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Book Details
Abstract
Covering the breadth of zeolite chemistry and catalysis, this book provides the reader with a complete introduction to field, covering synthesis, structure, characterisation and applications.
Beginning with the history of natural and synthetic zeolites, the reader will learn how zeolite structures are formed, synthetic routes, and experimental and theoretical structure determination techniques. Their industrial applications are covered in-depth, from their use in the petrochemical industry, through to fine chemicals and more specialised clinical applications. Novel zeolite materials are covered, including hierarchical zeolites and two-dimensional zeolites, showcasing modern developments in the field. This book is ideal for newcomers who need to get up to speed with zeolite chemistry, and also experienced researchers who will find this a modern, up-to-date guide.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Contents | ix | ||
| Chapter 1 Zeolite Science and Perspectives | 1 | ||
| 1.1 Historical Background | 1 | ||
| 1.2 Natural Zeolites | 3 | ||
| 1.3 Synthesis | 5 | ||
| 1.3.1 Role of the Organic Additives | 7 | ||
| 1.3.2 Role of the Heteroatom | 11 | ||
| 1.3.3 Two-dimensional (2D) Zeolites | 13 | ||
| 1.3.4 Hierarchical Porous Structures | 15 | ||
| 1.4 Applications | 19 | ||
| 1.4.1 Zeolites as Heterogeneous Catalysts | 19 | ||
| 1.4.2 Zeolites for Adsorption and Separations | 23 | ||
| 1.5 Conclusions and Outlook | 26 | ||
| References | 28 | ||
| Chapter 2 Zeolite Structures | 37 | ||
| 2.1 Introduction | 37 | ||
| 2.2 Zeolite Framework Types | 38 | ||
| 2.2.1 Classification | 38 | ||
| 2.2.2 Database of Zeolite Structures | 39 | ||
| 2.2.3 Channels | 40 | ||
| 2.2.4 Building Units | 41 | ||
| 2.2.5 Natural Tiles | 46 | ||
| 2.2.6 Framework Density | 47 | ||
| 2.2.7 Coordination Sequences | 47 | ||
| 2.2.8 Vertex Symbols | 48 | ||
| 2.3 Zeolite Structures | 49 | ||
| 2.3.1 Framework Composition | 49 | ||
| 2.3.2 Extra-framework Species | 50 | ||
| 2.3.3 Stacking Faults and Disorder | 50 | ||
| 2.4 Examples of Framework Structures | 51 | ||
| 2.4.1 SOD | 51 | ||
| 2.4.2 LTA | 51 | ||
| 2.4.3 FAU | 52 | ||
| 2.4.4 EMT | 54 | ||
| 2.4.5 RHO | 54 | ||
| 2.4.6 MOR | 55 | ||
| 2.4.7 MFI | 55 | ||
| 2.4.8 FER | 56 | ||
| 2.4.9 CHA | 57 | ||
| 2.4.10 MWW | 57 | ||
| 2.4.11 *BEA | 58 | ||
| 2.4.12 *–SSO | 59 | ||
| 2.4.13 UTL | 61 | ||
| 2.4.14 Zeolite Frameworks with Extra-large Pores | 62 | ||
| 2.5 Structure Determination | 63 | ||
| 2.5.1 Information in a Powder Diffraction Pattern | 64 | ||
| 2.5.2 Powder Diffraction for Phase Identification | 65 | ||
| 2.5.3 Structural Analysis using Powder Diffraction Data | 66 | ||
| 2.5.4 Electron Diffraction | 67 | ||
| 2.5.5 Structural Analysis using HRTEM Images | 68 | ||
| 2.6 Conclusions | 69 | ||
| Acknowledgments | 70 | ||
| References | 70 | ||
| Chapter 3 Synthesis of Zeolites | 73 | ||
| 3.1 Introduction | 73 | ||
| 3.2 Basic Zeolite Synthesis | 75 | ||
| 3.2.1 Mineralizing Agents | 76 | ||
| 3.2.2 Effects of Water Concentration | 78 | ||
| 3.3 Gel Preparation and Crystallization | 79 | ||
| 3.4 Effects of Gel Composition | 83 | ||
| 3.4.1 Isomorphous Substitution | 84 | ||
| 3.4.2 Aluminophosphates | 86 | ||
| 3.5 Structure Directing Agents | 87 | ||
| 3.6 Molecular Modeling | 90 | ||
| 3.7 Nonconventional Synthesis Approaches | 92 | ||
| 3.8 Transformation of a Zeolite into a Catalyst | 93 | ||
| 3.9 High-throughput Syntheses | 95 | ||
| 3.10 Summary and Outlook | 96 | ||
| References | 97 | ||
| Chapter 4 Hierarchical Zeolites | 103 | ||
| 4.1 Introduction | 103 | ||
| 4.1.1 General Aspects and Definition | 103 | ||
| 4.1.2 Diffusion Limitations | 105 | ||
| 4.1.3 Reduction of Diffusion Path Length | 107 | ||
| 4.1.4 Preparation Principles of Hierarchical Zeolites | 108 | ||
| 4.2 Preparation Methods for Hierarchical All-zeolitic Materials | 111 | ||
| 4.2.1 Bottom-up Approaches | 112 | ||
| 4.2.2 Top-down Approaches | 117 | ||
| 4.2.3 Summary and Comparison | 121 | ||
| 4.3 Characterisation of Hierarchical Zeolites | 122 | ||
| 4.3.1 Structural Properties | 125 | ||
| 4.3.2 Textural Properties | 127 | ||
| 4.3.3 Transport/Diffusion Properties | 129 | ||
| 4.3.4 Mechanical and Hydrothermal Stability | 130 | ||
| 4.3.5 Catalytic Test Reactions | 133 | ||
| 4.4 Application of Hierarchical Systems Involving Zeolites | 136 | ||
| 4.4.1 Hierarchy in Zeolitic Composites | 136 | ||
| 4.4.2 Technical Applications of Hierarchical Zeolitic Composites | 137 | ||
| 4.5 Summary/Conclusions | 139 | ||
| References | 140 | ||
| Chapter 5 Two-dimensional Zeolites | 146 | ||
| 5.1 Introduction to 3D versus 2D Zeolites | 146 | ||
| 5.2 Types of Layers Spatial Arrangement | 148 | ||
| 5.2.1 2D Forms Prepared by Direct Synthesis | 149 | ||
| 5.2.2 Forms of Layered Zeolites Prepared by Post-synthesis Modifications | 154 | ||
| 5.2.3 Layer-like Materials | 158 | ||
| 5.3 Synthesis of 2D Zeolites | 160 | ||
| 5.3.1 Bottom-up – Hydrothermal Synthesis | 160 | ||
| 5.3.2 Top-down – Disassembly of Germanosilicates into Layered Zeolite Precursors | 168 | ||
| 5.4 Chemistry of 2D Zeolites – Modification of Interlamellar Space | 171 | ||
| 5.4.1 Detemplation by Thermal Combustion and Chemical Extraction | 172 | ||
| 5.4.2 Intercalation into Interlamellar Space | 172 | ||
| 5.4.3 Delamination/Exfoliation and Colloidal Suspensions | 179 | ||
| 5.5 Properties of 2D Zeolites and their Characterization | 181 | ||
| 5.6 Application of 2D Zeolites | 183 | ||
| 5.7 Conclusions | 184 | ||
| Acknowledgments | 185 | ||
| References | 185 | ||
| Chapter 6 Structure Determination | 194 | ||
| 6.1 What Does ‘Structure' Mean? | 194 | ||
| 6.2 X-ray Diffraction | 196 | ||
| 6.2.1 Diffraction from Atoms and Arrangements of Atoms | 197 | ||
| 6.2.2 Diffraction from Crystalline Materials | 197 | ||
| 6.2.3 The Ewald Sphere | 200 | ||
| 6.2.4 X-ray Generation and Synchrotrons | 201 | ||
| 6.3 Single-crystal X-ray Diffraction (SCXRD) | 202 | ||
| 6.3.1 Choosing a Good Crystal | 202 | ||
| 6.3.2 Diffractometers | 203 | ||
| 6.3.3 Initial Images and Calculation of the Orientation Matrix | 204 | ||
| 6.3.4 Data Collection Strategies | 205 | ||
| 6.3.5 Data Integration and Reduction | 206 | ||
| 6.3.6 Solving the Structure – Getting around the Phase Problem | 206 | ||
| 6.3.7 Refining the Structure | 207 | ||
| 6.3.8 Residual Factors | 208 | ||
| 6.3.9 Atomic Displacement Parameters and Occupancy Factors | 209 | ||
| 6.3.10 Constraints and Restraints | 210 | ||
| 6.3.11 Publication (CIFs and cifcheck) | 210 | ||
| 6.4 Powder X-ray Diffraction | 210 | ||
| 6.4.1 The Rietveld Method | 212 | ||
| 6.4.2 Restraints | 213 | ||
| 6.5 Pair Distribution Function (PDF) Analysis | 214 | ||
| 6.5.1 Disorder and Crystallographically Challenging Materials | 214 | ||
| 6.5.2 Total Scattering and Relation to the Functions S(Q), F(Q), and G(r) | 215 | ||
| 6.5.3 The Pair Distribution Function, g(r), G(r), and R(r) | 217 | ||
| 6.5.4 Data Collection | 218 | ||
| 6.5.5 Data Processing | 219 | ||
| 6.5.6 Interpretation and Modelling | 219 | ||
| 6.6 Solid-state NMR | 224 | ||
| 6.6.1 Interactions in NMR Spectroscopy | 225 | ||
| 6.6.2 Important NMR Experiments | 227 | ||
| 6.7 Gas Adsorption Measurements | 233 | ||
| 6.7.1 Surface Area and Porosity Measurements | 235 | ||
| References | 237 | ||
| Chapter 7 Spectroscopy of Zeolites | 240 | ||
| 7.1 Introduction | 240 | ||
| 7.2 Routine Characterization Techniques | 242 | ||
| 7.3 Zeolite Synthesis | 242 | ||
| 7.3.1 Simultaneous Synchrotron-based Spectroscopy | 243 | ||
| 7.3.2 NMR Spectroscopy | 245 | ||
| 7.3.3 Raman Spectroscopy | 247 | ||
| 7.4 Zeolite Modification | 249 | ||
| 7.4.1 Fluorescence and UV-Vis Microscopy | 250 | ||
| 7.4.2 Integrated Light and Electron Microscopy | 251 | ||
| 7.4.3 NMR and X-ray Fluorescence | 252 | ||
| 7.4.4 X-ray Microscopy and Tomography | 252 | ||
| 7.4.5 Positron Annihilation Spectroscopy | 253 | ||
| 7.5 Zeolite Catalysis | 255 | ||
| 7.5.1 UV-Vis Spectroscopy | 255 | ||
| 7.5.2 Single Molecule Fluorescence Microscopy | 257 | ||
| 7.5.3 IR Spectroscopy | 258 | ||
| 7.5.4 Raman Spectroscopy | 258 | ||
| 7.5.5 NMR Spectroscopy | 261 | ||
| 7.5.6 X-ray Absorption, Emission, and Diffraction | 263 | ||
| 7.6 Zeolite Deactivation and Regeneration | 263 | ||
| 7.6.1 IR, NMR, Raman and UV-Vis Spectroscopy | 265 | ||
| 7.6.2 NMR and EPR Spectroscopy | 265 | ||
| 7.6.3 Micro-spectroscopy and Fluorescence Microscopy | 267 | ||
| 7.6.4 X-ray Microscopy and Tomography | 267 | ||
| 7.6.5 IR Spectroscopy | 271 | ||
| 7.6.6 NMR and UV-Vis Spectroscopy | 272 | ||
| 7.7 Conclusions | 272 | ||
| List of Abbreviations | 273 | ||
| Acknowledgments | 273 | ||
| References | 273 | ||
| Chapter 8 Electron Microscopy of Zeolites | 277 | ||
| 8.1 Introduction | 277 | ||
| 8.2 Highlights of the Techniques | 279 | ||
| 8.2.1 Electron Gun | 279 | ||
| 8.2.2 Scanning Electron Microscopy | 280 | ||
| 8.2.3 Transmission Electron Microscopy | 283 | ||
| 8.2.4 Scanning Transmission Electron Microscopy | 284 | ||
| 8.2.5 Energy Dispersive X-ray Spectroscopy | 285 | ||
| 8.2.6 Electron Tomography | 286 | ||
| 8.3 Electron Microscopic Imaging of Zeolites | 286 | ||
| 8.3.1 Crystal Size and Morphology | 286 | ||
| 8.3.2 Zeolite Structures | 292 | ||
| 8.3.3 Defects in Zeolites | 297 | ||
| 8.3.4 Catalytic Metal Nanoparticles in Zeolites | 302 | ||
| 8.4 Summary | 304 | ||
| Acknowledgments | 305 | ||
| References | 306 | ||
| Chapter 9 Zeolites in Industrial Catalysis | 310 | ||
| 9.1 Introduction | 310 | ||
| 9.2 Economic Impact: Market Volumes and Sales | 312 | ||
| 9.3 Overview of the Rich Variety of Synthetic Zeolite Applications | 312 | ||
| 9.4 Catalytic Applications | 314 | ||
| 9.5 Critical Properties for Catalysis | 315 | ||
| 9.6 Common Secondary Synthesis and Stabilization Methods | 316 | ||
| 9.6.1 Framework Stabilization | 316 | ||
| 9.6.2 Acidity Control | 317 | ||
| 9.6.3 Porosity Modification | 318 | ||
| 9.7 Recap of Important Properties | 321 | ||
| 9.8 Refining & Petrochemical Applications | 322 | ||
| 9.8.1 Overview | 322 | ||
| 9.8.2 FCC | 323 | ||
| 9.8.3 Hydrocracking | 327 | ||
| 9.8.4 Dewaxing and Hydroisomerization | 333 | ||
| 9.8.5 Olefin Oligomerization and Conversion Technologies | 334 | ||
| 9.8.6 Light Naphtha Isomerization | 336 | ||
| 9.8.7 Aromatic Alkylation and Transalkylation | 336 | ||
| 9.8.8 Paraffin Conversion into Aromatics | 337 | ||
| 9.8.9 Methanol-to-Olefins (MTO) | 338 | ||
| 9.8.10 NOx Selective Catalytic Reduction (SCR) - Acid Catalyst with Redox Active Metal | 342 | ||
| 9.9 Remaining Challenges and Conclusions | 344 | ||
| References | 344 | ||
| Chapter 10 Application of Zeolites in the Production of Light Olefins and BTX Petrochemical Intermediates | 351 | ||
| 10.1 Introduction | 351 | ||
| 10.2 Production of Light Olefins | 354 | ||
| 10.2.1 Catalytic Cracking | 354 | ||
| 10.2.2 Methanol-to-olefins (MTO) | 361 | ||
| 10.2.3 Oxidative Dehydrogenation (ODH) of Short-chain Alkanes | 368 | ||
| 10.3 Production of BTX Aromatics | 371 | ||
| 10.3.1 Aromatization of LPG | 371 | ||
| 10.3.2 Catalytic Reforming of Naphtha | 374 | ||
| 10.3.3 Non-oxidative Methane Dehydroaromatization (MDA) | 377 | ||
| 10.4 Production of para-Xylene | 383 | ||
| 10.4.1 Isomerization of C8-alkylaromatics | 383 | ||
| 10.4.2 Disproportionation/Transalkylation of Toluene | 388 | ||
| 10.4.3 Alkylation of Toluene with Methanol | 392 | ||
| 10.5 Concluding Remarks | 394 | ||
| Acknowledgments | 396 | ||
| References | 397 | ||
| Chapter 11 Zeolites for Fine Chemistry | 409 | ||
| 11.1 Introduction | 409 | ||
| 11.2 Features of Zeolites as Catalysts – General Aspects | 410 | ||
| 11.3 Electrophilic Aromatic Substitution | 412 | ||
| 11.3.1 Acylation of Monocyclic Aromatic Hydrocarbons | 414 | ||
| 11.3.2 Acylation of Monocyclic Arenes Containing Hydroxyl-/Alkoxy-groups | 415 | ||
| 11.3.3 Acylation of Polycyclic Arenes | 417 | ||
| 11.3.4 Alkylation of Aromatic Compounds | 418 | ||
| 11.4 Reactions of Carbonyl Compounds | 420 | ||
| 11.4.1 Acetalization | 420 | ||
| 11.4.2 Hydroxyalkylation | 421 | ||
| 11.4.3 Aldol Condensation | 422 | ||
| 11.5 Cyclization and Cycloaddition | 423 | ||
| 11.5.1 Diels-Alder Reaction | 423 | ||
| 11.5.2 Other Cyclization Reactions | 425 | ||
| 11.6 Isomerization | 427 | ||
| 11.6.1 Terpenes | 427 | ||
| 11.6.2 Carbohydrates | 428 | ||
| 11.7 Red-ox Reactions | 429 | ||
| 11.7.1 Epoxidation | 430 | ||
| 11.7.2 Baeyer-Villiger Reaction | 432 | ||
| 11.7.3 Oppenauer-Meerwein-Ponndorf-Verley Oxidation-Reduction | 433 | ||
| 11.8 Concluding Remarks | 435 | ||
| References | 436 | ||
| Chapter 12 Biomass Conversion over Zeolite Catalysts | 441 | ||
| 12.1 Introduction | 441 | ||
| 12.2 Valorization of Oleaginous Feedstock over Zeolite Catalysts | 444 | ||
| 12.2.1 Catalytic Cracking of Triglycerides | 446 | ||
| 12.2.2 Hydrocracking/Hydroisomerization of Triglycerides | 448 | ||
| 12.3 Thermocatalytic Valorization of Lignocellulosic Feedstock over Zeolites | 450 | ||
| 12.3.1 Catalytic Pyrolysis | 453 | ||
| 12.3.2 Catalytic Upgrading of Pyrolysis Bio-oil | 455 | ||
| 12.4 Chemocatalytic Valorization of Lignocellulosic Biomass over Zeolites | 458 | ||
| 12.4.1 From Sugars to Platform Molecules | 459 | ||
| 12.4.2 From Platform Molecules to Valuable Chemicals | 464 | ||
| 12.4.3 Cascade Reactions: Multifunctional Zeolites | 468 | ||
| 12.5 Concluding Remarks | 472 | ||
| Acknowledgments | 474 | ||
| References | 474 | ||
| Chapter 13 Zeolite Membranes in Catalysis | 481 | ||
| 13.1 Introduction | 481 | ||
| 13.2 Zeolite Membranes | 483 | ||
| 13.2.1 Synthesis | 485 | ||
| 13.2.2 Supports | 487 | ||
| 13.2.3 Characterization | 490 | ||
| 13.3 Zeolite Membrane Reactors | 492 | ||
| 13.3.1 Reactor Level | 493 | ||
| 13.3.2 Particle Level | 496 | ||
| 13.3.3 Crystal Level | 509 | ||
| 13.4 Conclusion and Outlook | 510 | ||
| References | 511 | ||
| Subject Index | 519 |