIONS Other titles in the Elsevier Applied Biotechnology Series K. Carr-Brion (ed.). Measurement and Control in Bioprocessing M. Y. Chisti. Airlift Bioreactors W. M. Fogarty/C. T. Kelly (eds). Microbial Enzymes and Biotechno- logy, 2nd Edition T. U. R. Harris (ed.). Protein Production by Biotechnology R. Isaacson (ed.). Methane from Community Wastes A. M. Martin (ed.). Bioconversion of Waste Materials to Industrial Products A. M. Martin (ed.). Biological Degradation of Wastes E. J. Vandamme (ed.). Biotechnology of Vitamins, Pigments and Growth Factors MEMBRANES IN BIOPROCESSING: THEORY ANO APPLICATIONS Edited by J. A. HOWELL School of Chemical Engineering, University of Bath, Claverton Down, Bath, UK, BA2 7A Y. V. SANCHEZ Laboratoire de Genie Chimique et Electrochimie, Universite Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse Cedex, France. R. W. FIELD School of Chemical Engineering, University of Bath, Claverton Down, Bath, UK, BA2 7A Y. rm SPRINGER-SCIENCE+BUSINESS MEDIA, B.V Fint edition 1993 © 1993 Springer Science+Business Media Dordrecht Originally published by Chapman & Hali in 1993 Softcover reprint of the hardcover 1 st edition 1993 ISBN 978-94-010-4954-2 Apart from any fair dcaling for the PU\}1oscs of research or private study. or criticism or review. as pemlitted umler the UK Copyright Designs and Patents Act. 1988. this publicat ion may not bc reproduced. stored. or transmitted. in any fOlm or hy any mcans. without the prior pennission in writing of Ihe publishers. or in Ihe case of reprographic reproduclion only in accoflblllce wilh the tenns of the licenccs is,uc<.l hy thc Copyright Licensing Agcncy in Ihe UK. Of in accordance with the Icnns of licenccs issued by Ihe appropriate Reproduction Rights Organization outside the UK. Enquiries conceming reproduction outside the temls statcd here should be sent to the puhlishers at the Glasgow address printed on this page. llic publisher makcs no representation. express or implied. with regard to the accuracy of the iruonnation contained in this book and calmot accept any legal responsibility or liability for any elTors or omissions that may be made. A catalogue record for Ihis book is available from the British LibralY LibralY of Congress Cataloging·in-Public'ltion data Membranes in bioprocessing: theory and applications/edited by I.A. Howell, V. Sanchez, R.W. Field. p. cm.-(Elsevierapplied bio\echnology series) Includes bibliographical references and index. ISBN 978-94-010-4954-2 ISBN 978-94-011-2156-9 (eBook) DOI 10.1007/978-94-011-2156-9 1. Membrane separation 1. Howell, Iohn A. II. Sanchez, V. III. Field, R.W. IV. Series. TP248.25.M46M47 1993 660' .2842-dc20 92-20213 CIP CONTENTS List of Contributors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Vll 1. Introduction 1. A. HOWELL............................................. 1 2. Nature of Membranes M. MULDER............................................... 13 3. Transport Processes in Membrane Systems R. W. FIELD....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 (Section 3.3.4. Mass transfer in pervaporation and its mathematical description-H. STRATHMANN and R. M. McDONOGH) 4. Separation by Membranes P. AIMAR. 113 5. Design of Membrane Systems J. A. HOWELL............................................. 141 (Section 5.5. Case Study 1: Ultrafiltration of potable water-Po APTEL and J.-L. BERSILLON) (Section 5.6. Case Study 2: Microfiltration of mycelial broth-Po CROCKER) 6. Fouling Phenomena J. A. HOWELL and M. NySTROM........................ 203 7. Flux Enhancement M. NYSTROM and 1. A. HOWELL. 243 8. Electrochemical Aspects of Microfiltration and Ultrafiltration W. R. BOWEN 265 9. The Use of Pervaporation in Biotechnology H. STRATHMANN and R. M. McDONOGH.............. 293 Index 329 v LIST OF CONTRIBUTORS PIERRE AIMAR Laboratoire de Genie Chimique et Electrochimie, CNRS, Universite Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse Cedex, France PHILLIPE APTEL Lyonnaise des Eaux Dumez, 38 Rue du President Wilson, 78230 Le Pecq, France JEAN-LUC BERSILLON Lyonnaise des Eaux Dumez, 38 Rue du President Wilson, 78230 Le Pecq, France RICHARD BOWEN Department of Chemical Engineering, University College of Swansea, Uni- versity of Wales, Singleton Park, Swansea, UK, SA2 8PP PETER CROCKER Harwell Laboratory, Harwell, Oxfordshire, UK, OXll ORA ROBERT FIELD School of Chemical Engineering, University of Bath, Claverton Down, Bath, UK, BA2 7AY JOHN HOWELL School of Chemical Engineering, University of Bath, Claverton Down, Bath, UK, BA2 7AY RICHARD McDONOGH Schleicher & Schvell GmbH, Hahnestrabe 3, J.if..3354 Dassel, Germany MARCEL MULDER Faculty of Chemical Engineering, University of Twente, PO Box 217, 7500 Enschede, The Netherlands VII viii List of Contributors MARIANNE NYSTROM Department of Chemical Technology, Lappeenranta University of Technol- ogy, PB20, 43821 Lappeenranta, Finland HEINER STRATHMANN Faculty of Chemical Engineering, University of Twente, PO Box 217, 7500 Enschede, The Netherlands Chapter 1 INTRODUCTION 1. A. HOWELL School of Chemical Engineering, University of Bath, Claverton Down, Bath, UK, BA2 7A Y 1.1 WHAT IS A MEMBRANE PROCESS? Every day over 20 million litres of brackish water are pumped out of the ground near Jeddah in Saudi Arabia and passed through thin sheets of cellulose acetate known as reverse osmosis membranes before being used as part of the city's water supply. In St Maurice les Chateauneuf, France three million litres a day of ground water are ultrafiltered to supply the city and on test sites in Australia settled sewage is being disinfected by being passed through microfiltration membranes. Many of the foods we eat and beverages we drink have used membranes during their processing. Orange juice can be concentrated by membranes to make a concentrate which retains more of the flavour than does evaporation. Milk can be concentrated slightly by means of a membrane before making a cheese in a process which produces no whey. Gases rising from the ground in a waste tip can be piped away and the carbon dioxide separated from the methane by a membrane process allowing the methane then to be used as a fuel, simultaneously saving energy and reducing the greenhouse effect since methane is more effective as a greenhouse gas than carbon dioxide. In all these processes materials are separated by a semi-permeable membrane which allows the passage of one or more of the materials much more readily than the others. We have all observed that a toy balloon inflated by air or helium will slowly deflate over time. Graham in 1854 also observed this and, being of a curious bent as are most scientists, decided to study the effect. He observed that some gases would leave the balloon faster than others. In each case the gases were diffusing through the rubber skin of the balloon due to the slight pressure difference between 2 J. A. Howell the gases on one side and the other. Some diffused faster and as one might expect the light gas hydrogen diffused the fastest. A mixture of gases could be partially separated in this way. In another classic experiment the French scientist the Abbe Nollet observed in 1748 that if he stored a salt brine inside a pig's bladder and immersed this in water the bladder would expand. This was more curious since the solution inside the bladder was at a slightly higher pressure than the solution outside due to the tension in the bladder. What was happening? As most of us have already learned, this was osmosis with the water being driven into the solution inside the bladder by its chemical potential gradient. This gradient of chemical potential is often called the osmotic pressure. This is not a good term since it implies that there is an actual hydrostatic pressure forcing the liquid through the membrane. In fact a pressure can be used to stop the natural diffusion down the potential gradient. If we set up such a cell as outlined in Fig. 1.1 we need a pump to provide the pressure, a cell to hold a membrane which is selective in that it will allow water to pass easily through it but will not allow salt to pass. Let salt solution be on the upper side and water on the lower side of the membrane. If both sides are at the same pressure then water passes from the water side to the brine side. The salt is unable to cross the membrane. If the pressure on the brine side is now raised to equal the osmotic pressure no fluid flows. If the pressure is raised further to exceed the osmotic pressure then water will now flow from the brine side to the water side separating the water and salt. This phenomenon is called reverse osmosis and is the basis of a large industry providing clean water from brackish waters. Retentote recycle Retentote ...--_---'_--:::::"""Product Membrane Unit Feed pump Recycle pump Feed Tenk Permeete Fig. 1.1. Generalised membrane system feed and bleed. Many membrane processes have now been developed and several of them share common features with the sketch in Fig. 1.1. They require a source of pressure; they circulate fluid across the surface of the membrane; the membrane is selective, preferentially passing at least one but not all of the components on the upstream side. The fluid may be a solution, a Introduction 3 suspension, a mixture of gases or vapours. Not all the processes use pressure as the driving force and we shall therefore introduce the processes in common use in the biotechnology industries including pharmaceuticals, water and waste water, food and beverage as well as the major fermenta- tion industries. 1.2 WHAT IS A MEMBRANE? The difficulty of defining a membrane resides in the variety of uses to which membranes can be put. In fact a simple definition may be the best. A membrane is a thin barrier between two fluids which restricts the movement ofone or more components ofone or both fluids across the barrier. A membrane may be made from a wide variety of materials, organic and inorganic, in asymmetric or isotropic form, in sheets or tubes, in thick- nesses from 100 nm to over 1 mm in single component or composite form, with true pores or with regions of highly permeable solid material in a less permeable matrix. Polymeric membranes are discussed in detail in the next chapter. 1.3 A LITTLE HISTORY The use of membrane processes has been a relatively recent develop- ment in the process industries. Membranes were prepared commercially in the late 1920s for bacteriological laboratory use. These were symmetric microfiltration membranes. Large scale use did not become possible for reverse osmosis and ultrafiltration until asymmetric membranes were prepared. In these membranes the resistance to permeation is con- centrated in a very thin layer at the retentate side of the membrane. Sourirajan and Loeb in the early 1960s were able to synthesise an asymmetric cellulose acetate membrane by the phase inversion process. The technique is discussed in detail in Chapter 2 on membrane manu- facture. Shortly after that time Michaels managed to make an asym- metric polyionic membrane for ultrafiltration and there was then a wave of progress. Simultaneously gas separation membranes were being developed from polymer films following the pioneer work of Barrer. Microfiltration membranes used in a dead-end mode were very popular for cleaning a variety of fluid streams and sterile filtration was used widely from the mid 1960s. Electrodialysis was the first of the modern processes to develop a significant industrial base although it
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