Zeolites in Industrial Separation and Catalysis

Zeolites in Industrial Separation and Catalysis

By: Santi Kulprathipanja (editor)Hardback

Up to 2 WeeksUsually despatched within 2 weeks

Description

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.

About Author

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.

Contents

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

Product Details

  • ISBN13: 9783527325054
  • Format: Hardback
  • Number Of Pages: 618
  • ID: 9783527325054
  • weight: 1286
  • ISBN10: 3527325050

Delivery Information

  • Saver Delivery: Yes
  • 1st Class Delivery: Yes
  • Courier Delivery: Yes
  • Store Delivery: Yes

Prices are for internet purchases only. Prices and availability in WHSmith Stores may vary significantly

Close