Zeolites and Catalysis: Synthesis, Reactions and Applications (2 Volume set)

Zeolites and Catalysis......Page 5
Contents......Page 7
Preface......Page 23
List of Contributors......Page 27
1.1 Introduction......Page 31
1.2.2 Supersaturation......Page 33
1.2.3 Energetics......Page 34
1.2.5 Heterogeneous and Secondary Nucleation......Page 35
1.2.8 Crystal Surface Structure......Page 36
1.2.9 2D Nucleation Energetics......Page 38
1.2.10 Spiral Growth......Page 39
1.2.12 Growth Mechanisms: Rough and Smooth Surfaces......Page 40
1.3.1 Overview......Page 41
1.3.2 Zeolite Nucleation......Page 43
1.3.3 Crystal Growth on Zeolites and Zeotypes......Page 44
1.4.1.1 AFM......Page 45
1.4.1.3 Confocal Microscopy......Page 46
1.4.2.1 Nuclear Magnetic Resonance......Page 47
1.4.2.2 Mass Spectrometry......Page 49
1.4.2.3 Cryo-TEM......Page 50
1.4.3.1 Monte Carlo Modeling of Crystal Growth......Page 51
1.5.1 Zeolite A......Page 53
1.5.1.1 Thompson Synthesis......Page 54
1.5.1.2 Petranovskii Synthesis......Page 56
1.5.2 Silicalite......Page 58
1.5.3 LTL......Page 63
1.5.4 STA-7......Page 65
1.5.4.2 {001} Faces......Page 68
1.5.5.1 ZnPO4-Sodalite......Page 73
1.5.6 Metal Organic Frameworks......Page 77
1.6 Conclusions and Outlook......Page 79
References......Page 80
2.1 Introduction......Page 87
2.2 Aluminophosphates......Page 88
2.3 Mineralizers......Page 89
2.4 Dry Gel Conversion Syntheses......Page 91
2.5 Low Water Syntheses......Page 92
2.6 Germanium Zeolites......Page 93
2.7 Isomorphous Substitution......Page 95
2.8 Structure-Directing Agents......Page 97
2.9 SDA Modeling......Page 100
2.10 Co-templating......Page 102
2.11 Layered Precursors......Page 103
2.12 Nonaqueous Solvents......Page 107
2.13 Summary and Outlook......Page 109
References......Page 110
3.1 Introduction......Page 117
3.2 Hydrothermal, Solvothermal, and Ionothermal Synthesis......Page 119
3.3 Ionothermal Aluminophosphate Synthesis......Page 120
3.5 Ionothermal Synthesis of Metal Organic Frameworks and Coordination Polymers......Page 122
3.6 Ambient Pressure Ionothermal Synthesis......Page 123
3.7 The Role of Cation-Templating, Co-Templating, or No Templating......Page 125
3.8 The Role of the Anion – Structure Induction......Page 127
3.9 The Role of Water and Other Mineralizers......Page 129
3.11 Summary and Outlook......Page 131
References......Page 132
4.1 Introduction......Page 137
4.2 Templating of Dual-Void Structures......Page 138
4.3 Crystallization of Aluminophosphate-Type Materials......Page 143
4.4 Combined Use of Templating and Pore-Filling Agents......Page 146
4.5 Cooperative Structure-Directing Effects of Organic Molecules and Mineralizing Anions......Page 147
4.6 Cooperative Structure-Directing Effect of Organic Molecules and Water......Page 149
4.7 Control of Crystal Size and Morphology......Page 152
4.9 Use of Co-Templates for Tailoring the Catalytic Activity of Microporous Materials......Page 153
4.10 Summary and Outlook......Page 155
References......Page 157
5.1 Introduction......Page 161
5.2.1 Large Crystals of Natural Zeolites......Page 162
5.2.2 Synthesis of Large Zeolite Crystals......Page 163
5.3 Morphology Control of MFI Zeolite Particles (of Size Less than 100 µm)......Page 168
5.3.1 Dependence of Structure-Directing Agents (SDAs)......Page 169
5.3.2 Dependence on Alkali-Metal Cations......Page 171
5.4.1 Examples of MW Dependency......Page 172
5.4.2 Morphological Fabrication by MW......Page 173
5.4.3 Formation Scheme of Stacked Morphology......Page 176
5.5 Summary and Outlook......Page 179
References......Page 180
6.2 Direct Synthesis of Zeolites......Page 185
6.3 Post-synthetic Treatment and Modi.cation of Zeolites......Page 187
6.3.1.1 Experimental Procedures......Page 188
6.3.1.2 One-Step Method versus Two-Step Method......Page 189
6.3.1.3 Effects of the Ratio of Al(NO3)3 to Zeolite......Page 190
6.3.1.5 Applicable to Medium Pore Zeolite?......Page 191
6.3.2.1 Experimental Procedures......Page 192
6.3.2.3 Effects of Type of Acid, pH, Temperature, and Other Factors......Page 193
6.3.2.4 Experimental Results from Our Lab......Page 194
6.4 Summary and Outlook......Page 196
References......Page 197
7.1 Introduction......Page 201
7.2.1 Introduction......Page 202
7.2.2 The Framework: Secondary Building Units in Zeolite Structural Chemistry......Page 205
7.2.3 Assembling Sodalite Cages: Sodalite, A, Faujasites X and Y, and EMC-2......Page 207
7.2.4 Faujasitic Zeolites X and Y as Typical Examples......Page 208
7.2.5 Key Inorganic Cation-Only Zeolites Pre-1990......Page 209
7.2.6 Structures Templated by Simple Alkylammonium Ions......Page 212
7.2.7 Lessons from Nature......Page 214
7.3.1 Introduction......Page 215
7.3.2 Novel Structures and Pore Geometries......Page 217
7.3.3 Expansion of the Coordination Sphere of Framework Atoms......Page 221
7.3.4 The Current Limits of Structural Complexity in Zeolites......Page 223
7.3.5 Chirality and Mesoporosity......Page 225
7.3.6 Ordered Vacancies and Growth Defects......Page 227
7.3.7 Zeolites from Layered Precursors......Page 228
7.3.8 Substitution of Framework Oxygen Atoms......Page 229
7.4.1 Summary......Page 231
7.4.2 Outlook......Page 232
References......Page 234
8.1 Introduction......Page 239
8.2 Acidity Determination with IR Spectroscopy of Probe Molecules......Page 241
8.3 Zeolite Synthesis Processes......Page 248
8.4.1 Catalytic Decomposition of Nitric Oxides......Page 251
8.4.2 Methanol-to-Olefin Conversion......Page 255
8.5 IR Microspectroscopy......Page 261
8.6 Concluding Remarks and Look into the Future......Page 262
References......Page 264
9.1 Introduction......Page 267
9.2.1.1 Dealumination......Page 269
9.2.1.2 Desilication......Page 271
9.2.1.3 Detitanation......Page 272
9.2.2.1 Hard Template......Page 273
9.2.2.2 Soft Template......Page 274
9.2.3 Other Methods......Page 275
9.3.1 Gas Physisorption......Page 276
9.3.2 Thermoporometry......Page 281
9.3.3 Mercury Porosimetry......Page 285
9.3.4.1 SEM and TEM......Page 286
9.3.5.1 129Xe NMR Spectroscopy......Page 296
9.3.5.2 PFG NMR......Page 299
9.3.6 In situ Optical and Fluorescence Microscopy......Page 301
9.4 Summary and Outlook......Page 303
References......Page 304
10.1 Introduction......Page 313
10.2 Structure of Aluminum Species in Zeolites......Page 314
10.2.1 Reversible versus Irreversible Structural Changes......Page 315
10.2.3 Development of Activity and Changing Aluminum Coordination......Page 316
10.3.1 Aluminum Zoning......Page 319
10.3.2 Aluminum Distribution Over the Crystallographic T Sites......Page 322
10.4 Summary and Outlook......Page 326
References......Page 328
11.1 Introduction......Page 331
11.2 Methodology......Page 332
11.2.2 DFT Methods......Page 333
11.2.3 Basis Sets......Page 334
11.2.4 Zeolite Models......Page 336
11.3 Activation of Hydrocarbons in Zeolites: The Role of Dispersion Interactions......Page 337
11.4 Molecular-Level Understanding of Complex Catalytic Reactions: MTO Process......Page 346
11.5 Molecular Recognition and Confinement-Driven Reactivity......Page 351
11.6 Structural Properties of Zeolites: Framework Al Distribution and Structure and Charge Compensation of Extra-framework Cations......Page 356
11.7 Summary and Outlook......Page 360
References......Page 361
12.1 Introduction......Page 365
12.2.1 Modeling Zeolites and Nonframework Cations......Page 366
12.2.2 Modeling Guest Molecules......Page 367
12.3 Simulation Methods......Page 368
12.3.1 Computing Adsorption......Page 369
12.3.2 Computing Free Energy Barriers......Page 371
12.3.3 Computing Volume-Rendered Pictures, Zeolite Surface Areas, and Zeolite Pore Volumes......Page 373
12.3.4 Computing Diffusion......Page 374
12.4.1.1 Molecular Modeling of Confined Water in Zeolites......Page 376
12.4.1.2 Molecular Modeling of Hydrocarbons in Zeolites......Page 378
12.4.1.3 Molecular Modeling of Separation of Mixtures in Zeolites......Page 379
12.4.2.1 Carbon Dioxide Capture......Page 381
12.4.2.2 Natural Gas Purification......Page 382
12.5 Summary and Outlook......Page 383
References......Page 384
13.1 Introduction......Page 391
13.2 Diffusion and Reaction in Zeolites: Basic Concepts......Page 392
13.2.2 Self-Diffusivity......Page 394
13.2.4 Diffusion Measurement Techniques......Page 395
13.2.5 Relating Diffusion and Catalysis......Page 396
13.3.1 Concentration Dependence of Diffusion......Page 398
13.3.2 Single-File Diffusion......Page 400
13.3.3 Surface Barriers......Page 402
13.3.4 The Thiele Concept: A Useful Approach in Zeolite Catalysis?......Page 404
13.4 Pore Structure, Diffusion, and Activity at the Subcrystal Level......Page 405
13.5 Improving Transport through Zeolite Crystals......Page 409
13.6 Concluding Remarks and Future Outlook......Page 412
References......Page 413
14.2 Zeolite Membranes......Page 419
14.2.1 Membrane Reactors and Microreactors......Page 420
14.2.2 Zeolite-Based Gas Sensors......Page 422
14.2.3 Mixed-Matrix Membranes......Page 424
14.3 Host–Guest Interactions......Page 426
14.4.1 Medical Applications......Page 429
14.4.2 Veterinary Applications......Page 430
14.5.1 Racemic Separations......Page 431
14.5.2 Magnetic Zeolites......Page 432
14.5.3 Hydrogen Storage......Page 433
14.6 Summary and Outlook......Page 434
References......Page 436
15.2 Organization of Zeolite Microcrystals into Functional Materials by Self-Assembly......Page 441
15.2.1.1 Types of Linkages......Page 442
15.2.1.3 Methods......Page 445
15.2.1.4 Characteristic Points to Monitor the Quality of the Monolayers......Page 446
15.2.1.5 Four Key Processes Occurring during Monolayer Assembly......Page 447
15.2.1.6 Effect of Method on Rate, DCP, Coverage, and Binding Strength......Page 454
15.2.1.7 Factors Affecting Binding Strengths......Page 456
15.2.1.8 Driving Forces for Uniform Orientation and Close Packing......Page 457
15.2.2 Patterned Monolayer Assembly on Substrates......Page 459
15.2.4 Organization into 2D Arrays on Water......Page 461
15.2.5 Organization into Surface-Aligned Zeolite Microballs......Page 464
15.2.6 Self-Assembly of Substrate-Tethering Zeolite Crystals with Proteins......Page 465
15.2.7 In Situ Self-Organization of Zeolite Crystals into Arrays during Synthesis......Page 467
15.3 Monolayer Assembly of Zeolite Microcrystals by Dry Manual Assembly......Page 468
15.4 Current and Future Applications......Page 471
15.5 Summary and Outlook......Page 472
References......Page 474
16.1 Introduction......Page 479
16.2 Application of Zeolites in Slurry Processes......Page 480
16.2.1 TS-1 Based Catalyst for Liquid-Phase Oxidation Processes......Page 481
16.2.2 New Advance in Slurry Phase Reaction with Zeolitic Catalysts......Page 483
16.3 Rebalancing the Refinery Products Slate......Page 485
16.3.1 Bottom Cracking Conversion......Page 487
16.3.2 LCO Upgrading......Page 489
16.3.3 Olefins Oligomerization......Page 491
16.4 Advanced Separation Technologies......Page 492
16.5 Zeolites and Environmental Protection: Groundwater Remediation......Page 497
16.6.1 Zeolites......Page 501
16.6.2 Hierarchical Zeolites......Page 503
16.6.3 Silica-Based Crystalline Organic–Inorganic Hybrid Materials......Page 509
16.7 Summary and Outlook......Page 514
References......Page 515
17.1 Introduction......Page 523
17.2.1 Nature of Acid Sites......Page 524
17.2.2 Formation of Brønsted and Lewis Acid Sites......Page 526
17.3.1 Catalytic Test Reactions......Page 528
17.3.2 Titration with Bases......Page 530
17.3.3 Temperature-Programmed Desorption of Bases......Page 531
17.3.4 Microcalorimetry......Page 534
17.3.5 FTIR Spectroscopy......Page 538
17.3.6 NMR Spectroscopy......Page 544
17.4.1 Nature of Base Sites......Page 551
17.4.2 Formation of Base Sites......Page 552
17.5.1 Test Reactions......Page 553
17.5.2 Analytical and Spectroscopic Methods......Page 555
17.6.1 Nature of Metal Clusters......Page 559
17.6.2 Formation of Metal Clusters......Page 560
17.7.1 Test Reactions......Page 562
17.7.2 Analytical Methods......Page 18
References......Page 565
18.1.1 The Oil Refinery – Where to Find Zeolites in It, and Why – and the Place of Hydrocracking and Catalytic Cracking......Page 577
18.1.2 The Changing Environment for Refining......Page 579
18.2.1 The FCC Process......Page 581
18.2.2 The FCC Catalyst, and Catalytic Chemistry......Page 585
18.2.3 Residue Cracking and the Effect of Deposited Metals on the Catalyst......Page 588
18.2.4 Light Alkenes by Addition of ZSM-5......Page 589
18.3.1 The Hydrocracking Process......Page 591
18.3.2 Feedstocks and Products......Page 593
18.3.3 Hydrocracking Catalyst Systems, and Catalytic Chemistry......Page 596
18.3.4 Zeolite Y in Hydrocracking......Page 600
18.3.5 New Catalyst Developments......Page 605
18.4 Summary and Outlook......Page 606
References......Page 608
19.1 Introduction......Page 615
19.2.1 Process......Page 617
19.2.2 Reforming Chemistry......Page 621
19.2.3 Catalyst......Page 625
19.2.3.1 Zeolite Catalysts......Page 628
19.2.3.2 Commercial Catalysts......Page 630
19.3 Upgrading Diesel Fractions: Catalytic Dewaxing......Page 631
19.3.1 Shape Selectivity......Page 632
19.3.1.1 Catalytic Dewaxing via Shape Selective Cracking......Page 635
19.3.1.2 Dewaxing via Isomerization......Page 637
19.3.2 Commercial Applications......Page 639
19.3.2.1 Commercial Processes......Page 640
19.4 Summary and Outlook......Page 648
References......Page 649
20.2 Zeolites under Study......Page 653
20.3 Toluene Disproportionation......Page 655
20.3.1 Zeolite Modification by Silicon Deposition......Page 656
20.3.3 Zeolite Modification by Dealumination......Page 657
20.3.4 Zeolite Modification by Metal Deposition......Page 658
20.3.5 Factors Affecting Toluene Disproportionation......Page 659
20.4 Ethylbenzene Disproportionation......Page 660
20.4.2 Kinetic Investigations of Ethylbenzene Disproportionation......Page 661
20.5 Disproportionation and Transalkylation of Trimethylbenzene......Page 663
20.6.1 Ethylation of Benzene......Page 665
20.6.2 Methylation of Toluene......Page 666
20.6.2.1 Modification of the External Surface of Zeolites......Page 668
20.6.3 Ethylation of Toluene and Ethylbenzene......Page 670
20.7 Miscellaneous......Page 672
20.8 Summary and Outlook......Page 673
References......Page 674
21.1 Introduction......Page 679
21.2.1 Oxidative Conversion: OCM and Methylation Processes......Page 681
21.2.2 Nonoxidative Methane Homologation and Alkylation Processes......Page 684
21.2.3 Nonoxidative Methane Dehydroaromatization (MDA)......Page 685
21.3.1 Selective Synthesis of Short-Chain (C2 –C4) Ole.ns......Page 689
21.3.2.1 Conventional FTS......Page 693
21.3.2.2 Modified (Bifunctional) FTS......Page 698
21.3.3.1 One-Step Synthesis of Dimethyl Ether (DME) from Syngas......Page 700
21.3.3.2 Syngas to Higher (C2+) Oxygenates......Page 704
21.3.3.3 Carbonylation of MeOH and DME......Page 706
21.4 Summary and Outlook......Page 708
References......Page 710
22.1 Introduction......Page 717
22.2 Mechanism and Kinetics of the MTO and MTG Reactions......Page 720
22.3.1 Catalysts and Reaction Conditions......Page 727
22.3.2 Deactivation......Page 728
22.3.3 Process Technology and Design......Page 729
22.3.4 Commercial Aspects/Economic Impact......Page 730
22.3.5 Future Perspectives......Page 731
22.4.2 Deactivation......Page 732
22.5 Methanol to Propene (MTP)......Page 733
22.6 TIGAS Process......Page 735
22.7.2 Thermodynamic Considerations......Page 736
22.8 Summary and Outlook......Page 737
References......Page 738
23.1 Introduction......Page 743
23.2.1 TS-1......Page 745
23.2.2 Ti-Beta......Page 752
23.2.3 Ti-MWW......Page 754
23.2.4 Other Titanium-Containing Zeolites......Page 761
23.2.5 Solvent Effects and Reaction Intermediate......Page 762
23.3 Other-Metal-Containing Zeolites......Page 766
23.4 Conclusion......Page 768
References......Page 770
24.1 Introduction......Page 775
24.2 A Glimpse into Opportunities and Issues......Page 776
24.3 Fields of Applications......Page 786
24.4 Summary and Outlook......Page 799
References......Page 800
25.2.1 Friedel–Crafts Acylation......Page 805
25.2.2 Hydroxyalkylation of Aromatic Compounds......Page 810
25.2.3 Diels–Alder Reactions......Page 813
25.2.4 Acetalization of Carbonyl Compounds......Page 817
25.2.5 Fischer Glycosidation Reactions......Page 819
25.2.6 Isomerization Reactions: Isomerization of 
α-Pinene and α-Pinene Oxide......Page 822
25.2.7.1 Epoxidation Reactions......Page 825
25.2.7.2 Baeyer–Villiger Oxidations......Page 829
25.2.7.3 Meerwein–Ponndorf Verley Reduction and Oppenauer Oxidation (MPVO)......Page 833
25.3 Base-Catalyzed Reactions......Page 838
25.3.1 The Knoevenagel Condensation......Page 839
25.3.2 Michael Addition......Page 843
25.3.3 Aldol Condensations......Page 846
References......Page 849
26.2 Zeolites in Electrolyte Membrane......Page 857
26.2.1 Zeolite Conductivities......Page 859
26.2.2 Zeolite/Polymer Composite Membranes......Page 863
26.2.2.2 Zeolite/PFSA Composite Membranes......Page 869
26.2.2.3 Zeolite/Chitosan Composite Membranes and Others......Page 870
26.2.3 Zeolite and Mesoporous Inorganic Membranes......Page 871
26.3 Zeolite Electrocatalysts......Page 872
26.4 Zeolites and Molecular Sieves in Fuel Processing......Page 874
26.4.2.1 Reforming of Hydrocarbons......Page 875
26.4.2.4 CO Removal from H2-Rich Gas......Page 879
26.4.3 Hydrogen Storage......Page 880
References......Page 886
Index......Page 893