Zeolite Microporous Solids: Synthesis, Structure, and Reactivity

Zeolite Microporous Solids: Synthesis, Structure, and Reactivity

NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NArO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is publisbed by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences B Physics C Mathematlcal and Physical Sciences D Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences G Ecological Sciences H Cel! Biology I Global Environmental Change Plenum Publishing Corporation London and New York Kluwer Academic Publishers Dordrecht, Boston and London Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo NATO-PCo-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords anel/or abstracts) to more than 30000 contributions from international scientists published in aii sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German ( WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series C: Mathematical and Physical Sciences - Voi. 352

Zeolite Microporous Solids: Synthesis, Structure, and Reactivity edited by Eric G. Derouane Facultes Universitaires N.-D. de la Paix, Namur, Belgium Francisco Lemos Instituto Superior Tecnico, Lisboa, portugal Claude Naccache Institut de Recherches sur la Catalyse, CNRS, Villeurbanne, France and Fernando Ramoa Ribeiro Instituto Superior Tecnico, Lisboa, Portugal SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

Proceedings of the NArO Advanced Study Institute on Zeolite Microporous Solids: Synthesis, Structure, and Reactivity Sintra-Estoril, Portugal May 13-25, 1991 Printed an acid-free papar ISBN 978-94-010-5150-7 ISBN 978-94-011-2604-5 (ebook) DOI 10.1007/978-94-011-2604-5 AII Rights Reserved 1992 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1992 Softcover reprint ofthe hardcover Ist edition 1992 No part of the material protected by this copyright notice may be reproduced ar utilized in any farm or by any means, electronic or mechanical, including phatacopying, recording or by any informatian starage and retrieval system, without written permission from the copyright owner.

TABLE OF CONTENTS Preface v Part I. Synthesis 1 P.A. Jacobs Some thennodynamic and kinetic effects related to zeolite crystallization 3 J.-P. Gilson Organic and inorganic agents in the synthesis of molecular sieves 19 J.L. Guth Non-conventional crystalline microporous solids 49 T.J. Pinnavaia and H. Kim Molecular engineering of lamellar solids. I. Principles derived from the piuaring of smectite clays 79 T.J. Pinnavaia, T. Kwon, and S.K. Yun Molecular engineering of layered structures II. Synthetic approaches to some new pillared derivatives 91 Part II. Characterization 105 J.C. Vedrine General overview of the characterization of zeolites 107 L.V.C. Rees, J. Hampson, and P. Briickner Sorption of single gases and their binary mixtures in zeolites 133 L.V.C. Rees and Dongmin Shen Frequency-response measurements of diffusion of sorbates in zeolites 151 J.M. Newsam Diffraction Studies of zeolites 167 D. Barthomeuf Spectroscopic investigations of zeolite properties 193 C. Fyfe, H. Grondey, Y. Feng, H. Gies, and G.T. KokotaiIo The impact of NMR spectroscopy in molecular sieve characterization I. Low Sit Al ratio materials 225 C. Fyfe, H. Grondey, Y. Feng, H. Gies, and G.T. KokotaiIo The impact of NMR spectroscopy in molecular sieve characterization II. Investigations of highly siliceous systems 247 Part III. Modification, Reactivity, and Catalytic Activity 271 H.G. Karge Modification of zeolites and new routes to ion-exchange 273

vi Y. Ben Taarit Zeolite framework substitution reliable characterization methods 291 J. Dwyer Evaluation and tailoring of acid-base properties of zeolites Part 1 303 J. Dwyer Evaluation and tailoring of acid-base properties of zeolites Part 2 321 Y. Ben Taarit Catalysis by exchanged cations and zeolite framework sites 347 A. Corma Zeolites in oil refining and petrochemistry 373 M. Guisnet and P. Magnoux Composition of the carbonaceous compounds responsible for zeolite deactivation. Modes of formation 437 M. Guisnet and P. Magnoux Deactivation of zeolites by coking. Prevention of deactivation and regeneration 457 Part IV. Novel Developments and Vistas 475 J.A. Martens, H. Geerts, P.J. Grobet, and P.A. Jacobs Molecular sieves with pore openings consisting of more than 12-T atoms 477 R.A. Van Santen, A.J.M. De Man, and G.J. Kramer Chemical bonding in zeolites 493 J.A. Martens and P.A. Jacobs Some aspects of molecular shape-selective catalysis with hydrocarbons in zeolites 511 J.A. Rabo New applications of nonclassical molecular sieve catalysts 531 R. Parton, D. De Vos, and P.A. Jacobs Enzyme mimicking with zeolites 555 W.F. Hoelderich Microporous materials in organic synthesis 579 Concluding Remarks: S.M. Csicsery 601 List of Participants 613 Subject Index 629

PREFACE Intensive research on zeolites, during the past thirty years, has resulted in a deep understanding of their chemistry and in a true zeolite science, including synthesis, structure, chemical and physical properties, and catalysis. These studies are the basis for the development and growth of several industrial processes applying zeolites for selective sorption, separation, and catalysis. In 1983, a NATO Advanced Study Institute was organized in Alcabideche (portugal) to establish the State-of-the-Art in Zeolite Science and Technology and to contribute to a better understanding of the structural properties of zeolites, the configurational constraints they may exert, and their effects in adsorption, diffusion, and catalysis. Since then, zeolite science has witnessed an almost exponential growth in published papers and patents, dealing with both fundamentals issues and original applications. The proposal of new procedures for zeolite synthesis, the development of novel and sophisticated physical techniques for zeolite characterization, the discovery of new zeolitic and related microporous materials, progresses in quantum chemistry and molecular modeling of zeolites, and the application of zeolites as catalysts for organic reactions have prompted increasing interest among the scientific community. An important and harmonious interaction between various domains of Physics, Chemistry, and Engineering resulted therefrom. Thus, during the last decade, an increasing number of novel zeolite-type microporous solids have been discovered. They stimulated important new developments in molecular shape-selective heterogeneous catalysis for the production of fine chemicals and for synthetic organic chemistry. A number of recent reports clearly demonstrated that biomimetic chemistry in zeolites could be achieved by modeling enzymes within zeolite cavities. Novel interesting applications were also found in the chemistry of petroleum and petrochemicals, the catalytic potential for upgrading oil being correlated with the chemistry and the pore geometry of the zeolites. Therefore, it appeared necessary to present in an integrated fashion a comprehensive, critical, and unified survey of the current State-of-the-Art knowledge of zeolite science with special attention to novel chemical, physical and structural features, and new methods or techniques of zeolite characterization such as Magic Angle Spinning Nuclear Magnetic Resonance, Scanning Transmission Electron Microscopy, X-Ray, Electron and Neutron Diffractions, theoretical computations, and molecular graphic modeling. These are the reasons which have stimulated us to organize the NATO ASI on "Zeolite Microporous Solids: Synthesis, Structure, and Reactivity" of which the lectures are collected in this volume, with the difficult task to cover such a broad field. vii

viii The organizers would like to thank all the lecturers who have made a wonderful work in collecting, analyzing, and discussing the most relevant facts and reports available in the journal and patent literatures, and who have accepted to contribute to this publication in the NATO AS! Series. Special thanks are due to Dr. S.M. Csicsery who, at the last minute, has been asked and has accepted to deliver the concluding remarks. The organizers acknowledge the benevolent help and the efficiency of Dr. Z Gabelica and Dr. F. di Renzo who contributed to the preparation of the final manuscript of the AS! proceedings. They also wish to thank the local committee for all the "hard" work it achieved, which has been the key to the success of this meeting. Acknowledgements are also due to all the participants who by their efforts and continuous and active attendance, by their comments and their questions, have contributed greatly to the success of the Institute. Last, but not least, the organizers express their deepest gratitude to the Scientific Affairs Division of NATO, and to its Science Committee, for having generously supported this NATO Advanced Study Institute. Alcabideche May 1991 Eric G. Derouane Francisco Lemos Claude Naccache Fernando Ramoa Ribeiro