Zeolites in Industrial Separation and Catalysis

Zeolites in Industrial Separation and Catalysis......Page 2
Contents......Page 8
Preface......Page 22
List of Contributors......Page 26
1.1.1 Molecular Sieves and Zeolites......Page 28
1.1.2 Nomenclature......Page 29
1.1.3 Early History......Page 30
1.1.4 Natural Zeolites......Page 31
1.2 History of Molecular Sieve Materials......Page 32
1.2.1 Aluminosilicate Zeolites and Silica Molecular Sieves......Page 33
1.2.2.1 The 1980s......Page 34
1.2.2.2 The 1990s......Page 38
1.2.2.3 The New Millennium......Page 41
1.3 Synthesis......Page 42
1.4 Applications......Page 43
1.6.1 Materials......Page 44
1.7 History of International Conferences and Organizations......Page 45
References......Page 47
Further Reading......Page 53
2.1 Introduction......Page 54
2.2 Building Units for Zeolite Frameworks......Page 55
2.3 Zeolite Framework Types......Page 58
2.4 Pores, Channels, Cages and Cavities......Page 59
2.5 Materials Versus Framework Types......Page 61
2.6 Structures of Commercially Significant Zeolites......Page 62
2.6.1 Linde Type A (LTA)......Page 63
2.6.2 Faujasite (FAU)......Page 65
2.6.3 Mordenite (MOR)......Page 67
2.6.4 Chabazite (CHA)......Page 69
2.6.5 ZSM-5 (MFI)......Page 72
2.6.6 Linde Type L (LTL)......Page 74
2.6.7 Beta Polymorphs *BEA and BEC......Page 76
2.6.8 MCM-22 (MWW)......Page 78
2.7 Hypothetical Zeolite Frameworks......Page 81
References......Page 82
3.1 Introduction......Page 88
3.2.1 Hydrothermal Synthesis–The Key to Metastable Phases......Page 89
3.2.2 Typical Zeolite Syntheses......Page 90
3.2.3 Important Synthesis Parameters–Zeolites......Page 92
3.2.4 Typical Aluminophosphate Syntheses......Page 93
3.2.6 Dewatering, Filtration and Washing of Molecular Sieve Products......Page 94
3.3.1 Chemical Engineering Considerations in Zeolite Forming......Page 95
3.3.2 Ceramic Engineering Considerations in Zeolite Forming......Page 96
3.3.4 Other Zeolite Forms–Colloids, Sheets, Films and Fibers......Page 97
3.4.1 Post-Forming Crystallization......Page 98
3.4.2 Stabilization and Chemical Modification of Zeolites......Page 99
3.4.3 Ion Exchange and Impregnation......Page 101
3.5 Selected New Developments in Catalyst and Adsorbent Manufacture......Page 102
References......Page 104
4.1.1 Importance of Characterization......Page 112
4.2.1 Identification of the Structure of a Newly Invented Zeolite......Page 113
4.3.1 Interpretation of Powder Diffraction Data for Zeolites......Page 118
4.3.2 Phase Identification and Quantification......Page 119
4.3.3 Unit Cell Size Determination......Page 121
4.3.4 Crystallite Size......Page 122
4.3.5 Rietveld Refinement......Page 123
4.4.1 Importance of Electron Microscopy for Characterizing Zeolites......Page 124
4.4.2.1 Morphological Characterization......Page 125
4.4.2.2 Compositional Characterization......Page 127
4.4.3.1 Sample Preparation......Page 131
4.4.3.2 Structural Characterization......Page 132
4.4.3.3 Morphological Characterization......Page 133
4.4.3.4 Compositional Characterization......Page 135
4.4.3.5 STEM Application to Metals in Zeolites and Coke Analysis......Page 136
4.5.1 Introduction to Infrared Spectroscopy......Page 138
4.5.2 Modes of Measurement......Page 139
4.5.3 Framework IR......Page 141
4.5.3.1 Zeolite Structure......Page 142
4.5.3.2 Tracking Zeolite Framework Si/Al......Page 143
4.5.3.3 Zeolite Synthesis......Page 145
4.5.4 Methods Requiring Sample Pretreatment......Page 146
4.5.5 Hydroxyl IR......Page 147
4.5.6 Acidity......Page 150
4.5.6.1 General Theory......Page 151
4.5.6.3 Quantitation of Sites......Page 152
4.5.6.4 Pyridine Adsorption......Page 154
4.5.6.5 Ammonia......Page 157
4.5.6.6 Low-Temperature Acidity Probes......Page 158
4.5.6.7 Carbon Monoxide......Page 159
4.5.6.9 Measurement of External Acidity......Page 161
4.5.6.10 Other Probes......Page 162
4.5.8 Characterization of Metal-Loaded Zeolites......Page 163
4.5.8.1 Cation Exchange for Adsorption/Separation......Page 164
4.5.8.3 Noble Metal-Loading for Catalysis......Page 165
4.5.8.4 Non-Noble Metal-Loading for Catalysis......Page 166
4.6.1 Introduction to NMR......Page 167
4.6.1.2 Cross Polarization......Page 169
4.6.1.4 Dipolar Recoupling......Page 170
4.6.1.5 Pulsed Field Gradient NMR–diffusion......Page 171
4.6.2.1 29Si NMR......Page 172
4.6.2.2 27Al NMR......Page 174
4.6.2.3 31P NMR......Page 176
4.6.2.4 1H NMR......Page 177
4.6.2.6 Diffusion of Hydrocarbons in Zeolites......Page 178
4.7.1 Nitrogen Physisorption......Page 179
4.7.2 Thermal and Mechanical Analyses......Page 181
4.7.3 Adsorption Capacity......Page 183
4.7.4 Acid Sites......Page 184
4.8.1 Future Characterization Directions......Page 185
References......Page 187
5.2.1 Gas Separation......Page 200
5.2.2.2 Non-Aromatic Hydrocarbons......Page 201
5.2.2.4 Trace Component Removal......Page 202
5.3.5.1 Sulfur Removal......Page 203
5.3.5.2 Oxygenate Removal......Page 215
5.3.5.6 Metal Removal......Page 217
5.4 Summary Review of Zeolites in Adsorptive Separation......Page 218
References......Page 219
6.2 Impacts of Adsorptive Separation Versus Other Separation Processes......Page 230
6.3 Liquid Phase Adsorption......Page 233
6.3.1 Sanderson’s Model of Intermediate Electronegativity......Page 234
6.4 Modes of Operation......Page 235
6.4.2 Pulse Test Procedure......Page 236
6.4.3 Breakthrough Procedure......Page 237
6.5.1 Equilibrium-Selective Adsorption......Page 238
6.5.1.2 Metal Cation Exchanged in Zeolite......Page 239
6.5.1.3 Zeolite SiO2/Al2O3 Molar Ratio......Page 243
6.5.1.4 Moisture Content in Zeolite......Page 245
6.5.1.5 Characteristics of the Desorbent......Page 246
6.5.1.6 Operating Temperature......Page 247
6.5.2 Rate-Selective Adsorption......Page 248
6.5.3 Shape-Selective Adsorption......Page 249
6.5.4 Ion Exchange......Page 250
6.5.5 Reactive Adsorption......Page 251
Acknowledgments......Page 252
References......Page 253
7.1 Introduction......Page 256
7.2.1.1 Industrial Uses and Demand......Page 258
7.2.1.2 Method of Production......Page 259
7.2.1.3 Characteristics of Zeolitic Adsorptive Process......Page 262
7.2.2.2 Method of Production......Page 268
7.2.2.3 Characteristics of Zeolitic Adsorptive Process......Page 269
7.3 Other Significant Processes......Page 270
7.3.2.2 Method of Production......Page 271
7.4 Summary......Page 272
References......Page 273
8.2 Normal Paraffin Separations......Page 276
8.2.1.1 Selectivity......Page 277
8.2.1.2 Capacity......Page 278
8.2.1.5 Zeolite Types......Page 279
8.2.2 Desorbent Critical Characteristics......Page 280
8.2.2.3 Ease of Separation......Page 281
8.2.2.5 Reactivity......Page 282
8.2.3.1 Adsorbent Allocation within the Molex Process......Page 283
8.2.3.2 Critical Sorbex Zone Parameters......Page 284
8.2.4.2 Unique Operating Parameters......Page 285
8.2.5.2 Unique Operating Parameters......Page 287
8.2.6 Heavy Normal Paraffin Separation (C10–18)......Page 288
8.2.6.2 Unique Operating Parameters......Page 289
8.3.1 Industrial Use and Demand......Page 290
8.3.2 Unique Operating Parameters......Page 291
8.4 Olefin Separations......Page 292
8.4.1.2 Unique Operating Parameters......Page 293
8.4.2.1 Industrial Use and Demand......Page 294
8.4.2.2 Unique Operating Parameters......Page 295
8.6 Liquid Adsorption Acid Separations......Page 296
8.6.2.2 Unique Operating Parameters......Page 297
References......Page 298
9.1 Introduction......Page 300
9.2 Regeneration......Page 302
9.3 Adsorption Equilibrium......Page 303
9.3.2 Langmuir......Page 304
9.3.4 Universal Isotherm......Page 305
9.3.7 Kelvin Equation and Capillary Condensation......Page 306
9.4 Mass Transfer in Formed Zeolite Particles......Page 307
9.4.1 Adsorption Wave Speed......Page 309
9.4.2 Adsorption Wave Shape and Length......Page 310
9.4.3 Linear Driving Force Approximation and Resistance Modeling......Page 311
9.4.4.2 Macro-Pore Diffusion......Page 313
9.4.4.3 Intra-Crystalline Diffusion......Page 314
9.5 Industrial TSA Separations (Purification)......Page 315
9.5.1 Dehydration......Page 316
9.5.2 De-Sulfurization......Page 321
9.5.3 CO2 Removal......Page 322
9.6 Industrial PSA......Page 323
9.6.1 PSA Air Separation......Page 324
9.6.2 PSA H2 Purification......Page 326
9.6.3 PSA Dehydration......Page 327
9.7.1 Desiccant Wheels......Page 328
9.7.2 Enthalpy Control Wheels......Page 329
Nomenclature......Page 330
References......Page 331
10.1 Introduction......Page 334
10.2.1 In Situ Crystallization......Page 336
10.2.2 Secondary (Seeded) Growth......Page 338
10.2.3 Characterization of Zeolite Membranes......Page 340
10.3.1 Permeation Through Zeolite Membranes......Page 341
10.3.2 Zeolite Membrane Separation Mechanisms......Page 343
10.3.3 Influence of Zeolite Framework Flexibility......Page 346
10.4.1 Liquid-Liquid Separation......Page 347
10.4.2 Gas/Vapor Separation......Page 349
10.4.3 Reactive Separation Processes......Page 350
10.5 Summary......Page 351
References......Page 352
11.1.2 Polymer Membranes......Page 356
11.1.3 Zeolite Membranes......Page 358
11.2 Compositions of Mixed-Matrix Membranes......Page 359
11.2.2 Zeolite/Polymer Mixed-Matrix Membranes......Page 360
11.3 Concept of Zeolite/Polymer Mixed-Matrix Membranes......Page 361
11.4.1.1 Selection of Polymer Materials......Page 363
11.4.1.2 Selection of Zeolite Materials......Page 364
11.4.2 Modification of Zeolite and Polymer Materials......Page 366
11.5.1 Mixed-Matrix Dense Films......Page 368
11.5.2 Asymmetric Mixed-Matrix Membranes......Page 369
11.5.2.1 Flat Sheet Asymmetric Mixed-Matrix Membranes......Page 370
11.5.2.2 Hollow Fiber Asymmetric Mixed-Matrix Membranes......Page 372
11.6 Applications of Zeolite/Polymer Mixed-Matrix Membranes......Page 373
11.6.2 Liquid Separation Applications......Page 374
11.7 Summary......Page 375
References......Page 376
12.1.1 R&D Uses Versus Industrial Application of Zeolite Catalysis......Page 382
12.2.1.2 Pentane/Hexane Isomerization......Page 383
12.2.2.1 Light Olefin Oligomerization......Page 385
12.2.3.2 Benzene Alkylation......Page 391
12.2.5.1 Use of Zeolites in FCC Type Feeds......Page 396
12.2.6.2 Methane to Aromatics......Page 404
12.2.8 Hydrotreating and Hydrocracking......Page 410
12.2.9.2 Other Oxidations......Page 414
References......Page 420
13.1 Introduction......Page 430
13.2.1 Langmuir Isotherm and Reaction Kinetics......Page 431
13.2.2 Nitrogen Adsorption......Page 433
13.2.3.1 Pure Component Adsorption and Specificity with Respect to Zeolite Topology......Page 435
13.2.3.2 Energetics of Adsorption......Page 438
13.2.3.3 Adsorption of Mixtures......Page 440
13.2.3.4 Compensation between Enthalpy and Entropy......Page 442
13.3 Diffusion......Page 443
13.4.1 Bronsted Acidity......Page 447
13.4.2 Significance of Acid Strength......Page 448
13.4.4 Lewis Acidity......Page 450
13.4.5 External acidity......Page 451
13.5 Carbocations......Page 452
13.5.1 Carbenium Ions and Alkoxides......Page 453
13.6 Elementary Steps of Hydrocarbon Conversion over Zeolites......Page 456
13.7.1 Tools......Page 457
13.7.1.1 Footprints and Kinetic Diameters......Page 458
13.7.1.2 Constraint Index......Page 459
13.7.1.4 Spaciousness Index......Page 461
13.7.3.1 Meta-Xylene Disproportionation......Page 462
13.7.3.3 Alkane Hydrosiomerization......Page 463
13.7.4.1 Alkane Hydroisomerization......Page 465
13.7.4.2 Oligomerization of Propylene......Page 468
13.7.4.4 Hydrocracking of n-Hexadecane......Page 470
13.7.4.5 Meta-Xylene Isomerization......Page 472
13.7.5 Crystal Size Effects......Page 473
13.8.1.1 Unimolecular Mechanism......Page 474
13.8.2 Alkene Oligomerization......Page 475
13.8.3.1 Isobutane Alkylation by 2-Butylene......Page 477
13.8.3.2 Aromatic–Alkene and Aromatic–Alcohol......Page 480
13.8.4.1 Classic Cracking Mechanism, Bimolecular......Page 482
13.8.4.2 Monomolecular Cracking Mechanism......Page 483
13.8.4.3 Kinetics of Cracking......Page 485
13.8.4.4 Effect of Pore Size and Acid Site Density on Cracking......Page 488
13.8.5.1 Transalkylation and Disproportionation......Page 489
13.8.5.2 Ethylbenzene Conversion to Xylenes......Page 490
13.8.6 Methanol to Olefins......Page 491
References......Page 497
14.2 Metal-Zeolite Catalyzed Light Paraffin Isomerization......Page 506
14.2.2 Bifunctional Paraffin Isomerization Mechanism......Page 507
14.2.3 Zeolitic Paraffin Isomerization Catalysis......Page 509
14.2.4 Industrial Zeolitic Isomerization Catalysts and Processes......Page 510
14.3.1 General Considerations......Page 511
14.3.2 Cis–Trans and Double Bond Isomerization......Page 512
14.3.3 Skeletal Isomerization (Butenes, Pentenes, Hexenes)......Page 513
14.4 C8 Aromatics Isomerization......Page 515
14.4.1.1 Feed Composition and Characteristics......Page 516
14.4.1.2 Reaction Product Composition and Characteristics......Page 517
14.4.1.3 Isomerization Reactions......Page 518
14.4.2.1 General Aspects......Page 521
14.4.3.1 Process Variables......Page 522
14.4.3.2 Commercial Catalysts......Page 523
14.4.3.3 Modeling/Optimization of Commercial Units......Page 524
14.4.3.4 Process Flow Schemes......Page 525
14.4.4 Future Developments......Page 526
References......Page 527
15.2.1.1 Process Chemistry: Feeds, Products and Reactions......Page 532
15.2.1.2 Catalysts......Page 533
15.3.1 Motor Fuel Alkylation......Page 534
15.3.1.1 Process Chemistry: Feeds, Products and Reactions......Page 535
15.3.1.2 Catalysts......Page 536
15.3.1.3 Physicochemical Characterization of Active Sites......Page 538
15.4.1.2 Catalysts......Page 539
15.4.1.3 Physicochemical Characterization of Active Sites......Page 540
15.4.2.1 Process Chemistry: Feeds, Products and Reactions......Page 541
15.4.3.1 Process Chemistry: Feeds, Products and Reactions......Page 542
15.4.3.3 Physicochemical Characterization of Active Sites......Page 543
15.5.2 Catalysts......Page 544
15.6.1.1 Process Chemistry: Feeds, Products and Reactions......Page 545
15.6.1.3 Physicochemical Characterization of Active Sites......Page 546
15.6.2.3 Physicochemical Characterization of Active Sites......Page 547
15.7.1 Methanol to C2–C4 Olefins......Page 548
15.7.2 Methanol to Aromatics......Page 549
15.7.3 Catalysts......Page 550
15.7.3.1 Physicochemical Characterization of Active Sites......Page 551
15.7.4 Reaction Mechanism of Methanol to Hydrocarbons......Page 554
References......Page 555
16.1 Introduction......Page 562
16.2.1 Framework Types and Compositions......Page 563
16.2.2 Stabilization Methods......Page 566
16.2.3 Property–Function Relationship......Page 569
16.2.3.1 Acid Strength Requirements for Product Control and Influence of Spatial Distribution on Selectivity......Page 571
16.2.3.2 Pore Geometry and Framework Composition......Page 572
16.3.1 Heteroatom Removal: Desulfurization Denitrogenation and Deoxygenation......Page 573
16.3.2.1 Paraffin Cracking......Page 578
16.3.2.2 Aromatic and Naphthene Ring Opening......Page 581
16.4 Fluidized Catalytic Cracking......Page 583
16.4.1 Process Configuration and Catalysts......Page 584
16.5 Hydrocracking and Hydroisomerization......Page 587
16.5.2 Catalyst Requirements for the Hydrocracker......Page 588
16.5.3 The Changing Role of the Hydrocracker in a Reformulated Fuels Environment......Page 592
References......Page 593
Index......Page 598