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Zeolites in Industrial Separation and Catalysis

ISBN: 978-3-527-32505-4
618 pages
April 2010
Zeolites in Industrial Separation and Catalysis (3527325050) cover image
This first book to offer a practical overview of zeolites and their commercial applications provides a practical examination of zeolites in three capacities. Edited by a globally recognized and acclaimed leader in the field with contributions from major industry experts, this handbook and ready reference introduces such novel separators as zeolite membranes and mixed matrix membranes.
The first part of the book discusses the history and chemistry of zeolites, while the second section focuses on separation processes. The third and final section treats zeolites in the field of catalysis.
The three sections are unified by an examination of how the unique properties of zeolites allow them to function in different capacities as an adsorbent, a membrane and as a catalyst, while also discussing their impact within the industry.
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Preface XIX

List of Contributors XXIII

1 Introduction 1
Edith M. Flanigen, Robert W. Broach, and Stephen T. Wilson

1.1 Introduction 1

1.1.1 Molecular Sieves and Zeolites 1

1.1.2 Nomenclature 2

1.1.3 Early History 3

1.1.4 Natural Zeolites 4

1.2 History of Molecular Sieve Materials 5

1.2.1 Aluminosilicate Zeolites and Silica Molecular Sieves 6

1.2.2 The Materials Explosion Since the 1980s 7

1.3 Synthesis 15

1.4 Applications 16

1.5 Markets 17

1.6 The Future 17

1.6.1 Materials 17

1.6.2 Applications 18

1.7 History of International Conferences and Organizations 18

1.8 Historical Epilog 20

References 20

Further Reading 26

2 Zeolite Types and Structures 27
Robert W. Broach

2.1 Introduction 27

2.2 Building Units for Zeolite Frameworks 28

2.3 Zeolite Framework Types 31

2.4 Pores, Channels, Cages and Cavities 32

2.5 Materials Versus Framework Types 34

2.6 Structures of Commercially Signifi cant Zeolites 35

2.6.1 Linde Type A (LTA) 36

2.6.2 Faujasite (FAU) 38

2.6.3 Mordenite (MOR) 40

2.6.4 Chabazite (CHA) 42

2.6.5 ZSM-5 (MFI) 45

2.6.6 Linde Type L (LTL) 47

2.6.7 Beta Polymorphs *BEA and BEC 49

2.6.8 MCM-22 (MWW) 51

2.7 Hypothetical Zeolite Frameworks 54

Acknowledgments 55

References 55

3 Synthesis of Zeolites and Manufacture of Zeolitic Catalysts and Adsorbents 61
Robert L. Bedard

3.1 Introduction 61

3.2 Synthesis of Zeolites and Aluminophosphate Molecular Sieves 62

3.2.1 Hydrothermal Synthesis – The Key to Metastable Phases 62

3.2.2 Typical Zeolite Syntheses 63

3.2.3 Important Synthesis Parameters – Zeolites 65

3.2.4 Typical Aluminophosphate Syntheses 66

3.2.5 Important Synthesis Parameters – Aluminophosphates 67

3.2.6 Dewatering, Filtration and Washing of Molecular Sieve Products 67

3.3 Forming Zeolite Powders into Usable Shapes 68

3.3.1 Chemical Engineering Considerations in Zeolite Forming 68

3.3.2 Ceramic Engineering Considerations in Zeolite Forming 69

3.3.3 Bound Zeolite Forms 70

3.3.4 Other Zeolite Forms – Colloids, Sheets, Films and Fibers 70

3.4 Finishing: Post-Forming Manufacturing of Zeolite Catalysts and Adsorbents 71

3.4.1 Post-Forming Crystallization 71

3.4.2 Stabilization and Chemical Modification of Zeolites 72

3.4.3 Ion Exchange and Impregnation 74

3.4.4 Drying and Firing 75

3.5 Selected New Developments in Catalyst and Adsorbent Manufacture 75

References 77

4 Zeolite Characterization 85
Steven A. Bradley, Robert W. Broach, Thomas M. Mezza, Sesh Prabhakar, and Wharton Sinkler

4.1 Introduction 85

4.1.1 Importance of Characterization 85

4.2 Multi-Technique Methodology 86

4.2.1 Identifi cation of the Structure of a Newly Invented Zeolite 86

4.3 X-Ray Powder Diffraction Characterization of Zeolitic Systems 91

4.3.1 Interpretation of Powder Diffraction Data for Zeolites 91

4.3.2 Phase Identifi cation and Quantifi cation 92

4.3.3 Unit Cell Size Determination 94

4.3.4 Crystallite Size 95

4.3.5 Rietveld Refi nement 96

4.4 Electron Microscopy Characterization of Zeolitic Systems 97

4.4.1 Importance of Electron Microscopy for Characterizing Zeolites 97

4.4.2 Scanning Electron Microscopy 98

4.4.3 Transmission Electron Microscopy 104

4.5 Infrared Spectroscopy Characterization of Zeolitic Systems 111

4.5.1 Introduction to Infrared Spectroscopy 111

4.5.2 Modes of Measurement 112

4.5.3 Framework IR 114

4.5.4 Methods Requiring Sample Pretreatment 119

4.5.5 Hydroxyl IR 120

4.5.6 Acidity 123

4.5.7 In Situ/In Operando Studies 136

4.5.8 Characterization of Metal-Loaded Zeolites 136

4.6 NMR Characterization of Zeolitic Systems 140

4.6.1 Introduction to NMR 140

4.6.2 Applications 145

4.7 Physical/Chemical Characterization 152

4.7.1 Nitrogen Physisorption 152

4.7.2 Thermal and Mechanical Analyses 154

4.7.3 Adsorption Capacity 156

4.7.4 Acid Sites 157

4.8 Conclusions 158

4.8.1 Future Characterization Directions 158

References 160

5 Overview in Zeolites Adsorptive Separation 173
Santi Kulprathipanja and Robert B. James

5.1 Introduction 173

5.2 Industrial Adsorptive Separation 173

5.2.1 Gas Separation 173

5.2.2 Liquid Separation 174

5.3 R&D Adsorptive Separation 176

5.3.1 Aromatic Hydrocarbon Separation 176

5.3.2 Non-Aromatic Hydrocarbon Separation 176

5.3.3 Carbohydrate Separation 176

5.3.4 Pharmaceutical Separation 176

5.3.5 Trace Impurities Removal 176

5.4 Summary Review of Zeolites in Adsorptive Separation 191

Acknowledgments 192

References 192

6 Aspects of Mechanisms, Processes, and Requirements for Zeolite Separation 203
Santi Kulprathipanja

6.1 Introduction 203

6.2 Impacts of Adsorptive Separation Versus Other Separation Processes 203

6.3 Liquid Phase Adsorption 206

6.3.1 Sanderson’s Model of Intermediate Electronegativity 207

6.4 Modes of Operation 208

6.4.1 Adsorption Isotherms 209

6.4.2 Pulse Test Procedure 209

6.4.3 Breakthrough Procedure 210

6.5 Zeolite Separation Processes 211

6.5.1 Equilibrium-Selective Adsorption 211

6.5.2 Rate-Selective Adsorption 221

6.5.3 Shape-Selective Adsorption 222

6.5.4 Ion Exchange 223

6.5.5 Reactive Adsorption 224

6.6 Summary 225

Acknowledgments 225

References 226

7 Liquid Industrial Aromatics Adsorbent Separation 229
Stanley J. Frey

7.1 Introduction 229

7.2 Major Industrial Processes 231

7.2.1 p-Xylene 231

7.2.2 m-Xylene 241

7.3 Other Signifi cant Processes 243

7.3.1 2,6-Dimethylnaphthalene 244

7.3.2 Ethylbenzene 244

7.3.3 p-Cresol 245

7.4 Summary 245

References 246

8 Liquid Industrial Non-Aromatics Adsorptive Separations 249
Stephen W. Sohn

8.1 Introduction 249

8.2 Normal Paraffi n Separations 249

8.2.1 Characteristics of Adsorbent for Normal Paraffin Extraction 250

8.2.2 Desorbent Critical Characteristics 253

8.2.3 Simulated Moving Bed Operation: Sorbex Process 256

8.2.4 Light Normal Paraffin Separation (Gasoline Range nC5–6) 258

8.2.5 Intermediate Normal Paraffin Separation (C6–10) 260

8.2.6 Heavy Normal Paraffin Separation (C10–18) 261

8.3 Mono-Methyl Paraffins Separation (C10–16) 263

8.3.1 Industrial Use and Demand 263

8.3.2 Unique Operating Parameters 264

8.4 Olefin Separations 265

8.4.1 C4 Separations 266

8.4.2 Detergent Range Olex C10–16 267

8.5 Carbohydrate Separation 269

8.5.1 Industrial Use and Demand 269

8.5.2 Unique Operating Parameters 269

8.6 Liquid Adsorption Acid Separations 269

8.6.1 Citric Acid Separation 270

8.6.2 Free Fatty Acid Separation 270

8.7 Summary 271

References 271

9 Industrial Gas Phase Adsorptive Separations 273
Stephen R. Dunne

9.1 Introduction 273

9.2 Regeneration 275

9.3 Adsorption Equilibrium 276

9.3.1 Henry's Law: A Linear Isotherm 277

9.3.2 Langmuir 277

9.3.3 Potential Theory 278

9.3.4 Universal Isotherm 278

9.3.5 Freundlich 279

9.3.6 Langmuir−Freundlich 279

9.3.7 Kelvin Equation and Capillary Condensation 279

9.4 Mass Transfer in Formed Zeolite Particles 280

9.4.1 Adsorption Wave Speed 282

9.4.2 Adsorption Wave Shape and Length 283

9.4.3 Linear Driving Force Approximation and Resistance Modeling 284

9.4.4 Diffusion Mechanisms in Formed Zeolites 286

9.5 Industrial TSA Separations (Purifi cation) 288

9.5.1 Dehydration 289

9.5.2 De-Sulfurization 294

9.5.3 CO2 Removal 295

9.5.4 VOC Removal 296

9.5.5 Mercury Removal 296

9.6 Industrial PSA 296

9.6.1 PSA Air Separation 297

9.6.2 PSA H2 Purifi cation 299

9.6.3 PSA Dehydration 300

9.7 Industrial Dehydration (Bulk Removal) 301

9.7.1 Desiccant Wheels 301

9.7.2 Enthalpy Control Wheels 302

9.8 Non-Regenerable Adsorption 303

9.9 Summary 303

Nomenclature 303

Greek 304

References 304

10 Zeolite Membrane Separations 307
Jessica O’Brien-Abraham and Jerry Y.S. Lin

10.1 Introduction 307

10.2 Synthesis and Properties of Zeolite Membranes 309

10.2.1 In Situ Crystallization 309

10.2.2 Secondary (Seeded) Growth 311

10.2.3 Characterization of Zeolite Membranes 313

10.3 Transport Theory and Separation Capability of Zeolite Membranes 314

10.3.1 Permeation Through Zeolite Membranes 314

10.3.2 Zeolite Membrane Separation Mechanisms 316

10.3.3 Infl uence of Zeolite Framework Flexibility 319

10.4 Zeolite Membranes in Separation and Reactive Processes 320

10.4.1 Liquid−Liquid Separation 320

10.4.2 Gas/Vapor Separation 322

10.4.3 Reactive Separation Processes 323

10.5 Summary 324

Acknowledgment 325

References 325

11 Mixed-Matrix Membranes 329
Chunqing Liu and Santi Kulprathipanja

11.1 Introduction 329

11.1.1 Scope of This Chapter 329

11.1.2 Polymer Membranes 329

11.1.3 Zeolite Membranes 331

11.2 Compositions of Mixed-Matrix Membranes 332

11.2.1 Non-zeolite/Polymer Mixed-Matrix Membranes 333

11.2.2 Zeolite/Polymer Mixed-Matrix Membranes 333

11.3 Concept of Zeolite/Polymer Mixed-Matrix Membranes 334

11.4 Material Selection for Zeolite/Polymer Mixed-Matrix Membranes 336

11.4.1 Selection of Polymer and Zeolite Materials 336

11.4.2 Modifi cation of Zeolite and Polymer Materials 339

11.5 Geometries of Zeolite/Polymer Mixed-Matrix Membranes 341

11.5.1 Mixed-Matrix Dense Films 341

11.5.2 Asymmetric Mixed-Matrix Membranes 342

11.6 Applications of Zeolite/Polymer Mixed-Matrix Membranes 346

11.6.1 Gas Separation Applications 347

11.6.2 Liquid Separation Applications 347

11.7 Summary 348

References 349

12 Overview and Recent Developments in Catalytic Applications of Zeolites 355
Christopher P. Nicholas

12.1 History of Catalytic Uses of Zeolites 355

12.1.1 R&D Uses Versus Industrial Application of Zeolite Catalysis 355

12.2 Literature Review of Recent Developments in Catalytic Uses of Zeolites 356

12.2.1 Isomerization Reactions 356

12.2.2 Oligomerization Reactions 358

12.2.3 Alkylation Reactions 364

12.2.4 Aromatics Reactions 369

12.2.5 Chain-Breaking Reactions 369

12.2.6 Dehydroaromatization 377

12.2.7 Methanol to Olefi ns 383

12.2.8 Hydrotreating and Hydrocracking 383

12.2.9 Reactions Using Heteroatom Substituted Zeolites 387

12.3 Future Trends in Catalysis by Zeolites 393

References 393

13 Unique Aspects of Mechanisms and Requirements for Zeolite Catalysis in Refining and Petrochemicals 403
Hayim Abrevaya

13.1 Introduction 403

13.2 Adsorption 404

13.2.1 Langmuir Isotherm and Reaction Kinetics 404

13.2.2 Nitrogen Adsorption 406

13.2.3 Hydrocarbon Adsorption 408

13.3 Diffusion 416

13.4 Acidity 420

13.4.1 Bronsted Acidity 420

13.4.2 Significance of Acid Strength 421

13.4.3 Significance of Acid Site Density 423

13.4.4 Lewis Acidity 423

13.4.5 External acidity 424

13.5 Carbocations 425

13.5.1 Carbenium Ions and Alkoxides 426

13.5.2 Carbonium Ions 429

13.6 Elementary Steps of Hydrocarbon Conversion over Zeolites 429

13.7 Shape Selectivity 430

13.7.1 Tools 430

13.7.2 Reactant Shape Selectivity 435

13.7.3 Transition State Shape Selectivity 435

13.7.4 Product Shape Selectivity 438

13.7.5 Crystal Size Effects 446

13.8 Reaction Mechanisms 447

13.8.1 Alkene Skeletal Isomerization 447

13.8.2 Alkene Oligomerization 448

13.8.3 Alkylation 450

13.8.4 Alkane Cracking 455

13.8.5 Aromatic Transformation 462

13.8.6 Methanol to Olefi ns 464

13.9 Key Remaining Questions 470

References 470

14 Industrial Isomerization 479
John E. Bauer, Feng Xu, Paula L. Bogdan, and Gregory J. Gajda

14.1 Introduction 479

14.2 Metal−Zeolite Catalyzed Light Paraffi n Isomerization 479

14.2.1 General Considerations 480

14.2.2 Bifunctional Paraffi n Isomerization Mechanism 480

14.2.3 Zeolitic Paraffi n Isomerization Catalysis 482

14.2.4 Industrial Zeolitic Isomerization Catalysts and Processes 483

14.2.5 Summary 484

14.3 Olefin Isomerization 484

14.3.1 General Considerations 484

14.3.2 Cis–Trans and Double Bond Isomerization 485

14.3.3 Skeletal Isomerization (Butenes, Pentenes, Hexenes) 486

14.3.4 Skeletal Isomerization (Longer-Chain Olefins) 488

14.3.5 Olefin Isomerization Summary 488

14.4 C8 Aromatics Isomerization 488

14.4.1 The Chemistry of C8 Aromatics Isomerization 489

14.4.2 C8 Aromatics Isomerization Catalysts 494

14.4.3 C8 Aromatics Isomerization Processes 495

14.4.4 Future Developments 499

14.4.5 C8 Aromatics Isomerization Summary 500

References 500

15 Processes on Industrial C–C Bond Formation 505
Deng-Yang Y. Jan and Paul T. Barger

15.1 Introduction 505

15.2 Olefin Oligomerization 505

15.2.1 C2/C3/C4 Olefi n Oligomerization 505

15.3 Paraffin/Olefin Alkylation 507

15.3.1 Motor Fuel Alkylation 507

15.4 Benzene Alkylation 512

15.4.1 Ethylbenzene (Ethylene Alkylation), Cumene and Detergent Linear Alkylbenzene 512

15.4.2 Para-Xylene (Methylation of Toluene) 514

15.4.3 Styrene and Ethylbenzene from Methylation of Toluene 515

15.5 Alkylbenzene Disproportionation and Trans-Alkylation 517

15.5.1 Process Chemistry: Feeds, Products and Reactions 517

15.5.2 Catalysts 517

15.5.3 Physicochemical Characterization of Active Sites 518

15.6 Paraffin/Olefin to Aromatics 518

15.6.1 C3/C4 Paraffin to Aromatics and C3/C4 Paraffin/Olefin to Aromatics 518

15.6.2 C6/C7 Paraffin to Aromatics (Zeolitic Reforming) 520

15.7 Methanol to Olefi ns and Aromatics 521

15.7.1 Methanol to C2–C4 Olefi ns 521

15.7.2 Methanol to Aromatics 522

15.7.3 Catalysts 523

15.7.4 Reaction Mechanism of Methanol to Hydrocarbons 527

15.8 Summary 528

References 528

16 Bond Breaking and Rearrangement 535
Suheil F. Abdo

16.1 Introduction 535

16.2 Critical Zeolite Properties 536

16.2.1 Framework Types and Compositions 536

16.2.2 Stabilization Methods 539

16.2.3 Property–Function Relationship 542

16.3 Chemistry of Bond Scission Processes 546

16.3.1 Heteroatom Removal: Desulfurization Denitrogenation and Deoxygenation 546

16.3.2 Boiling Point Reduction 551

16.4 Fluidized Catalytic Cracking 556

16.4.1 Process Confi guration and Catalysts 557

16.4.2 The Changing Role of the FCC: Transportation Fuel Production or Petrochemical Feed Production 560

16.5 Hydrocracking and Hydroisomerization 560

16.5.1 Process Confi gurations and Catalysts 561

16.5.2 Catalyst Requirements for the Hydrocracker 561

16.5.3 The Changing Role of the Hydrocracker in a Reformulated Fuels Environment 565

16.6 Conclusions 566

References 566

Index 571

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Dr. Santi Kulprathipanja has worked for UOP, A Honeywell Company, since 1978. He is curently a Fellow and has been recognized as a distinguished UOP inventor for being named on over 100 U.S. patents. His list of UOP innovations includes the processes used to make unleaded gasoline and biodegradable detergents, p-xylene separation - Parex(TM), Citric acid separation, the catalytic converter, the inventor of mixed matrix membranes, and the science behind the UOP MX Sorbex (TM) process, the building blocks for modern plastics. He has also been involved with developing technology that removes carcinogenic materials from fuel and other chemicals, and research technology that desulfurizes fuel in order to reduce emissions and remove odors for a cleaner environment. Dr. Kulprathipanja has edited a book entitled "Reactive Separation Process", authored numerous book chapters and published over 70 reference articles. He has also taught and supervised graduate students in the area of separation technology.
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