Studies in Surface Science and Catalysis

Advisory Editors: B. Delmon and J.T. Yates

Vol. 49

ZEOLITES: FACTS, FIGURES, FUTURE Proceedings of the 8th International Zeolite Conference, Amsterdam, The Netherlands, July 1 0 - 1 4 , 1989

PartB

Editors

P.A.Jacobs K. U. Leuven, Leuven, Belgium

R.A. van Santen T.U. Eindhoven, Eindhoven, The Netherlands

ELSEVIER Amsterdam — Oxford — New York — Tokyo 1989

CONTENTS

PartA

Preface (by the Editors)

Acknowledgments (by the Conference Chairman)

Organizing Committee

Scientific Committee '

Financial Support

XV

XVII

XVIII

XIX

XX

I. Plenary Lectures

1. Advances in the structural analysis of zeolites, zeolitic precursors and their

analogues

J.M. Thomas ... ... ... ... ... ... ... ... 3

2. Towards a comprehensive mathematical theory for the topology and

geometry of microporous materials

J.V.Smith 29

3. Application of zeolites in fluid catalytic Cracking and related processes

A. Corma 49

4. Zeolites: Catalysts for the synthesis of organic Compounds

W.F. Hölderich 69

5. Zeolites and other microporous materials

D.E.W. Vaughan 95

9.

II. Synthesis and Modification

Are the general laws of crystal growth applicable to zeolite synthesis?

(Keynote lecture)

F. Di Renzo, F. Fajula, F. Figueras, S.Nicolas,

T. des Courieres... ... ... ... ... ... ... ... 119

Growth of single crystals of borozeosilite and titanozeosilite

Shilun Qiu, Wenqin Pang, Shangqing Yao ... ... ... ... 133

Synthesis and characterization of zeolitic microporous alumino-borates

Jianhua Wang, Shouhua Feng, Ruren Xu ... ... ... ... 143

Some aspects of the synthesis, characterisation and properties of zeolite

Nu-2

N.A. Briscoe, J.L. Casci, J.A. Daniels, D.W. Johnson,

M.D. Shannon, A. Stewart 151

10. Applications of MAS-NMR spectroscopy to the Studie of faujasite

synthesis (Keynote Lecture)

D.M. Ginter, C.J. Radke, A.T. Bell 161

11. Kinetic Studies of the crystallization of aluminophosphate and silico-

aluminophosphate molecular sieves

H. Weyda, H. Lechert 169

12. Hydrothermal crystallisation of silica molecular sieves and clathrasils from

amine containing reaction mixtures

K.R. Franklin, B. M. Lowe 179

13. A mechanism study of framework Si-Al Substitution in Y zeolite during

aqueous fluorosilicate treatment

Yigong He, Caiying Li, Enze Min ... ... ... ... ... 189

14. Synthesis of aluminophosphates and dement substituted alumino­

phosphate VPI-5 (Keynote lecture)

M.E. Davies, C. Montes, P.E Hathaway, J.M. Garces 199

15. Isomorphic Substitution of Silicon in SAPO-37

JA. Martens, C. Janssens, P.J. Grabet, H.K. Beyer, P.A. Jacobs ... 215

16. Iron Incorporation into FAPO-5 molecular sieves

A.F. Ojo, J. Dwyer, R.V. Parish 227

17. Synthesis of high-silica sodalite from aqueous Systems: a combined

experimental and model-based approach

J. Keysper, C.J.J. den Ouden, M.F.M. Post 237

18. Synthesis and spectroscopic studies of Co substituted ZSM-5 zeolites

R. Mostowicz, AJ . Dabrowski, J.M. Jabtonski 249

19. Transformation of zeolite A into hydroxysodalite. III. The influence of

temperature on the kinetics of transformation

E. Grujic, B. Subotic, Lj.A. Despotovic ... ... ... ... 261

20. Ion-exchange properties of silanated and disilanated mordenites: the

influence of different modification steps on the ammonium-exchange

capacity

P. de Hulsters, F. Goovaerts, J. Philippaerts, Y. Yan,

E.F Vansant 271

21. Synthesis and characterization of FAPO-5 crystallized from clear

homogeneous Solutions

Wenqin Pang, Shilun Qui, Qiubin Kan, Zhiyun Wu,

Shaoyi Peng, Guochuan Fan, Di Tian ... ... ... ... ... 281

22. Syntheses of pentasil silica-zeolites from nonaqueous Systems

Qisheng Huo, Shouhua Feng, Ruren Xu ... ... ... ... 291

23. Sequence of high silica zeolites found during synthesis experiments in the

presence of a quaternary adamantammonium cation

S.I. Zones, R.A. Van Nordstrand, D.S. Santilli.D.M. Wilson, L.Yuen,

L.D. Scampavia ... ... ... ... ... ... ... ... 299

VII

24. Synthesis of ZSM-5 and ZSM-11 zeolites with TBA and TBP cations and

their structural characterization

V. KauciC, S. GasperSid, S. Hocevar 311

25. The effects of varying the tetraalkylammonium template on high-silica

zeolite synthesis

A. Nastro, F. Crea, D.T. Hayhurst, F. Testa, R. Aiello,

L. Toniolo ... ... ... ... ... ... ... ... 321

26. Zeolite chemistry VII. Framework Substitution for aluminum in zeolites

via secondary synthesis treatment

G.W. Skeels, E.M. Flanigen 331

27. Study of cationic (Li + , N a + , K + ) specificity in hydrated Silicate and

aluminosilicate structure formation processes

V.G. Il'in, N.V. Turutina, V.N. Solomakha 345

28. Isomorphous replacements in the framework of mordenite

E.E. Senderov, A.M. Bychkov, I.V. Mishin, A.L. Klyachko,

H.K. Beyer 355

29. Synthesis of zeolite Na-A in the presence of triethanolamine

G. Scott, A.G. Dixon, A. Sacco Jr., R.W. Thompson ... ... ... 363

III. New Materials and Pillared Clays 30. The next generation: synthesis, characterization and structure of metal

sulfide-based microporous solids (Keynote lecture)

R.L. Bedard, S.T. Wilson, L.D.Vail, J.M. Bennett, E.M. Flanigen ... 375

31. Preparation and properties of clays pillared with zirconium and their use in

HPLC separations

A Dyer, T Gallardo, C.W. Roberts 389

32. Selective placement of Fe + ions in pillared clay catalysts

A. Kostapapas, S.L. Suib, R.W. Coughlin, M.L. Occelli 399

33. The synthesis of beryllophosphate zeolites

G. Harvey, W.M. Meier 411

34. Germanium-rich MFI zeolites: the first example of an extended framework

Substitution of Silicon by another tetravalent dement

Z. Gabelica, J.L. Guth 421

35. The incorporation of selenium into the Channels of mordenite

O. Terasaki, K. Shiokawa, M. Ito, K. Yamazaki, D. Watanabe,

J.M.Thomas ... ... ... ... ... ... ... ... 431

36. Ultralarge pore molecular sieves: characterization of the 14Ä pore mineral

Cacoxenite

R. Szostak, R. Kuvadia, J. Brown, TL . Thomas ... ... ... 439

37. Synthesis and characterization of CoAPO and CoAPSO molecular sieves

S. Ernst, L. Puppe, J. Weitkamp ... ... 447

VIII

38. Preparation and acidic properties of antimonosilicate with MFI structure

K. Yamagishi, S. Namba, T. Yashima ... ... ... ... ... 459

39. The pillaring of a synthetic hectorite with organic cations

M.L. Occelli, P.S. Iyer, J.V. Sanders 469

40. The preparation of characterization of some pillared clays

Lubin Zheng, Yushi Hao, Longxiang Tao ... ... ... ... 481

IV. Natural Zeolites and Utilization

42. Cünoptololite to heulandite transformation in burial diagenesis

S. Ogihara, A. Iijma 491

43. Zeolitic alteration of lacustrine tuffs, Western Snake River Piain, Idaho

R.A. Sheppard 501

44. Zeolites in heat recovery

S. Ulku, M. Mobedi 511

45. Regenerative zeolite heat pump

D.I. Tchernev 519

46. Clinoptilolite from basaltic vulcanic glass in the Cuban Carolinas Deposit

L.A. Reyes, N.Vega 527

48. Effects of exchangeable cations on the thermal behavior of fibrous zeolites

A. Yamazaki, R. Otsuka ... ... ... ... ... ... 533

V. Characterization

49. Multitechnique analysis of the lattice structures of highly siliceous zeolites

(Keynote lecture)

CA. Fyfe, H. Gies, G.T. Kokotailo, Y. Feng, H. Strobl, B. Marler,

D.E. Cox 545

50. Spectroscopy of cobalt in CoAPO-5

R.A. Schoonheydt, R. De Vos, J. Pelgrims, H. Leeman ... ... 559

51. NMR Evaluation of receptor sites in molecular sieve catalysts

E.G. Derouane, J.B.Nagy, B. De Roover, C. Fernandez ... ... 569

53. 1 2 9 X e NMR studies of type NaY, ZSM-5 and ZSM-20 zeolite

crystallization

T. Ito, J. Fraissard, J. B.Nagy, N. Dewaele, Z. Gabelica,

A. Nastro, E.G. Derouane ... 579

54. Assessment of a reaction mechanism for catalytic dimerization of ethylene

on palladium exchanged Na-X and Ca-X zeolites based on reaction

intermediates detected by electron spin echo methods

A.K. Ghosh, L. Kevan 589

55. The use of high resolution electron microscopy in fundamental zeolite

research

H.W. Zandbergen, D. van Dyck 599

IX

57. High temperature NMR of zeolites

R. Janssen, P.P.M.A. Dols, G.A.H., Tijink, W.S. Veeman 609

58. D NMR of Cg hydrocarbon molecules in K-L zeolites

B.G. Silbernagel, A.R. Garcia, R. Hulme, J.M. Newsam ... ... 615

59. MAS NMR studies on superacid sites

E. Brunner, H. Ernst, D. Freude, T. Fröhlich, M. Hunger,

H.Pfeifer 623

61. The characteriation of zeolites by gas adsorption

M.J.G. Janssen, C.W.M. van Oorschot 633

62. On the relation between NH3 adsorption data and lattice constant of

steamed NH4NaY and NH4RENaY

J.W. Roelofsen, H. Mathies, R.L. de Groot 643

63. Studies of acidity of HM by improved IR-TPD technique

Zhiyuan Xue, Leiming Zhu, Quanzhi Li, Ruiming Zhang ... ... 651

64. Strenght of acid sites in zeolites using UV-visible spectroscopy:

effect of AI content

C. Naccache, Fang Ren Chen, G. Coudurier ... ... ... ... 661

66. Proton NMR study of water absorbed in mordenite

C. Cruz, D. Diaz, A. Leyva, M. Chacon ... ... ... ... 669

67. Isomorphous Substitution of Si in zeolite Single crystals. Part II. On the

boron distribution and coordination in (B)-ZSM-5

J.C. Jansen, R. de Ruiter, E. Biron, H. van Bekkum ... ... ... 679

P a r t B

VI. Structure and Theory

68. On the use of graphs in zeolite structural chemistry (Keynote lecture)

W.M.Meier 691

69. Modelling of the adsorption of aromatics on silicalite on molecular

Statistical basis (Keynote lecture)

B. Grauert, K. Fiedler, H. Stach, J. Jänchen ... ... ... ... 701

70. Hypothetical two and three dimensional Channel zeolite framework

structures

G.T. Kokotailo, CA. Fyfe, H. Gies, D.E. Cox 715

71. Synthesis and idealized topology of AIPO4-52, a new member of the ABC

six-ring family

J.M. Bennett, R.M. Kirchner, S.T. Wilson 731

72. Quantum-chemical Interpretation of intrazeolite chemistry phenomena

A.G Pelmenshchikov, G M . Zhidomirov, K.I. Zamaraev ... ... 741

73. Molecular dynamics by numerical Simulation of methane in NaA zeolite

E. Cohen de Lara, R. Kahn, A.M. Goulay, M. Lebars ... ... 753

74. Rigid ion and shell model calculations of IR spectra of zeolitic silica

polymorphs

B.W.H. van Beest, A.J.M. de Man, R.A. Jackson, C.R.A. Catlow,

R.A. van Santen... ... ... ... ... ... ... ... 763

75. Effects of long-range interactions in zeolite-like Systems: dynamical

behavior of water in ferrierite from molecular dynamics Simulation

L. Leherte, D.P. Vercauteren, E.G. Derouane, G.C. Lie,

E. Clementi, J.-M Andre 773

76. A quantitative understanding of molecular interactions in molecular sieves

using the electronegativity equalization method

L. Uytterhoeven... ... ... ... ... ... ... ... 785

77. Theoretical studies of Sorption in zeolites

R. Vetrivel, C.R.A. Catlow, E.A. Colbourn 795

78. The compositional dependence of Si chemical shifts in faujasite

framework zeolites

M.T. Melchior, J.M. Newsam 805

79. Initial adsorption heat and interaction energy of four linear molecules in

zeolites A

Y. Delaval, E. Cohen de Lara, Nguyen-Tan Tai ... ... ... 815

80. Ion exchange of Ni ions in siliceous ZSM-5

C.J.J. den Ouden, A.F.H. Wielers, H.P.C.E. Kuipers,

M. Vaarkamp, M. Mackay, M.F.M. Post 825

81. Geometrical relationships and charge linkage between encapsulated

molecules and host aluminophosphate-based frameworks

J.J. Pluth, J.V. Smith 835

VII. Adsorption and Diffusion

82. Interaction of hydrocarbons and water with ZSM5

A. Jentys, G. Mirth, J. Schwank, J.A. Lercher... 847

83. Effect of template removal and rehydration on the stmcture of AIPO4 and

AIPO4- based microporous crystalline solids

M. Goepper, F. Guth, L. Delmotte, J.L Guth, H. Kessler 857

84. Liquid phase adsorption, diffusion and counter diffusion of aromatic

hydrocarbons on ZSM-5 zeolites

N.V. Choudary, R.V. Jasra, S.G.T. Bhat, T.S.R. Prasada Rao ... 867

85. A comparative study of adsorption and diffusion of vapor alcohols and

alcohol from aqueous Solutions in silicalite

Y.S. Lin, Y.H. Ma 877

86. Molecular sieve films from zeolite-silica microcomposites

T. Bein, K. Brown, C.J. Brinker 887

XI

87. Intracrystalline diffusion of linear paraffins and benzene in silicalite

studied by the ZLC method

M. Eic, D.M. Ruthven 897

88. Self-diffusion studies by NMR tracer uptake measurements

C. Forste, J. Kärger, H. Pfeifer 907

89. Diffusion of hydrocarbons in silicalite using a frequency-response method

N.G. Van-Den-Begin, L.V.C. Rees 915

90. Peculiarities of the mass transport across zeolite crystal surfaces

M. KoÖirik, A. Zikänova, P. Struve, M. Bülow ... ... ... 925

91. Interaction of benzene or ethylbenzene with zeolites Y and AIPO4-5

A. de Mallmann, S. Dzwigaj, D. Barthomeuf ... ... ... ... 935

92. Sorption of aromatic Compounds from Solutions by zeolite 13X

K. Al-Zaid, F. Owaysi, S. Akashah, Y.A. Eltekov 945

94. Fluid adsorption in zeolites at high pressures

A.A. Fomkin ... ... ... ... ... ... ... ... 953

95. FTIR spectra of bases sorbed on H + ZSM-5 - A study of hydrogen bonding

L.M. Parker, D.M. Bibby, G.R. Bums 963

VIII. Metals in Zeolites

96. Design of metal Clusters in NaY zeolite (Keynote lecture)

S.T. Homeyer, W.M.H. Sachtier 975

97. X-Ray absorption studies of the interaction between Pd and Co in bimetal

exchanged zeolite Y

K. Moller, T. Bein 985

98. The chemistry of Pt-NaY zeolite preparation

B.F. Chmelka, R.R. Rosin, G.T. Went, A.T. Bell, C.J. Radke,

E.E.Petersen 995

99. Faujasite embedded platinum: zeolite framework texture and effect of

metal dispersion on syngas conversion

N.J.. Jaeger, J. Rathousky, G. Schulz-Ekloff, A. Svensson,

A. Zukal 1005

101. Preparation and characterization of Mo-containing zeolites

J. Valyon, A. Meszaros-Kis ... ... ... ... ... ... 1015

102. Characterization and sulfidation of stabilized HY zeolites containing Ni,

Mo and the NiMo association

A. Ezzamarty, E. Catherine, D. Cornet, J.F. Hemidy, A. Janin,

J.C. Lavalley, J. Leglise, P. Meriaudeau 1025

103. Y pure faujasite and interchanged with several metals (Pt, Ni, Co, Cu):

a structural and physico-chemical study

D.R. Acosta, J. Orozco, M. Briceno, H. Alfaro, M. Ogura ... ... 1035

104. Iron particle characterization in NaX zeolite by temperature dependent

Mössbauer and FMR studies

H.M. Ziethen, A.X. Trautwein, H. Winkler, F. Schmidt 1043

105. Studies on interaction of carbon monoxide with transition metal ion-

exchanged zeolites A

H. Förster, U. Witten 1053

106. On the preparation of nickel loaded AIPO4-5

B. Kraushaar-Czarnetzki, J.H.C. van Hooff ... ... ... ... 1063

IX. Catalysis

107. Reactions of electrophilic substitutions on zeolite catalysts. Aniline

alkylation by methanol (Keynote lecture)

K.G. Ione, O.V. Kikhtyanin 1073

108. New applications of zeolite Systems in catalytic organic synthesis

Kh.M. Minachev, Ya.I. Isakov, T.A. Isakova ... ... ... ... 1085

109. Selective alkylation of aniline with methanol over boronsilicate

molecular sieve

S.I. Woo, J.K. Lee, S.B. Hong, Y.K. Park, Y.S. Uh 1095

110. Development of high selective catalyst for N,N-dimethylanaline production

P.Y. Chen, S.J. Chu, R S . Chang, T.K. Chuang 1105

111. The spaciousness index: a useful catalytic method for probing the effective

pore width of molecular sieves (Keynote lecture)

J. Weitkamp, S. Ernst, C.Y. Chen 1115

112. Characterisation of zeolite shape selectivity - the shape selectivity index

F. Joensen, N. Blom, N.J. Tapp, E.G. Derouane, C. Fernandez ... 1131

113. Influence of the pore geometry of medium pore zeolites ZSM-5, -22, -23,

-48 and -50 on shape selectivity in reactions of aromatic hydrocarbons

R. Kumar, G.N. Rao, P. Ratnasamy 1141

114. Hydrothermally stable chabazites for the selective preparation of olefins

from methanol

S. Cartlidge, R. Patel 1151

115. Stability of GaMFI catalysts in the aromatization of propane

L. Petit, J.P. Bournonville, F. Raatz 1163

116. On the nature of active sites for dehydrogenation of saturated

hydrocarbons in HZSM-5 zeolites modified by zinc and gallium oxides

V.B. Kazansky, L.M. Kustov, A.Yu. Khodakov 1173

117. Pt loaded high-Ga Silicates for aromatization of light paraffins and

methane

T. Inui, Y. Ishihara, K Kamachi, H. Matsuda.. ... ... ... 1183

118. Propene oligomerization over boron modified ZSM-5

B. Andersen, CT. O'Connor, M. Kojima ... ... ... ... 1193

XIII

119. Acetone conversion and deactivation of zeolites

L. Kubelkovä, J. Cejka, J. Novakova, V. BosäÖek, I. Jirka, P. Jirü ... 1203

120. A vapor phase Beckmann rearrangement over high-silicious ZSM-5

H. Sato, K. Hirose, M. Kitamura, Y. Nakamura ... ... ... 1213

121. Dehydrogenation of alcohols on HZSM-5 zeolites

C.P. Bezouhanova, Chr. Dimitrov, V. Nenova, Yu. Kalvachev,

H. Lechert 1223

122. Selective ammoxidation of propane on vanadoaluminophosphate catalysts

A. Miyamoto, Y. Iwamoto, H. Matsuda, T. Inui ... ... ... 1233

123. On the properties of pure and isomorphic-substituted zeolites in the

presence of gaseous oxygen: selective transformation of propane

L.W. Zatorski, G. Centi, J. Lopez Nieto, F. Trifiro, G. Bellussi,

V. Fattore 1243

124. The concentration of catalytically active Brönsted sites on zeolites

W.K. Hall, J. Engelhardt, G.A. Sill 1253

125. Octane enhancement induced by zeolites in fluid catalytic cracking

J. Biswas, I.E. Maxwell ... ... ... ... ... ... ... 1263

126. Hydrothermal aging of cracking catalysts. IV. Destabilizing effect of

vanadium on USY zeolites and FCC catalysts

P. Gallezot, B. Feron, M. Bourgogne, Ph. Engelhard 1281

127. The effect of dealumination procedure on the acidity and catalytic

properties of Y zeolites

E.H. van Broekhoven, S. Daamen, R.G. Smeink, H. Wijngaards,

J.Nieman 1291

128. Carbon monoxide hydrogenation catalyzed by zeolite-supported ruthenium

carbonyl Clusters in the presence of methyl iodide

T. Tatsumi, H. Odajima, K. Yamaguchi, H. Tominaga ... ... 1301

129. Preservation of zeolite crystallinity in the presence of metal contaminants

M.L. Occelli, J.M. Stencel 1311

130. UV-Visible spectroscopic investigations and related studies on coke

formation over industrial H-ZSM-5-based catalysts

H.G. Karge, M. Laniecki, M. Ziotek, G. Onyestyak, A. Kiss,

P. Kleinschmit, M. Siray 1327

131. Hydroisomerization and hydrocracking of alkanes. 5. Hydroisomerization

and hydrocracking of n hexane and n heptane on PtHY catalysts. Effect of

the distribution of metallic and acid sites

F. Alvarez, F.R. Ribeiro, G. Giannetto, F.Chevalier, G. Perot,

M. Guisnet 1339

132. Isomerization of Cg aromatic cuts on modified zeolite catalysts with

different structures

M.F. Ribeiro, Ch. Travers, F. Raatz, Ch. Marcilly, F.R. Ribeiro ... 1349

XIV

133. Influence of the tortuosity and the acidity of H-ZSM-5 on the selectivities

in ethylation of toluene

F. Lonyi, J. Engelhardt, D. Kallo 1357

134. Hydroisomerization and hydrocracking of alkanes. 4. Methylcyclohexane

transformation on PtUSHY catalysts

F. Alvarez, A. Montes, G. Perot, M. Guisnet ... 1367

135. Poisoning by Ni of the zeolite component of FCC catalysts: a model study

V. Cadet, F. Raatz, J. Lynch, Ch. Marcilly 1377

136. The formation of toluene disproportionation intermediates on zeolite

catalysts

Fang Ren Chen, G. Coudurier, C. Naccache ... ... ... ... 1387

137. Cracking and hydrocracking properties of zeolite omega

B. Chauvin, V. Rajoafanova, B. Coq, F. Figueras, F. Fajula,

T. des Courieres 1397

138. Catalytic properties of a zeolite System in bicyclo[2.2.1]hepta-2,5-diene

reactions

B.I. Azbel, N.F. Goldshleger, E.T. Epelbaum, Yu.Yu. Yampolskii,

M. Khidekel, Ya.I. Isakov, Kh. M. Minachev 1407

139. Modification of zeolite Y by tungsten oxide

G.J. Hutchings, G. Buckles 1413

140. On the role of Ga, Pt, PtCu and PtGa in HZSM-5 for the cyclisation of

propane into aromatics

P. Meriaudeau, G. Sapaly, C. Naccache 1423

141. Fe-ZSM-5: physico chemical and catalytic properties

D.H. Lin, G. Coudurier, J.C. Vedrine 1431

Author Index... 1449

Keyword Index ... ... ... ... ... ... ... ... ... 1455

Studies in Surface Science and Catalysis (other volumes in the series) ... ... 1463

Proceedings of previous International Zeolite Conferences ... ... ... 1466

The figures given before the article titles indicate the paper numbers used during the Conference