Guidelines for Mastering the Properties of Molecular Sieves: Relationship between the Physicochemical Properties of Zeolitic Systems and Their Low Dimensionality

423 Pages·1991·11.89 MB·English

by  Machteld Mertens, Johan A. Martens, Piet J. Grobet, Peter A. Jacobs (auth.), Denise Barthomeuf, Eric G. Derouane, Wolfgang Hölderich (eds.)

Guidelines for Mastering
the Properties of
Molecular Sieves
Relationship between the
Physicochemical Properties of
Zeolitic Systems
and Their Low Dimensionality
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Series B: Physics
Guidelines for Mastering
the Properties of
Molecular Sieves
Relationship between the
Physicochemical Properties of
Zeol itic Systems
and Their Low Dimensionality
Edited by
Denise Barthomeuf
Universite Paris VI
Paris, France
Eric G. Derouane
Universite Notre Dame de la Paix
Namur, Belgium
and
Wolfgang Holderich
BASF
Ludwigshafen, Federal Republic of Germany
Plenum Press
New York and London
Published in cooperation with NATO Scientific Affairs Division
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Proceedings of a NATO Advanced Research Workshop on
Physicochemical Properties of Zeolitic Systems
and Their Low Dimensionality,
held April 24-28, 1989,
in Chantilly, France
Library of Congress Cataloging in Publication Data
NATO Advanced Research Workshop on Physicochemical Properties of Zeolitic
Systems and Their Low Dimensionality (1989: Chantilly, France)
Guidelines for mastering the properties of molecular sieves: relationship be-
tween the physicochemical properties of zeolitic systems and their low dimen-
sionality 1 edited by Denise Barthomeuf, Eric G. Derouane, and Wolfgang
Holderich.
p. cm.-(NATO ASI series. Series B, Physics; vol. 221)
"Published in cooperation with NATO Scientific Affairs Division."
"Proceedings of a NATO Advanced Research Workshop on Physicochemical
Properties of Zeolitic Systems and Their Low Dimensionality, held April 24-28,
1989, in Chantilly, France"-T.p. verso.
Includes bibliographical references and index.
ISBN-13: 978-1-4684-5789-6 e-ISBN-13: 978-1-4684-5787-2
001: 10.1007/978-1-4684-5787-2
1. Molecular sieves-Congresses. 2. Zeolites-Congresses. I. Barthomeuf,
Denise. II. Derouane, E. G. III. Holderich, Wolfgang. IV. North Atlantic Treaty
Organization. Scientific Affairs Division. V. Title. VI. Series: NATO ASI series.
Series B., Physics; v. 221.
TP159.M6N38 1989 90-7497
660'.284245-dc20 CIP
© 1990 Plenum Press, New York
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SPECIAL PROGRAM ON CONDENSED SYSTEMS
OF LOW DIMENSIONALITY
This book contains the proceedings of a NATO Advanced Research
Workshop held within the program of activities of the NATO
Special Program on Condensed Systems of Low Dimensionality,
running from 1983 to 1988 as part of the activities of the NATO
Science Committee.
Other books previously published as a result of the activities of
the Special Program are:
Volume 148 INTERCALATION IN LAYERED MATERIALS
edited by M. S. Dresselhaus
Volume 152 OPTICAL PROPERTIES OF NARROW-GAP LOW-
DIMENSIONAL STRUCTURES
edited by C. M. Sotomayor Torres, J. C. Portal,
J. C. Maan, and R. A. Stradling
Volume 163 THIN FILM GROWTH TECHNIQUES FOR LOW-
DIMENSIONAL STRUCTURES
edited by R. F. C. Farrow, S. S. P. Parkin,
P. J. Dobson, J. H. Neave, and A. S. Arrott
Volume 168 ORGANIC AND INORGANIC LOW-DIMENSIONAL
CRYSTALLINE MATERIALS
edited by Pierre Delhaes and Marc Drillon
Volume 172 CHEMICAL PHYSICS OF INTERCALATION
edited by A. P. Legrand and S. Flandrois
Volume 182 PHYSICS, FABRICATION, AND APPLICATIONS OF
MULTILAYERED STRUCTURES
edited by P. Dhez and C, Weisbuch
Volume 183 PROPERTIES OF IMPURITY STATES IN SUPERLATTICE
SEMICONDUCTORS
edited by C. Y. Fong, Inder P. Batra, and S. Ciraci
Volume 188 REFLECTION HIGH-ENERGY ELECTRON
DIFFRACTION AND REFLECTION ELECTRON
IMAGING OF SURFACES
edited by P. K. Larsen and P. J. Dobson
Volume 189 BAND STRUCTURE ENGINEERING IN
SEMICONDUCTOR MICROSTRUCTURES
edited by R. A. Abram and M. Jaros
Volume 194 OPTICAL SWITCHING IN LOW-DIMENSIONAL SYSTEMS
edited by H. Haug and L. Banyai
Volume 195 METALLIZATION AND METAL-SEMICONDUCTOR INTERFACES
edited by Inder P. Batra
Volume 198 MECHANISMS OF REACTIONS OF ORGANOMETALLIC
COMPOUNDS WITH SURFACES
edited by D. J. Cole-Hamilton and J. O. Williams
SPECIAL PROGRAM ON CONDENSED SYSTEMS
OF LOW DIMENSIONALITY
Volume 199 SCIENCE AND TECHNOLOGY OF FAST ION CONDUCTORS
edited by Harry L. Tuller and Minko Balkanski
Volume 200 GROWTH AND OPTICAL PROPERTIES OF WIDE-GAP II-VI
LOW-DIMENSIONAL SEMICONDUCTORS
edited by T. C. McGill, C. M. Sotomayor Torres,
and W. Gebhardt
Volume 202 POINT AND EXTENDED DEFECTS IN SEMICONDUCTORS
edited by G. Benedev, A. Cavallini, and W. SchrOter
Volume 203 EVALUATION OF ADVANCED SEMICONDUCTOR MATERIALS
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edited by David Cherns
Volume 206 SPECTROSCOPY OF SEMICONDUCTOR MICROSTRUCTURES
edited by Gerhard Fasol, Annalisa Fasolino,
and Paolo Lugli
Volume 213 INTERACTING ELECTRONS IN REDUCED DIMENSIONS
edited by Dionys Baeriswyl and David K. Campbell
Volume 214 SCIENCE AND ENGINEERING OF ONE- AND
ZERO-DIMENSIONAL SEMICONDUCTORS
edited by Steven P. Beaumont and Clivia M. Sotomayor Torres
Volume 217 SOLID STATE MICROBATTERIES
edited by James R. Akridge and Minko Balkanski
PREFACE
Low dimensionality is a multifarious concept which applies to very
diversified materials. Thus, examples of low-dimensional systems are
structures with one or several layers, single lines or patterns of lines,
and small clusters isolated or dispersed in solid systems. Such low-
dimensional features can be produced in a wide variety of materials systems
with a broad spectrum of scientific and practical interests. These features,
in turn, induce specific properties and, particularly, specific transport
properties.
In the case of zeolites, low dimensionality appears in the network of
small-diameter pores of molecular size, extending in one, two or three di-
mensions, that these solids exhibit as a characteristic feature and which
explains the term of "molecular sieves" currently used to name these ma-
terials. Indeed, a large number of industrial processes for separation of
gases and liquids, and for catalysis are based upon the use of this low-
dimensional feature in zeolites. For instance, zeolites constitute the
first class of catalysts employed allover the world.
Because of the peculiarity and flexibility of their structure (and
composition), zeolites can be adapted to suit many specific and diversified
applications. For this reason, zeolites are presently the object of a
large and fast-growing interest among chemists and chemical engineers.
The usual forms of zeolites consist of AI04 and Si0
4 tetrahedra linked
to~ether in such a way that cages, from 0.3 to 1.3 nm in size, are formed
wh1ch, in turn, are associated to create a continuous network of pores
extending in one, two, or three dimensions. The presence of such micro-
pores in a three-dimensional crystal generates fascinating properties.
Molecules of gases or liquids, with the proper size, adsorb in the cages
and they reach a state which is different from that observed either in
free molecules or upon adsorption on other porous solids. In the zeolites
micropores, molecules are immersed in electrostatic field and electrostatic
field gradients since the framework charges distributed in the walls of the
cages surround them at molecular distances. In addition, the high curva-
ture of the cavities modify the interactions caused by Van derWaals forces.
It follows that very unexpected selectivities are observed for adsorption
or for catalysis.
The aim of the Workshop was, first, to describe the present state of
the art in order to, then, find the guidelines that may be used to depict
and synthesize tailor-made zeolites for specific applications in catalysis
or adsorbtion.
vii
This approach requires progress in the fields of synthesis and
techniques of characterization, as well as studies of the influence of the
charged cages on the adsorbed molecules and of the resulting selectivities
in adsorption and catalysis. These points constitute the various chapters
of the Workshop.
The organization of the Workshop was made possible with the financial
support of NATO and of the Catalysis Division of the Societe Fran~aisede
Chimie and with the help of the Laboratory of Surface Reactivity and
Structure at the University of Paris. The kind assistance of Miss F.
Armanini and Mr. A. Shikholeslami are particularly acknowledged. Moreover
the laboratory of Catalysis at the University of Namur was of great help
for the preparation of the book especially Dr. Z. Gabelica.
Many thanks are pre'!lented to all of those who contributed to the
Workshop' and to the book of Proceedings.
P.C. GRAVELLE D. BARTHOMEUF
viii
CONTENTS
ORIENTATION OF CHEMICAL PROPERTIES BY DIRECT SYNTHESIS OF MOLECULAR SIEVES
Effects of substitution in SAPO-n frameworks on their properties
as acid catalysts ••.•••...•.•.........•.•......•..•.....•.•.•
M. Mertens, J.A. Martens, P.J. Grobet, P.A. Jacobs
Zeolite synthesis and crystal tailoring ......•..•........•..•.....• 53
F. Fajula
New mobilizing and templating agents in the synthesis of crystalline
microporous solids . •• . . . . • • . . . . • . . . . . . . . . . • . •. . . . . . . • . . . • . . . 69
J.L. Guth, P. Caullet, A. Seive, J. Patarin, F. Delprato
13 129 .
A C- and Xe-NMR study of the role of the tetraalkylammonLum
cations in the synthesis of high-silica zeolites ........••.•• 87
Q. Chen, J.B. Nagy, J. Fraissard, J. El Hage-Al Asswad, Z. Gabelica,
E.G. Derouane, R. Aiello, F. Crea, G. Giordano, A. Nastro
Promoter effects on phase growth in aluminophosphate and silicalumino-
phosphate gel systems .•.....•.........••....•..•............. 95
R. Szostak
CHARACTERISATION OF STRUCTURAL AND PHYSICOCHEMICAL PROPERTIES
IDF ZEOLITIC SYSTEMS
Recent advances in techniques for characterizing zeolite
structures .......•..•.......•......•......•......•........... 99
D.E.W. Vaughan, M.M.J. Treacy and J.M. Newsam
Recent progress in the understanding of chemical properties
of zeolites ...•..•..•.....•............•......•.......•..•... 12 I
J.C. Vedrine
The determination of (Si,Al) distribution in zeolites .•.••......... 145
A. Alberti, G. Gottardi, T. Lai
Solid state ion exchange -Phenomenon and mechanism ....•............ 157
H.G. Karge, V. Mavrodinova, Z. Zheng, H.K. Beyer
STATIC AND DYNAMIC PARAMETERS IN ADSORPTION AND
CATALYSIS IN ZEOLITES
Temperature dependence of the mobility of molecules sorbed in type A
zeolites ........•...................•................•...... 169
E. Cohen de Lara, R. Kahn
NMR-studies of molecular motion of hydrocarbons in different
faujasites .................................................. 183
H.T. Lechert, W.D. Basler, M. Jia
Zeolitic heteropolyoxometalates ................................... 193
J.B. Moffat, G.B. Mc Garvey, J.B. Mc Monagle, V. Nayak, H. Nishi
LOCALIZED AND OVERALL PROPERTIES RELATED TO THE NATURE AND STRUCTURAL
ORGANIZATION OF THE FRAMEWORK ATOMS
On lattice dynamics, stability and acidity of zeolites 201
R.A. Van Santen, B.M.H. Van Beest, A.J.M. de Man
Confinement effects in sorption and catalysis by zeolites 225
E.G. Derouane
Cooperative and localised effects in catalysis over zeolites ...... 241
J. Dwyer
Long range versus short range interactions in zeolites ............ 263
W.J. Mortier, R. Vetrivel
Acid function in zeolites recent progress ....................... 273
J.A. Rabo, G.J. Gajda
Directing activity and selectivity of large pore acid zeolites
through the control of their physicochemical properties ..... 299
A. Corma
ORIENTATION OF THE PATH OF REACTIONS (CATALYSIS, ADSORPTION) BY
CHEMICAL OR OTHER GEOMETRIC OR NON GEOMETRIC EFFECTS
Is the shape selectivity always responsible for the orientation of,
the reaction path in zeolite catalysis? ................... 319
W.F. Hoelderich
Factors influencing the selectivity of hydrocracking in
zeolites ................................................... 343
J. Weitkamp, S. Ernst
Hydroisomerization and hydrocracking of alkanes.6. Influence of
the pore structure on the selectivity of Pt-zeolite ........ 355
G. Giannetto, F. Alvarez, F.R. Ribeiro, G. Perot, M. Guisnet
The structural elements of faujasite and their impact on cracking
selectivity................................................ 365
A.W. Peters, W.C. Cheng, M. Shatlock, R.F. Wormsbecher, E.T.
Habib Jr.
OVERVIEW OF THE WORKSHOP
Relationship between the physicochemical properties of zeolitic
systems and their low dimensionality....................... 373
E.G. Derouane
DISCUSSION REPORTS
Orientations of Chemical Properties by direct synthesis of
molecular sieves........................................... 381
D.E.W. Vaughan, R.M. Szostak
x