Edited by Santi Kulprathipanja Zeolites in Industrial Separation and Catalysis Edited by Santi Kulprathipanja Zeolites in Industrial Separation and Catalysis Further Reading R. Xu, W. Pang, J. Yu, Q. Huo, J. Chen Chemistry of Zeolites and Related Porous Materials Synthesis and Structure 2007 ISBN: 978-0-470-82233-3 I. Chorkendorff, J.W. Niemantsverdriet Concepts of Modern Catalysis and Kinetics 2007 ISBN: 978-3-527-31672-4 B. Cornils, W.A. Herrmann, M. Muhler, C H. Wong (Eds.) Catalysis from A to Z A Concise Encyclopedia 2007 ISBN: 978-3-527-31438-6 S.M. Roberts Catalysts for Fine Chemical Synthesis Volume 4. Microporous and Mesoporous Solid Catalysts 2006 ISBN: 978-0-471-49054-8 R.A. van Santen, M. Neurock Molecular Heterogeneous Catalysis A Conceptual and Computational Approach 2006 ISBN: 978-3-527-29662-0 J. Hagen Industrial Catalysis A Practical Approach 2006 ISBN: 978-3-527-31144-6 F. Schüth, K.S.W. Sing, J. Weitkamp (Eds.) Handbook of Porous Solids 5 Volumes 2002 Hardcover ISBN: 978-3-527-30246-8 Edited by Santi Kulprathipanja Zeolites in Industrial Separation and Catalysis The Editor Dr. Santi Kulprathipanja UOP, A Honeywell Company 25 E. Algonquin Road Des Plaines, IL 60017 USA 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 the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfi lm, 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 specifi cally marked as such, are not to be considered unprotected by law. Cover Design Formgeber, Eppelheim Typesetting Toppan Best-set Premedia Limited Printing and Binding Bell & Bain Ltd., Glasgow Printed in Great Britain Printed on acid-free paper ISBN: 978-3-527-32505-4 V Zeolites in Industrial Separation and Catalysis. Edited by Santi Kulprathipanja Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-32505-4 Contents Preface XIX List of Contributors XXIII 1 Introduction 1 Edith M. Flanigen, Robert W. Broach, and Stephen T. Wilson 1.1 Introduction 1 1.1.1 Molecular Sieves and Zeolites 1 1.1.2 Nomenclature 2 1.1.3 Early History 3 1.1.4 Natural Zeolites 4 1.2 History of Molecular Sieve Materials 5 1.2.1 Aluminosilicate Zeolites and Silica Molecular Sieves 6 1.2.2 The Materials Explosion Since the 1980s 7 1.2.2.1 The 1980s 7 1.2.2.2 The 1990s 11 1.2.2.3 The New Millennium 14 1.3 Synthesis 15 1.4 Applications 16 1.5 Markets 17 1.6 The Future 17 1.6.1 Materials 17 1.6.2 Applications 18 1.7 History of International Conferences and Organizations 18 1.8 Historical Epilog 20 References 20 Further Reading 26 2 Zeolite Types and Structures 27 Robert W. Broach 2.1 Introduction 27 2.2 Building Units for Zeolite Frameworks 28 VI Contents 2.3 Zeolite Framework Types 31 2.4 Pores, Channels, Cages and Cavities 32 2.5 Materials Versus Framework Types 34 2.6 Structures of Commercially Signifi cant Zeolites 35 2.6.1 Linde Type A (LTA) 36 2.6.2 Faujasite (FAU) 38 2.6.3 Mordenite (MOR) 40 2.6.4 Chabazite (CHA) 42 2.6.5 ZSM-5 (MFI) 45 2.6.6 Linde Type L (LTL) 47 2.6.7 Beta Polymorphs *BEA and BEC 49 2.6.8 MCM-22 (MWW) 51 2.7 Hypothetical Zeolite Frameworks 54 Acknowledgments 55 References 55 3 Synthesis of Zeolites and Manufacture of Zeolitic Catalysts and Adsorbents 61 Robert L. Bedard 3.1 Introduction 61 3.2 Synthesis of Zeolites and Aluminophosphate Molecular Sieves 62 3.2.1 Hydrothermal Synthesis – The Key to Metastable Phases 62 3.2.2 Typical Zeolite Syntheses 63 3.2.3 Important Synthesis Parameters – Zeolites 65 3.2.4 Typical Aluminophosphate Syntheses 66 3.2.5 Important Synthesis Parameters – Aluminophosphates 67 3.2.6 Dewatering, Filtration and Washing of Molecular Sieve Products 67 3.3 Forming Zeolite Powders into Usable Shapes 68 3.3.1 Chemical Engineering Considerations in Zeolite Forming 68 3.3.2 Ceramic Engineering Considerations in Zeolite Forming 69 3.3.3 Bound Zeolite Forms 70 3.3.4 Other Zeolite Forms – Colloids, Sheets, Films and Fibers 70 3.4 Finishing: Post-Forming Manufacturing of Zeolite Catalysts and Adsorbents 71 3.4.1 Post-Forming Crystallization 71 3.4.2 Stabilization and Chemical Modifi cation of Zeolites 72 3.4.3 Ion Exchange and Impregnation 74 3.4.4 Drying and Firing 75 3.5 Selected New Developments in Catalyst and Adsorbent Manufacture 75 References 77 4 Zeolite Characterization 85 Steven A. Bradley, Robert W. Broach, Thomas M. Mezza, Sesh Prabhakar, and Wharton Sinkler 4.1 Introduction 85 4.1.1 Importance of Characterization 85 Contents VII 4.2 Multi-Technique Methodology 86 4.2.1 Identifi cation of the Structure of a Newly Invented Zeolite 86 4.3 X-Ray Powder Diffraction Characterization of Zeolitic Systems 91 4.3.1 Interpretation of Powder Diffraction Data for Zeolites 91 4.3.2 Phase Identifi cation and Quantifi cation 92 4.3.3 Unit Cell Size Determination 94 4.3.4 Crystallite Size 95 4.3.5 Rietveld Refi nement 96 4.4 Electron Microscopy Characterization of Zeolitic Systems 97 4.4.1 Importance of Electron Microscopy for Characterizing Zeolites 97 4.4.2 Scanning Electron Microscopy 98 4.4.2.1 Morphological Characterization 98 4.4.2.2 Compositional Characterization 100 4.4.3 Transmission Electron Microscopy 104 4.4.3.1 Sample Preparation 104 4.4.3.2 Structural Characterization 105 4.4.3.3 Morphological Characterization 106 4.4.3.4 Compositional Characterization 108 4.4.3.5 STEM Application to Metals in Zeolites and Coke Analysis 109 4.5 Infrared Spectroscopy Characterization of Zeolitic Systems 111 4.5.1 Introduction to Infrared Spectroscopy 111 4.5.2 Modes of Measurement 112 4.5.3 Framework IR 114 4.5.3.1 Zeolite Structure 115 4.5.3.2 Tracking Zeolite Framework Si/Al 116 4.5.3.3 Zeolite Synthesis 118 4.5.4 Methods Requiring Sample Pretreatment 119 4.5.5 Hydroxyl IR 120 4.5.6 Acidity 123 4.5.6.1 General Theory 124 4.5.6.2 Selection of Probe Molecules 125 4.5.6.3 Quantitation of Sites 125 4.5.6.4 Pyridine Adsorption 127 4.5.6.5 Ammonia 130 4.5.6.6 Low-Temperature Acidity Probes 131 4.5.6.7 Carbon Monoxide 132 4.5.6.8 Nitrogen (N 2 ) 134 4.5.6.9 Measurement of External Acidity 134 4.5.6.10 Other Probes 135 4.5.7 In Situ/In Operando Studies 136 4.5.8 Characterization of Metal-Loaded Zeolites 136 4.5.8.1 Cation Exchange for Adsorption/Separation 137 4.5.8.2 Metal-Loading for Catalysis 138 4.5.8.3 Noble Metal-Loading for Catalysis 138 4.5.8.4 Non-Noble Metal-Loading for Catalysis 139 VIII Contents 4.6 NMR Characterization of Zeolitic Systems 140 4.6.1 Introduction to NMR 140 4.6.1.1 Spin-Half Nuclei 142 4.6.1.2 Cross Polarization 142 4.6.1.3 Quadrupolar Nuclei 143 4.6.1.4 Dipolar Recoupling 143 4.6.1.5 Pulsed Field Gradient NMR – diffusion 144 4.6.2 Applications 145 4.6.2.1 29 Si NMR 145 4.6.2.2 27 Al NMR 147 4.6.2.3 31 P NMR 149 4.6.2.4 1 H NMR 150 4.6.2.5 17 O and Other Nuclei 151 4.6.2.6 Diffusion of Hydrocarbons in Zeolites 151 4.7 Physical/Chemical Characterization 152 4.7.1 Nitrogen Physisorption 152 4.7.2 Thermal and Mechanical Analyses 154 4.7.3 Adsorption Capacity 156 4.7.4 Acid Sites 157 4.8 Conclusions 158 4.8.1 Future Characterization Directions 158 References 160 5 Overview in Zeolites Adsorptive Separation 173 Santi Kulprathipanja and Robert B. James 5.1 Introduction 173 5.2 Industrial Adsorptive Separation 173 5.2.1 Gas Separation 173 5.2.2 Liquid Separation 174 5.2.2.1 Aromatics 174 5.2.2.2 Non-Aromatic Hydrocarbons 174 5.2.2.3 Non-Petrochemicals 175 5.2.2.4 Trace Component Removal 175 5.3 R&D Adsorptive Separation 176 5.3.1 Aromatic Hydrocarbon Separation 176 5.3.2 Non-Aromatic Hydrocarbon Separation 176 5.3.3 Carbohydrate Separation 176 5.3.4 Pharmaceutical Separation 176 5.3.5 Trace Impurities Removal 176 5.3.5.1 Sulfur Removal 176 5.3.5.2 Oxygenate Removal 188 5.3.5.3 Nitrogenate Removal 190 5.3.5.4 Iodide Removal 190 5.3.5.5 Aromatic Removal 190 5.3.5.6 Metal Removal 190 [...]... 8.6.2.1 8.6.2.2 8.7 Mono-Methyl Paraffins Separation (C10–16) Industrial Use and Demand 263 Unique Operating Parameters 264 Olefin Separations 265 C4 Separations 266 Industrial Use and Demand 266 Unique Operating Parameters 266 Detergent Range Olex C10–16 267 Industrial Use and Demand 267 Unique Operating Parameters 268 Carbohydrate Separation 269 Industrial Use and Demand 269 Unique Operating Parameters 269... definition of a zeolite and describes their basic and composite building units and how they are linked in zeolite frameworks It defines pores, channels, cages and cavities; and it gives references for finding detailed Zeolites in Industrial Separation and Catalysis Edited by Santi Kulprathipanja Copyright © 2010 WILEY- VCH Verlag GmbH & Co KGaA, Weinheim ISBN: 97 8-3 -5 2 7-3 250 5-4 XX Preface information about... pore zeolites with 10-ring pores, 0.45–0.60 nm in free diameter (ZSM-5), (iii) large pore zeolites with 12-ring pores of 0.6–0.8 nm (e.g., zeolites X, Y) and (iv) extra-large pore zeolites with 14ring pores (e.g., UTD-1) The zeolite framework should be viewed as somewhat flexible, with the size and shape of the framework and pore responding to changes in temperature and guest species For example, ZSM-5... mordenite and clinoptilolite [23] Mordenite and clinoptilolite are used in small volume in adsorbent applications including air separation and in drying and purification [24] Natural zeolites have also found use in bulk applications as fillers in paper, in pozzolanic cements and concrete, in fertilizer and soil conditioners and as dietary supplements in animal husbandry 1.2 History of Molecular Sieve Materials... mordenite, erionite and over a half-dozen other zeolites have been prepared by steaming and acid extraction These materials are reported to be hydrophobic and organophilic and represent a range of pore sizes from 0.4 to 0.8 nm A very large number of high-silica zeolites prepared by direct synthesis have now been reported, including beta, ZSM-5, -1 1, -1 2, -2 1, -3 4, NU-1, FU-1 and ferrisilicate and borosilicate... silicoaluminophosphate (SAPO) family [30] includes over 16 microporous structures, eight of which were never before observed in zeolites The SAPO family includes a silicon analog of the 18-ring VPI-5, Si-VPI-5 [31], a number of large-pore 12-ring structures including the important SAPO-37 (FAU), medium-pore structures with pore sizes of 0.6–0.65 nm and small-pore structures with pore sizes of 0.4–0.43 nm, including... 2,6-Dimethylnaphthalene 244 Industrial Uses and Demand 244 Method of Production 244 Ethylbenzene 244 Industrial Uses and Demand 244 Method of Production 244 p-Cresol 245 Industrial Uses and Demand 245 Method of Production: Adsorbent–Desorbent 245 Summary 245 References 246 8 Liquid Industrial Non-Aromatics Adsorptive Separations 249 Stephen W Sohn Introduction 249 Normal Paraffin Separations 249 Characteristics... CHA (-3 4, -4 4, -4 7), ERI (-1 7), GIS (-4 3), LEV (-3 5), LTA (-4 2), FAU (-3 7) and SOD (-2 0) Also shown is the pore size and saturation water pore volume for each structure type The structures include the first very large pore molecular sieve, VPI-5, with an 18-ring one-dimensional channel with a free pore opening of 1.25 nm [29], large pore (0.7–0.8 nm), intermediate pore (0.6 nm), small pore (0.4 nm) and. .. on an in nitely extending three-dimensional, four-connected framework of AlO4 and SiO4 tetrahedra linked to each other by the sharing of oxygen ions Each AlO4 tetrahedron in the framework bears a net negative charge which is balanced by an extra-framework cation The framework structure contains Zeolites in Industrial Separation and Catalysis Edited by Santi Kulprathipanja Copyright © 2010 WILEY- VCH... Adsorption Acid Separations 269 Citric Acid Separation 270 Industrial Use and Demand 270 Unique Operating Parameters 270 Free Fatty Acid Separation 270 Industrial Use and Demand 270 Unique Operating Parameters 270 Summary 271 References 271 9 Industrial Gas Phase Adsorptive Separations 273 Stephen R Dunne Introduction 273 Regeneration 275 Adsorption Equilibrium 276 Henry's Law: A Linear Isotherm 277 . Limited Printing and Binding Bell & Bain Ltd., Glasgow Printed in Great Britain Printed on acid-free paper ISBN: 97 8-3 -5 2 7-3 250 5-4 V Zeolites in Industrial Separation and Catalysis. Edited. by Santi Kulprathipanja Zeolites in Industrial Separation and Catalysis Edited by Santi Kulprathipanja Zeolites in Industrial Separation and Catalysis Further Reading R. Xu, W. Pang, J. Yu,. 97 8-3 -5 2 7-2 966 2-0 J. Hagen Industrial Catalysis A Practical Approach 2006 ISBN: 97 8-3 -5 2 7-3 114 4-6 F. Schüth, K.S.W. Sing, J. Weitkamp (Eds.) Handbook of Porous Solids 5 Volumes 2002 Hardcover ISBN: 97 8-3 -5 2 7-3 024 6-8 Edited