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BY
GAS SEPARATION

ADSORPTION PROCESSES
 SERIES ON CHEMICAL ENGINEERING

Series Editor: Ralph T. Yang (Univ. of Michigan)

Advisory Board: Robert S. Langer (Massachusetts Inst. of Tech.)
Donald R. Paul (Univ. of Texas)
John M. Prausnitz (Univ. of California, Berkeley)
Eli Ruckenstein (State Univ. of New York)
James Wei (Princeton Univ.)
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Vol. 1 Gas Separation by Adsorption Processes

Ralph T. Yang (Univ. of Michigan)

Vol. 2 Adsorption Analysis: Equilibria and Kinetics

Duong D. Do (Univ. of Queensland)

Vol. 3 Batch Distillation: Design and Operation

Iqbal M. Mujtaba (Univ. of Bradford)
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—ifl^
Series
on C h e m i c a l

BY

University of Michigan
Ralph T. Yang
Engineering

GAS SEPARATION

ADSORPTION PROCESSES

Imperial College Press

Vol.1
 Published by
Imperial College Press
57 Shelton Street
Covent Garden
London WC2H9HE

Distributed by
World Scientific Publishing Co. Pte. Ltd.
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UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE

Library of Congress Cataloging-in-Publication Data

Yang, R. T.
Gas separation by adsorption processes / Ralph T. Yang.
p. cm. ~ (Series on chemical engineering ; vol. 1)
Originally published: Boston : Butterworths, cl987.
Includes bibliographical references and indexes.
ISBN-13 978-1-86094-047-7 (pbk)
ISBN-10 1-86094-047-1 (pbk)
1. Gases - Separation. 2. Gases - Adsorption and adsorption.
I. Title. II. Series.
TP242.Y36 1997
660'.2842 - dc21 97-11397
CIP

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

First published by Butterworth Publishers © 1987

First published 1997

Reprinted 1999, 2006, 2008

Copyright © 1997 by Imperial College Press

All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,
electronic or mechanical, including photocopying, recording or any information storage and retrieval
system now known or to be invented, without written permission from the Publisher.

For photocopying of material in this volume, please pay a copying fee through the Copyright
Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to
photocopy is not required from the publisher.

Printed in Singapore by World Scientific Printers

 CONTENTS

Preface ix

1. INTRODUCTORY REMARKS 1
1.1 Criteria for When to Use Adsorption Processes 2
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1.2 Categorizations of Adsorptive Separation Processes 3

1.2.1 Based on Method of Adsorbent Regeneration 3
1.2.2 Based on Feed Composition 3
1.2.3 Based on Mechanism of Separation 4
1.3 Current Status and Future Prospects 5

2. ADSORBENTS AND ADSORPTION ISOTHERMS 9

2.1 Industrial Sorbents 9
2.1.1 Activated Carbon 11
2.1.2 Molecular-Sieve Carbon 14
2.1.3 Activated Alumina 17
2.1.4 Silica Gel 18
2.1.5 Zeolites 19
2.1.6 Selection of Sorbent 25
2.2 Equilibrium Adsorption of Single Gases 26
2.2.1 Three Approaches for Isotherm Models 26
2.2.2 Physical Adsorption Forces 28
2.2.3 Isotherms Based on the Langmuir Approach 30
2.2.4 Isotherms Based on the Gibbs Approach 35
2.2.5 The Potential Theory 39

3. EQUILIBRIUM ADSORPTION OF GAS MIXTURES 49

3.1 Langmuir-Type Equations and Correlation 49
3.1.1 Extended Langmuir Equation 49
3.1.2 Loading Ratio Correlation 51
3.1.3 Other Theories 52
3.2 The Potential-Theory Approach 53
3.2.1 Direct Extension of the Dubinin-Radushkevich
(D-R) Equation 53
3.2.2 Theoretical Basis for the Lewis Relationship 54
3.2.3 The Model of Grant and Manes 56
3.3 Other Thermodynamic Models 61
3.3.1 The Method of Lewis et al. for Binary Mixtures 61

V
 vi Contents

3.3.2 The Method of Cook and Basmadjian for Binary

Mixtures 62
3.3.3 The Adsorbed Solution Theory of Myers and
Prausnitz 64
3.3.4 Nonideal Adsorbed Solution Models: Predictions
of Activity Coefficients 68
3.3.5 Vacancy Solution Theory 70
3.3.6 Two-Dimensional Gas Model 74
3.3.7 Simplified Statistical Thermodynamic Model of
Ruthven 77
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3.3.8 Lattice Solution Model of Lee 81

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3.3.9 Law-of-Mass-Action Models 83

3.4 Comparison of Models and Experiments 85
3.4.1 Comparison between Literature Data and
Models 86
3.4.2 Comparison and Use of Models 90
3.5 Experimental Techniques 92
3.5.1 Constant-Volume Method 92
3.5.2 Dynamic Method 93
3.5.3 Gravimetric Method 93
3.5.4 Chromatographic Methods 94

4. RATE PROCESSES IN ADSORBERS 101

4.1 Governing Equations for Adsorbers 102
4.2 Transport Processes in Adsorbers 104
4.2.1 External Transport Processes: Film Coefficients 105
4.2.2 Internal (Intraparticle) Transport Processes 108
4.2.3 Dispersion in Packed Beds 124
4.3 Linear Driving Force and Other Approximations for
Mass Transfer Rate 126
4.3.1 Applicability to Various Isotherms under
Adsorber Conditions 128
4.3.2 Application of LDF to Cyclic Processes 132
4.3.3 Parabolic Concentration Profile within Particle 133

5. ADSORBER DYNAMICS: BED PROFILES AND

BREAKTHROUGH CURVES 141
5.1 Equilibrium Theory: Isothermal, Single-Sorbate 142
5.1.1 Shapes of Isotherms 142
5.1.2 Velocity of Concentration Front 143
5.1.3 Breakthrough Curves 146
5.1.4 Effects of Axial Dispersion 148
5.2 Nonequilibrium Theory: Isothermal, Single-Sorbate 148
5.2.1 The Rosen Model 149
5.2.2 The Thomas Model 151
 Contents vii

5.2.3 Model for Zeolites 152

5.2.4 Other Models 156
5.3 Asymptotic (Constant-Pattern) Solutions 158
5.4 Nonisothermal or Adiabatic Adsorption 161
5.5 Desorption 165
5.5.1 Conditions for Regeneration with Cold Purge 170
5.5.2 Characteristic Purge Gas Temperature 171
5.5.3 Minimum Desorption Time and Gas
Consumption 172
5.6 Multicomponent Adsorption and Desorption 173
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5.6.1 Isothermal Equilibrium Theory 175

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5.6.2 Adiabatic Equilibrium Theory 186

5.6.3 Nonequilibrium Systems and Conclusions 193

CYCLIC GAS SEPARATION PROCESSES 201

6.1 Sorbent Regeneration 202
6.2 Temperature-Swing Adsorption and Inert Purge Cycle 204
6.2.1 Equilibrium-Theory Calculations 206
6.2.2 Nonequilibrium Models 207
6.2.3 Empirical Heat Transfer Model for Regeneration 208
6.2.4 Isothermal Inert Purge Cycle 211
6.3 Chromatography 212
6.4 Moving-Bed and Simulated Moving-Bed Processes 216
6.4.1 Hypersorption 217
6.4.2 Simulated Moving-Bed Process: Sorbex 219
6.5 Parametric Pumping and Cycling Zone Adsorption 221
6.5.1 Thermal Parametric Pumping 222
6.5.2 Pressure Parametric Pumping: Molecular Gate 225
6.5.3 Thermal Cycling Zone Adsorption 228
6.5.4 Pressure Cycling Zone Adsorption 230

PRESSURE-SWING ADSORPTION: PRINCIPLES AND

PROCESSES 237
7.1 Basic Concepts and Developments 238
7.1.1 Skarstrom Cycle and Guerin-Domine Cycle 238
7.1.2 Cocurrent Depressurization 241
7.1.3 Pressure Equalization 243
7.1.4 Pretreatment Beds 245
7.1.5 Purge by Strong Adsorptive 247
7.1.6 Temperature Equalization and Other
Developments 248
7.2 Commercial Processes 253
7.2.1 Air Drying 253
7.2.2 Hydrogen Purification 255
7.2.3 Bulk Separation of Normal Paraffins 260
 viii Contents

7.2.4 Air Separation: Oxygen Generation 263

7.2.5 Air Separation: Nitrogen Generation 268

8. PRESSURE-SWING ADSORPTION: MODELS AND

EXPERIMENTS 275
8.1 Models for Skarstrom Cycle 275
8.1.1 Analytic Model 276
8.1.2 Numerical Models: Isothermal 284
8.1.3 Adsorption and Desorption during Pressure-
Changing Steps 290
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8.1.4 Other Numerical Models 297

8.2 Models for PSA-Parametric Pumping 303
8.2.1 Analytic Model 303
8.2.2 Numerical Models 306
8.3 Multibed Process for Bulk Separation of Binary and
Multicomponent Mixtures 312
8.3.1 Experimental Method 312
8.3.2 Equilibrium Model, LDF Model, and Pore-
Diffusion Model 313
8.3.3 Bulk PSA Separations 323

Author Index 339

Subject Index 347

 PREFACE AND
ACKNOWLEDGMENTS

The last two decades have witnessed a tremendous growth of gas adsorption
processes that have made adsorption systems a key separations tool in chemical
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and petrochemical industries. The growth is a result of a series of significant

scientific and engineering developments, initiated by the invention of synthetic
zeolites and the pressure swing adsorption cycles. These inventions were followed
by a succession of technological and theoretical advances. Among them are the
developments of more efficient pressure swing adsorption (PSA) cycles, new and
improved adsorbents, theories of adsorption from mixtures, theories on multicom-
ponent adsorber dynamics, and modeling of PSA cycles.
The aim of this book is to present a comprehensive account and critical
analysis of these developments. The presentation is made in a systematic manner
with an emphasis on fundamental concepts and principles.
In Chapter 3 a detailed account is given on all theories and important
experimental observations on adsorption from mixtures, as predicted by the pure-
gas isotherms discussed in Chapter 2. Chapter 4 is a review of the important rate
processes encountered in the fixed-bed adsorber, which is the workhorse in
adsorption processes. The important aspects of the fixed-bed adsorber dynamics
are summarized in Chapter 5 for both pure-component and multicomponent
adsorptive gases. Chapter 6 reviews all cyclic adsorption processes for gas
separation. A detailed analysis is given in Chapter 7 on the basic engineering
concepts and designs of PSA cycles. Much of the information contained in this
chapter is drawn from the patent literature; whenever possible, concepts rather
than quantitative information are used. Chapter 8 is devoted to the theories and
models of PSA cycles, along with experimental observations.
The book is intended for engineers and scientists, in industrial, government,
or academic institutions, who are interested in gas separation processes. It could
also form part of a one-semester graduate-level course for students in chemical
engineering or related disciplines.
I assembled the greater part of the book during a sabbatical leave from the
State University of New York at Buffalo in the spring of 1985.
In the early stage of my research and in organizing my thoughts on the
subject, I have benefited greatly from discussions with a number of researchers in the
field as well as colleagues at the university. In particular, I should mention Dr. Frank
B. Hill and Dr. George E. Keller II. The untimely death of Frank Hill last October is
a huge loss to the field, and his contribution and friendship are sorely missed.

ix
 x Gas Separation by Absorption Processes

Thanks are due to my past and present students and associates, with whom I
have had so much pleasure in learning. The superb typing of Mrs. Darlene Innes
and the highly efficient editing and publication by the staff at Butterworths are
sincerely acknowledged. Finally, I would like to thank the U.S. Department of
Energy and the National Science Foundation for supporting the research which
substantially contributed to this book.

Ralph T. Yang
Buffalo, New York
August, 1985
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