Molecular Sieves Science and Technology

Editors: H.G. Karge • J. Weitkamp

Volume 1

Springer Berlin Heidelberg New York Barcelona Budapest Hong Kong London Milan Paris Santa Clara Singapore Tokyo

Synthesis

With contributions by J. S. Beck, G. Bellussi, E. N. Coker, P. Cool, S. Ernst, H. Gies, J. C. Jansen, C.T. Kresge, B. Marler, S. B. McCullen, R. Millini, G. Perego, W. J. Roth, S.A. Schunk, F. Schiith, R. Szostak, R.W. Thompson, E. F. Vansant, J. C. Vartuli, U. Werthmann

Springer

Editors: Dr. Hellmut G. Karge Fritz-Haber-Institut der Max-Planck-Gesellschaft Faradayweg 4 - 6 D-14195 Berlin Germany

Professor Dr.-Ing. Jens Weitkamp Institut ftir Technische Chemie I Universit~it Stuttgart D-70550 Stuttgart Germany

ISBN 3-540-63622-6 Springer-Verlag Berlin Heidelberg NewYork

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Synthesis / with contributions by J. Beck... - Berlin ; Heidelberg ; New York ; Barcelona ; Budapest ; Hong Kong ; London ; Milan ; Paris ; Santa Clara ; Singapore ; Tokyo : Springer, 1998

(Molecular sieves ; Vol. 1) ISBN 3-540-63622-6

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Preface to the Series

Following Springer's successful series Catalysis - Science and Technology, this series of monographs has been entitled Molecular Sieves - Science and Techno- logy. It will cover, in a comprehensive manner, all aspects of the science and application of zeolites and related microporous and mesoporous materials.

After about 50 years of prosperous research, molecular sieves have gained a firm and important position in modern materials science, and we are witnessing an ever increasing number of industrial applications. In addition to the more traditional and still prevailing applications of zeolites as water softeners in laundry detergents, as adsorbents for drying, purification and separation pur- poses, and as catalysts in the petroleum refining, petrochemical and chemical industries, novel uses of molecular sieves are being sought in numerous labo- ratories.

By 1998, the Structure Commission of the International Zeolite Association had approved approximately 100 different zeolite structures which, altogether, cover the span of pore diameters from about 0.3 nm to 2 nm. The dimensions of virtually all molecules (except macromolecules) chemists are concerned with fall into this same range. It is this coincidence of molecular dimensions and pore widths which makes zeolites so unique in adsorption and catalysis and enables molecular sieving and shape-selective catalysis. Bearing in mind that each zeo- lite structure can be modified by a plethora of post-synthesis techniques, an almost infinite variety of'molecular sieve materials are nowadays at the re- searcher's and engineer's disposal. In many instances this will allow the pro- perties of a zeolite to be tailored to a desired application. Likewise, remarkable progress has been made in the characterization of molecular sieve materials by spectroscopic and other physico-chemical techniques, and this is particularly true for structure determination. During the last decade, we have seen im- pressive progress in the application of quantum mechanical ab initio and other theoretical methods to zeolite science. The results enable us to obtain a deeper understanding of physical and chemical properties of zeolites and may render possible reliable predictions of their behavior. All in all, the science and application of zeolites is a flourishing and exciting field of interdisciplinary re- search which has reached a high level of sophistication and a certain degree of maturity.

The editors believe that, at the turn of the century, the time has come to collect and present the huge knowledge on zeolite molecular sieves. Molecular Sieves - Science and Technology is meant as a handbook of zeolites, and the term "zeo-

VI Preface to the Series

lites" is to be understood in the broadest sense of the word. While, throughout the handbook, some emphasis will be placed on the more traditional alumo- silicate zeolites with eight-, ten- and twelve-membered ring pore openings, materials with other chemical compositions and narrower and larger pores (such as sodalite, clathrasils, A1PO,-8,VPI-5 or cloverite) will be covered as well. Also included are microporous forms of silica (e.g., silicalite-1 or -2), alumo- phosphates, gallophosphates, silicoalumophosphates and titaniumsilicalites etc. Finally, zeolite-like amorphous mesoporous materials with ordered pore systems, especially those belonging to the M41S series, will be covered. Among other topics related to the science and application of molecular sieves, the book series will put emphasis on such important items as: the preparation of zeolites by hydrothermal synthesis; zeolite structures and methods for structure deter- mination; post-synthesis modification by, e.g., ion exchange, dealumination or chemical vapor deposition; the characterization by all kinds of physico-chemi- cal and chemical techniques; the acidic and basic properties of molecular sieves; their hydrophilic or hydrophobic surface properties; theory and modelling; sorption and diffusion in microporous and mesoporous materials; host/guest interactions; zeolites as detergent builders; separation and purification proces- ses using molecular sieve adsorbents; zeolites as catalysts in petroleum refining, in petrochemical processes and in the manufacture of organic chemicals; zeolites in environmental protection; novel applications of molecular sieve materials.

The handbook will appear over several years with a total of ten to fifteen volumes. Each volume of the series will be devoted to a specific sub-field of the fundamentals or application of molecular sieve materials and contain five to ten articles authored by renowned experts upon invitation by the editors. These articles are meant to present the state of the art from a scientific and, where applicable, from an industrial point of view, to discuss critical pivotal issues and to outline future directions of research and development in this sub-field. To this end, the series is intended as an up-to-date highly sophisticated collection of information for those Who have already been dealing with zeolites in industry or at academic institutions. Moreover, by emphasizing the description and critical assessment of experimental techniques which have been used in molecular sieve science, the series is also meant as a guide for newcomers, enabling them to collect reliable and relevant experimental data.

The editors would like to take this opportunity to express their sincere grati- tude to the authors who spent much time and great effort on their chapters. It is our hope that Molecular Sieves - Science and Technology turns out to be both a valuable handbook the advanced researcher will regularly consult and a useful guide for newcomers to the fascinating world of microporous and mesoporous materials.

Hellmut G. Karge Jens Weitkamp

Preface to Volume I

Obviously, the preparation of molecular sieve materials stands at the origin of their use in science and technology. Since the pioneering work of Barrer and his co-workers and the fascinating achievements of Milton, Breck, Flanigen and others in the Union Carbide laboratories, a wealth of zeolites and related micro- porous and mesoporous materials have been synthesized, and novel materials of this class will continue to be discovered. In almost all instances, hydrothermal synthesis is the method of choice for preparing zeolites, and structure-directing auxiliaries, often referred to as templates, frequently play a vital role. The techniques for hydrothermal synthesis of molecular sieves and the search for novel and more efficient structure-directing agents have reached a high level of sophistication, yet the scientific understanding of the very complex series of chemical events en route from the low-molecular weight reagents to the in- organic macromolecule remained rather obscure.

Consequently, Chapter 1 written by R. W. Thompson gives a modern account of our present understanding of zeolite synthesis. The fundamental mechanisms of zeolite crystallization (primary and secondary nucleation and growth) in hydrothermal systems are highlighted.

Chapter 2 by H. Gies, B. Marler and U. Werthmann critically reviews the methods for synthesizing porosils, the all-silica end members of zeolites. Depending on their pore or cage apertures the porosils are subdivided into clathrasils (at most six-membered ring windows) and zeosils (at least eight- membered ring windows), the latter being valuable adsorbents with hydro- phobic surface properties.

In Chapter 3, S. Ernst gives an overview on more recent achievements in the syntheses of alumosilicates with a pronounced potential as catalysts or ad- sorbents. Examples are zeolites MCM-22, NU-87 and SSZ-24, zeolites with intersecting ten- and twelve-membered ring pores and the so-called super-large pore alumosilicates.

Chapter 4 authored by]. C. Vartuli, W. J. Roth, ]. S. Beck, S.B. McCullen and C. T. Kresge is devoted to the synthesis and properties of zeolite-like amorphous materials of the M41S class with ordered mesopores. These mesoporous solids are currently being scrutinized in numerous laboratories for their potential as adsorbents and catalysts.

Apart from the pore width and pore architecture, the crystal size of a zeolite is often very important. In Chapter 5, E.N. Coker and ]. C. Jansen present a systematic evaluation of the attempts to synthesize either ultra-small (i. e.,

VIII Preface to Volume 1

much smaller than 1 ~m) or ukra-large (i.e., much larger than 1 btm) zeolite crystals.

The second most important class of molecular sieves besides the alumo- silicates are without any doubt the alumophosphates and their derivatives con- taining elements other than aluminum and/or additional elements in the frame- work. Chapter 6 authored by R. Szostak is a review covering the synthesis of these molecular sieve phosphates.

The subsequent Chapter 7 is devoted to the synthesis and characterization of molecular sieve materials containing transition metals in the framework. Authored by G. Perego, R. Millini and G. Bellussi, this Chapter focuses on titanium- silicalite-1 which has recently been found to be a unique catalyst for selective oxidations with hydrogen peroxide. Also covered in this Chapter is the synthesis of vanadium- and iron-containing molecular sieves.

In Chapter 8, S.A. Schunk and F. Schfith are going one step further by re- viewing the literature on microporous and mesoporous materials which are traditionally less familiar to the zeolite community, but rather scattered over the literature on solid-state chemistry. The main intention of this Chapter is to bring this wealth of knowledge to the attention of researchers who routinely look for applications of molecular sieves.

Last but not least, a class of porous materials closely related to zeolites is addressed in Chapter 9" P. Cool and E.F. Vansant discuss the basic principles of preparing pillared clays, and methods for the proper characterization of these fascinating materials are outlined.

Thus Volume 1 of Molecular Sieves - Science and Technology covers the syn- thesis methods for a broad variety of porous solids. In addition to the critical discussion of the synthesis procedures, the reader will find numerous references to the original literature. May we express our hope that Volume 1 of the series helps the community of scientists to prepare all those microporous and meso- porous materials they need for their purposes.

Hellmut G. Karge Jens Weitkamp

Contents

R. W. Thompson: Recent Advances in the Understanding of Zeolite Synthesis . . . . . . .

H. Gies, B. Marler, U. Werthmann: Synthesis of Porosils: Crystalline Nanoporous Silicas with Cage- and Channel-Like Void Structures . . . . . . . . . . . . . . . . . . . . . . . .

S. Ernst: Synthesis of more Recent Aluminosilicates with a Potential in Catalysis and Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

J. C. Vartuli, W.]. Roth, J.S. Beck, S.B. McCullen and C. T. Kresge: The Synthesis and Properties of M41S and Related Mesoporous Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

E.N. Coker and J. C. Jansen: Approaches for the Synthesis of Ultra-Large and Ultra-Small Zeolite Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

R. Szostak: Synthesis of Molecular Sieve Phosphates . . . . . . . . . . . . . . . . . .

G. Perego, R. Millini and G. Bellussi: Synthesis and Characterization of Molecular Sieves Containing Transition Metals in the Framework . . . . . . . . . . . . . . . . . . . .

S.A. Schunk and E Schiith: Synthesis of Zeolite-Like Inorganic Compounds . . . . . . . . . . . . . .

P. Cool and E.E Vansant: Pillared Clays: Preparation, Characterization and Applications . . . . .

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

35

65

97

121

157

187

229

265

289