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CATALYTIC SCIENCE SERIES — VOL. 3 Series Editor: Graham J. Hutchings Zeolites for Cleaner Technologies edited by Michel Guisnet Jean-Pierre Gilson Imperial College Press Michel Guisnet Michel Guisnet was born in Cambrai, France in 1939. He holds a graduate degree in Chemistry from the University of Lille and a Doctorate in Physical Chemistry from the University of Poitiers (1970). He was Assistant Professor in Organic Chemistry (Lille), Assistant Professor and later Professor in Physical Chemistry (1973) in Chemical Engineering (Chemical Reactors-Catalysis) at Poitiers Engineering School (ESIP). He assumed the position of Director of the Laboratoire de Catalyse en Chimie Organique (Poitiers University - CNRS) from 1981 to 1990. He is currently the head of the Chemical, Biological and Geological Engineering Doctoral School. The research interest of his group is in the field of acid and bifunctional zeolite catalysts for Refining, Petrochemical and Fine Chemical Industries, the aim being strongly related to the development of more selective and cleaner processes. Modification of zeolites and characterization, reaction mechanisms (isomerization, cracking, alkylation, hydrocracking, acetylation, etc.) and prevention of deactivation by coking and regeneration are his main research areas. He has been involved with some 400 international publications, 8 patents, Chairman of the first three International Symposia Heterogeneous Catalysis and Fine Chemicals (1988, 1990, 1993) Jean-Pierre Gilson Jean-Pierre Gilson was born in Namur, Belgium, in 1955. He studied Physical Chemistry at the University of Namur and received his Ph.D in 1982 for his work on the reactivity and characterization on the MFI zeolite. From 1982 to 1984, he worked in the Process Research Department of UOP, Des Plaines, USA, on reforming and aromatization catalysts. He then moved to Grace Davison, Columbia, USA and worked on octane enhancing catalysts from 1984 to 1987. Afterwards he joined Shell Research Laboratories in Amsterdam, The Netherlands, where he worked from 1987 till 1996 on various catalysis related subjects such as paraffins and aromatics isomerization, solid acid alkylation, lube oil manufacture and processing and Fischer-Tropsch liquids upgrading. He joined the Laboratoire de Catalyse et Spectrochimie at the ISMRA-CNRS in Caen, France in 1996, and has headed this laboratory since 1997. He teaches Physical Chemistry and Catalysis at the Caen Engineering School (ISMRA) and at the University of Caen. i CATALYTIC SCIENCE SERIES Series Editor: Graham J. Hutchings (Cardiff University) Vol. 1 Environmental Catalysis edited by F. ]. J. G. Janssen and R. A. van Santen Vol. 2 Catalysis by Ceria and Related Materials edited by A. Trovarelli Vol. 3 Zeolites for Cleaner Technologies edited by M. Guisnet and J.-P. Gilson Forthcoming: Heterogenised Homogeneous Catalysis by J.-A. M. Andersen CATALYTIC SCIENCE SERIES — VOL. 3 Series Editor: Graham J. Hutchings Zeolites for Cleaner Technologies edited by Michel Guisnet Universite de Poitiers, France Jean-Pierre Gilson Universite de Caen, France Imperial College Press ICP Published by Imperial College Press 57 Shelton Street Covent Garden London WC2H 9HE Distributed by World Scientific Publishing Co. Pte. Ltd. P O Box 128, Farrer Road, Singapore 912805 USA office: Suite IB, 1060 Main Street, River Edge, NJ 07661 UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. ZEOLITES FOR CLEANER TECHNOLOGIES Copyright © 2002 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. ISBN 1-86094-329-2 This book is printed on acid-free paper. Printed in Singapore by Mainland Press PREFACE Clean Technologies, Environmentally Friendly Processes, Clean Products and Green Chemistry..., are terms encountered with an increased frequency by politicians as well as by scientists. This is hardly surprising. On the one hand, the remarkable innovations witnessed during the 20th century by clever chemistry have led to significant improvements in food supply, health and quality of life. On the other hand however, the manufacture, processing, use and disposal of chemicals have unfortunately resulted in significant damage to human health and to our environment. It is an important objective for the Chemical Industry to break this link between innovation and damage. A minimalist attitude would be to simply comply with environmental regulations. A more responsible approach is necessary in which ".. .fundamental knowledge of chemical processes and products is applied to achieve elegant solutions with the ultimate goal of hazard-free, waste-free, energy efficient synthesis of non-toxic products without sacrificing efficacy offunc- 4- » (*) twn ... k '. The remarkable properties of zeolites allow the development of cleaner and more efficient processes for the production of fuels and chemicals. This was clearly highlighted during the lectures delivered by experts in the Petroleum Refining, the Petrochemicals and the Fine Chemicals Industries at the meeting Zeolites for Cleaner Technologies, a Pre-Conference School held in early July 2001 in Poitiers and organized before the 13th International Zeolite Conference (Montpellier, July 2001). While the emphasis was placed on catalytic processes, the significant role played by separations based on zeolite adsorbents was also demonstrated. Pollution abatement through ion-exchange, adsorption and catalysis over zeolites was also considered. The preparation of catalysts and the chemistry of catalytic processes were outlined in general lectures, both aspects being more specifically developed in the presentation of commercially proven processes or emerging technologies. The Poitiers School was held in an informal and friendly atmosphere, giving the opportunity to world famous academic and industrial experts, as well as PhD students, to exchange their views. The key role of zeolites in sustainable development and the constant creativity and dynamism of academic and industrial researchers in the synthesis of molecular sieves, and in the design and development of new zeolite catalysts were particularly emphasized. This book gathers the fifteen lectures presented at the Poitiers School with an introductory chapter; its targeted audience is industrial and academic chemists v VI Preface involved in research, development and education. The aim of the introductory chapter is to provide the basics on zeolites to newcomers to the field. It is, however, a minimum requirement, and the serious reader is encouraged to deepen and broaden his knowledge by going to the more specialized books cited in reference. The other chapters should constitute a valuable source of information for experienced researchers and serious newcomers; they will find the latest fundamental and industrial developments in zeolite science and technology with special emphasis on environmental issues. It is our secret hope that this book will become rapidly obsolete because of the fast pace of scientific and technological accomplishments in the field of zeolites applied to our environment. *Anastas P.T., Warner J.C., Green Chemistry : Theory and Practice, (Oxford University Press, New York, 1998). November 2001 Michel Guisnet Jean-Pierre Gilson The organization of the Poitiers School was made possible by the financial support of various institutions and companies; the help of the zeolite team of the Laboratory of Catalysis in Organic Chemistry from the Poitiers University is greatly appreciated. The kind assistance of this team, especially of P. Ayrault and D. Martin, during the preparation of this book is most particularly acknowledged. Support and Sponsorship UNM1TE P R O G R A M ME ° fc BE JB I'oiricrs Poitou-Charentes MfNfSlMU 1 A '$*& MtCHI-RCHt" TOTAL Conseil General Vlenne mUers tt :imu G R O UP AIR LtQUIDE DSM 1$ E^onMobil PROCATALYSE I Qhodia E2D GRACE Davison Vll This page is intentionally left blank CONTENTS Preface Acknowledgements 1. Introduction to Zeolite Science and Technology M. GuisnetandJ.-P. Gilson 2. The Chemistry of Catalytic Processes A. Corma and A. Martinez 3. Preparation of Zeolite Catalysts T.G. Roberie, D. Hildebrandt, J. Creighton andJ- 4. Refining Processes: Setting the Scene R. H. Jensen 5. Advances in Fluid Catalytic Cracking E.T. Habib, Jr., X. Zhao, G. Yaluris, W.C. Cheng, L.T. Boock and J.-P. Gilson 6. Hydrocracking J.A.R. Van Veen 7. C4-C6 Alkane Isomerization F. Schmidt and E. Kbhler 8. Base Oil Production and Processing M Daage 9. Para-Xylene Manufacturing: Catalytic Reactions and Processes F. Alario and M. Guisnet IX