Membrane Gas Separation Membrane Gas Separation YURI YAMPOLSKII A.V. Topchiev Institute of Petrochemical Synthesis, Moscow, Russia BENNY FREEMAN University of Texas at Austin, Austin, TX, USA A John Wiley & Sons, Ltd., Publication This edition fi rst published 2010 © (2010) John Wiley & Sons Ltd Registered offi ce John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offi ces, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. The right of the author to be identifi ed as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988. All rights reserved. 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No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging-in-Publication Data Yampolskii, Yuri Membrane gas separation / Yuri Yampolskii and Benny Freeman. p. cm. Includes bibliographical references and index. ISBN 978-0-470-74621-9 (cloth) 1. Gas separation membranes. 2. Polyamide membranes. 3. Gases–Separation. I. Yampolskii, Y. P. (Yuri Pavlovich) II. Title. TP248.25.M46F74 2010 660′.043–dc22 2010013153 A catalogue record for this book is available from the British Library. ISBN: HB: 9780470746219 Set in 10/12 pt Times by Toppan Best-set Premedia Limited. Printed and bound in Singapore by Markono Print Media Pte Ltd. Contents Preface xiii Contributors xvii I. Novel Membrane Materials and Transport in Them 1 1 Synthesis and Gas Permeability of Hyperbranched and Cross-linked Polyimide Membranes 3 Shinji Kanehashi, Shuichi Sato and Kazukiyo Nagai 1.1 Introduction 3 1.2 Molecular Designs for Membranes 6 1.3 Synthesis of Hyperbranched Polyimides 7 1.3.1 Amorphous Cross-linked Polyimides (Type II) 7 1.3.2 Hyperbranched Polyimides (Type III) 9 1.4 Gas Permeation Properties 13 1.4.1 Amorphous Cross-linked Polyimides (Type II) 13 1.4.2 Hyperbranched Polyimides (Type III) 17 1.4.3 Selectivity and Permeability 21 1.5 Concluding Remarks 21 References 23 2 Gas Permeation Parameters and Other Physicochemical Properties of a Polymer of Intrinsic Microporosity (PIM-1) 29 Peter M. Budd, Neil B. McKeown, Detlev Fritsch, Yuri Yampolskii and Victor Shantarovich 2.1 Introduction 29 2.2 The PIM concept 30 2.3 Gas Adsorption 31 2.4 Gas Permeation 33 2.5 Inverse Gas Chromatography 35 2.6 Positron Annihilation Lifetime Spectroscopy 39 2.7 Conclusions 40 Acknowledgements 40 References 40 vi Contents 3 Addition-type Polynorbornene with Si(CH3)3 Side Groups: Detailed Study of Gas Permeation, Free Volume and Thermodynamic Properties 43 Yuri Yampolskii, Ludmila Starannikova, Nikolai Belov, Maria Gringolts, Eugene Finkelshtein and Victor Shantarovich 3.1 Introduction 43 3.2 Experimental 45 3.3 Results and Discussion 45 3.3.1 Physical Properties 45 3.3.2 Gas Permeability 45 3.3.3 Sorption and Diffusion 50 3.3.4 Free Volume 50 3.4 Conclusions 55 References 56 4 Amorphous Glassy Perfl uoropolymer Membranes of Hyfl on AD®: Free Volume Distribution by Photochromic Probing and Vapour Transport Properties 59 Johannes Carolus Jansen, Karel Friess, Elena Tocci, Marialuigia Macchione, Luana De Lorenzo, Matthias Heuchel, Yuri P. Yampolskii and Enrico Drioli 4.1 Introduction and Scope 59 4.1.1 Free Volume and Free Volume Probing Methods for Polymers 60 4.1.2 Details of the Photochromic Probe Method 62 4.1.3 Relevance of Free Volume for Mass Transport Properties 64 4.2 Membrane Preparation 64 4.2.1 Materials 64 4.2.2 Procedures 64 4.2.3 Membrane Properties 67 4.3 Free Volume Analysis 68 4.3.1 Photoisomerization Procedures and UV-Visible Characterization 68 4.3.2 Probes and Spectrophotometric Analysis 68 4.3.3 Free Volume Distribution 69 4.4 Molecular Dynamics Simulations 71 4.5 Transport Properties 73 4.5.1 Permeation Measurements 73 4.5.2 Data Elaboration: Determination of the Time Lag and Steady State Permeability 74 4.5.3 Vapour Permeation Measurements 76 4.6 Correlation of Transport and Free Volume 79 4.7 Conclusions 80 References 81 Contents vii 5 Modelling Gas Separation in Porous Membranes 85 Aaron W. Thornton, James M. Hill and Anita J. Hill 5.1 Introduction 85 5.2 Background 86 5.3 Surface Diffusion 88 5.4 Knudsen Diffusion 89 5.5 Membranes: Porous Structures? 90 5.6 Transition State Theory (TST) 91 5.7 Transport Models for Ordered Pore Networks 94 5.7.1 Parallel Transport Model 94 5.7.2 Resistance in Series Transport Model 95 5.8 Pore Size, Shape and Composition 95 5.9 The New Model 98 5.9.1 Enhanced Separation by Tailoring Pore Size 99 5.9.2 Determining Diffusion Regime from Experimental Flux 101 5.9.3 Predictions of Gas Separation 102 5.10 Conclusion 105 List of Symbols 106 References 107 II. Nanocomposite (Mixed Matrix) Membranes 111 6 Glassy Perfl uorolymer–Zeolite Hybrid Membranes for Gas Separations 113 Giovanni Golemme, Johannes Carolus Jansen, Daniela Muoio, Andrea Bruno, Raffaella Manes, Maria Giovanna Buonomenna, Jungkyu Choi and Michael Tsapatsis 6.1 Introduction 113 6.2 Materials and Methods 114 6.3 Results and Discussion 116 6.4 Conclusions 122 Acknowledgements 123 References 123 7 Vapor Sorption and Diffusion in Mixed Matrices Based on Tefl on® AF 2400 125 Maria Chiara Ferrari, Michele Galizia, Maria Grazia De Angelis and Giulio Cesare Sarti 7.1 Introduction 125 7.2 Theoretical Background 126 7.2.1 NELF Model 127 7.2.2 Modelling Gas Solubility Into Mixed Matrix Glassy Membranes 128 7.2.3 Modelling Gas Diffusivity and Permeability in Mixed Matrix Glassy Membranes 130 viii Contents 7.3 Experimental 132 7.3.1 Materials 132 7.3.2 Vapor Sorption 133 7.4 Results and Discussion 134 7.4.1 Vapor Sorption in Mixed Matrices Based on AF 2400 134 7.4.2 Diffusivity 137 7.4.3 Correlations for Diffusivity 138 7.4.4 Permeability and Selectivity 138 7.5 Conclusions 140 Acknowledgements 141 References 141 8 Physical and Gas Transport Properties of Hyperbranched Polyimide–Silica Hybrid Membranes 143 Tomoyuki Suzuki, Yasuharu Yamada, Jun Sakai and Kumi Itahashi 8.1 Introduction 143 8.2 Experimental 145 8.2.1 Materials 145 8.2.2 Polymerization 145 8.2.3 Membrane Formation 145 8.2.4 Measurements 146 8.3 Results and Discussion 147 8.3.1 Polymer Characterization 147 8.3.2 Gas Transport Properties of HBPI–Silica Hybrid Membranes 151 8.3.3 O2/N2 and CO2/CH4 Selectivities of HBPI–Silica Hybrid Membranes 151 8.4 Conclusions 157 References 157 9 Air Enrichment by Polymeric Magnetic Membranes 159 Zbigniew J. Grzywna, Aleksandra Rybak and Anna Strzelewicz 9.1 Introduction 159 9.2 Formulation of the Problem 160 9.2.1 One-component Permeation Process – Fick’s and Smoluchowski Equation 161 9.2.2 Diffusion Equation for Two-component Gas Mixture (Without and With a Potential Field) 164 9.3 Experimental 165 9.3.1 Membrane Preparation 165 9.3.2 Experimental Setup 166 9.3.3 Time Lag Method and D1-D8 System 167 9.3.4 Permeation Data 170 9.4 Results and Discussion 172 9.5 Conclusions 175 Contents ix Acknowledgements 178 List of Symbols 178 References 180 III.