Introduction to Zeolite Science and Practice (eBook)

Front Cover 1
Introduction to Zeolite Science and Practice 4
Copyright Page 5
Contents 8
Preface 14
List of contributors 16
Chapter 1. The zeolite scene 18
Introduction 18
What makes zeolites so special? 18
Zeolite applications 22
Zeolite market volume 23
Economic impact 24
Zeolite R& D
Zeolite networks 27
Conclusion 28
References 29
Chapter 2. Zeolites and molecular sieves. An historical perspective 30
Early history 30
Industrial history 31
The 80's 32
Review of molecular sieve and zeolite fundamentals 34
History of molecular sieve materials 38
History of synthesis 45
The future 48
History of international conferences and organizations 49
Historical epilogue 50
References 50
Chapter 3. Structural subunits in silicate and phosphate structures 52
Introduction 52
Some basic concepts 54
Structural subunits (SSU) 57
Description of the structure types 68
Conclusions 89
References 92
Chapter 4. The preparation of molecular sieves 94
A. Synthesis of zeolites 94
Introduction 94
Preparatory 100
Zeolite product versus the synthesis mixture 107
The low temperature reaction mixture 109
The temperature raise of the reaction mixture 115
The high temperature reaction process 117
Isolation of the zeolite product 124
Reaction parameters 124
All silica molecular sieves 131
Clathrasils 132
Examples of systematic research 135
Literature sources pertaining zeolite preparation aspects 145
References 147
B. Synthesis of AlPO4-based molecular sieves 154
Introduction 154
Historical background 154
AlP04-based molecular sieves 155
Synthesis 156
Other issues 166
Final Comments 167
References 167
Chapter 5. Modified zeolites 170
Introduction 170
Extraction of aluminum from zeolite frameworks 171
Cracking catalyst development: historically a question of stability 173
Methods for dealuminating zeolite Y 174
Effect of sodium content 181
Aluminum extraction: characterization of framework and nonframework components 182
Spectroscopic techniques applied to understanding dealumination 186
Application of surface spectroscopic techniques 187
Does getting there by a different route get you the same place 188
And then there is reality 189
Modification of high silica zeolite structures: Differences from zeolite 190
Reactions of zeolites with fluoride 190
Enhancement in activity in ZSM-5 with steam 192
Hydrothermal enhancement of activity in metallosilicates 196
CVD methods applied to zeolites: SiCl4 treatment 199
Insertion of silicon into AlPO4 structures 201
CVD as a method of pore mouth restructuring 202
Internal pore modification 205
Coming full circle: putting aluminum back into the structure 207
Conclusion 208
References 209
Chapter 6. Clays from two to three dimensions 218
Introduction 218
Smectites 220
Properties of smectites 222
Pillared clays 239
Conclusion 253
References 254
Chapter 7. Techniques of zeolite characterization 258
Introduction 259
Zeolite structure and structural defects 261
Pore structure of zeolites 267
Chemical composition of zeolites 275
Determination of the framework Si/Al ratio 279
Determination of zeolite acidity 285
Zeolite stability 296
Zeolite morphology and particle size 299
References 300
Chapter 8. Solid state NMR spectroscopy applied to zeolites 302
Introduction 302
Basic principles and methods of high-resolution solid-state NMR 303
Multinuclear high-resolution solid-state NMR of zeolites 306
NMR of aluminophosphate molecular sieves 330
References 331
Chapter 9. Introduction to zeolite theory and modelling 334
Introduction 334
Theory on zeolite lattice stability 336
Theory on adsorption and acidity 343
Computer modelling techniques 352
Computer simulation of adsorption and diffusion 357
Future perspectives 371
References 372
Chapter 10. Ion exchange in zeolites 376
Introduction 376
A picture of the ion-exchange system 378
Equilibrium aspects of ion exchange in zeolites 382
The kinetics of ion exchange 392
Zeolites and detergency 399
Other recent developments and trends 404
References 405
Chapter 11. Diffusion in zeolite molecular sieves 408
Introduction 409
Diffusion in porous zeolite media: general principles 411
Experimental measurement of diffusitivities in molecular sieves 412
Numerical values of diffusivities 428
Diffusion and catalysis 451
Conclusions 455
List of symbols 456
References 458
Chapter 12. Introduction to acid catalysis with zeolites in hydrocarbon reactions 462
Screening of zeolite catalysts at the laboratory scale 462
Reaction mechanisms in zeolite catalyzed reactions 472
Shape-selective catalysis in acid zeolites 491
References 510
Chapter 13. Preparation of zeolitic catalysts 514
Introduction 514
Catalyst preparation procedure 516
Fluidized catalytic cracking (FCC) catalysts 528
Preparation of Ti catalysts for hydroxylation of phenol 539
Zeolite supported noble metal catalysts 541
Conclusion 544
References 544
Chapter 14. Coke formation on zeolites 548
Introduction 548
Methods of coke investigation and results 550
Particular phenomena related to coke formation 572
Summary and concluding remarks 582
Note 582
References 583
Chapter 15. Hydrocarbon processing with zeolites 588
Introduction 588
Oil-conversion processes 592
Gas-conversion processes 632
Future developments 643
References 645
Chapter 16. Zeolites in organic syntheses 648
Introduction 648
General aspects 649
Non-catalytic use of zeolites in organic synthesis 659
Zeolite-catalyzed isomerizations 666
Electrophilic substitution of arenes 681
Oxidation reactions 699
Zeolite-catalyzed cyclizations 711
Nucleophilic substitution and addition 719
Zeolite-catalyzed two- and multi-step syntheses 728
Final remarks 733
References 734
Appendix I - Zeolite structures 744
Appendix II - Pore sizes of zeolites 752
Keyword index 760
Studies in Surface Science and Catalysis (other volumes in the series) 768