Zeolites in catalysis properties and applications 1st edition by Jiří Čejka 1788011563 9781788011563

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ISBN-10 :  1788011563 

ISBN-13 :  9781788011563

Author:  Jiří Čejka 

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.

Zeolites in catalysis properties and applications 1st Table of contents:

Chapter 1 Zeolite Science and Perspectives
1.1 Historical Background
1.2 Natural Zeolites
1.3 Synthesis
1.3.1 Role of the Organic Additives
1.3.2 Role of the Heteroatom
1.3.3 Two-dimensional (2D) Zeolites
1.3.4 Hierarchical Porous Structures
1.4 Applications
1.4.1 Zeolites as Heterogeneous Catalysts
1.4.2 Zeolites for Adsorption and Separations
1.5 Conclusions and Outlook
References
Chapter 2 Zeolite Structures
2.1 Introduction
2.2 Zeolite Framework Types
2.2.1 Classification
2.2.2 Database of Zeolite Structures
2.2.3 Channels
2.2.4 Building Units
2.2.5 Natural Tiles
2.2.6 Framework Density
2.2.7 Coordination Sequences
2.2.8 Vertex Symbols
2.3 Zeolite Structures
2.3.1 Framework Composition
2.3.2 Extra-framework Species
2.3.3 Stacking Faults and Disorder
2.4 Examples of Framework Structures
2.4.1 SOD
2.4.2 LTA
2.4.3 FAU
2.4.4 EMT
2.4.5 RHO
2.4.6 MOR
2.4.7 MFI
2.4.8 FER
2.4.9 CHA
2.4.10 MWW
2.4.11 *BEA
2.4.12 *−SSO
2.4.13 UTL
2.4.14 Zeolite Frameworks with Extra-large Pores
2.5 Structure Determination
2.5.1 Information in a Powder Diffraction Pattern
2.5.2 Powder Diffraction for Phase Identification
2.5.3 Structural Analysis using Powder Diffraction Data
2.5.4 Electron Diffraction
2.5.5 Structural Analysis using HRTEM Images
2.6 Conclusions
Acknowledgements
References
Chapter 3 Synthesis of Zeolites
3.1 Introduction
3.2 Basic Zeolite Synthesis
3.2.1 Mineralizing Agents
3.2.2 Effects of Water Concentration
3.3 Gel Preparation and Crystallization
3.4 Effects of Gel Composition
3.4.1 Isomorphous Substitution
3.4.2 Aluminophosphates
3.5 Structure Directing Agents
3.6 Molecular Modeling
3.7 Nonconventional Synthesis Approaches
3.8 Transformation of a Zeolite into a Catalyst
3.9 High-throughput Syntheses
3.10 Summary and Outlook
References
Chapter 4 Hierarchical Zeolites
4.1 Introduction
4.1.1 General Aspects and Definition
4.1.2 Diffusion Limitations
4.1.3 Reduction of Diffusion Path Length
4.1.4 Preparation Principles of Hierarchical Zeolites
4.2 Preparation Methods for Hierarchical All-zeolitic Materials
4.2.1 Bottom-up Approaches
4.2.2 Top-down Approaches
4.2.3 Summary and Comparison
4.3 Characterisation of Hierarchical Zeolites
4.3.1 Structural Properties
4.3.2 Textural Properties
4.3.3 Transport/Diffusion Properties
4.3.4 Mechanical and Hydrothermal Stability
4.3.5 Catalytic Test Reactions
4.4 Application of Hierarchical Systems Involving Zeolites
4.4.1 Hierarchy in Zeolitic Composites
4.4.2 Technical Applications of Hierarchical Zeolitic Composites
4.5 Summary/Conclusions
References
Chapter 5 Two-dimensional Zeolites
5.1 Introduction to 3D versus 2D Zeolites
5.2 Types of Layers Spatial Arrangement
5.2.1 2D Forms Prepared by Direct Synthesis
5.2.2 Forms of Layered Zeolites Prepared by Post-synthesis Modifications
5.2.3 Layer-like Materials
5.3 Synthesis of 2D Zeolites
5.3.1 Bottom-up – Hydrothermal Synthesis
5.3.2 Top-down – Disassembly of Germanosilicates into Layered Zeolite Precursors
5.4 Chemistry of 2D Zeolites – Modification of Interlamellar Space
5.4.1 Detemplation by Thermal Combustion and Chemical Extraction
5.4.2 Intercalation into Interlamellar Space
5.4.3 Delamination/Exfoliation and Colloidal Suspensions
5.5 Properties of 2D Zeolites and their Characterization
5.6 Application of 2D Zeolites
5.7 Conclusions
Acknowledgements
References
Chapter 6 Structure Determination
6.1 What Does ‘Structure’ Mean?
6.2 X-ray Diffraction
6.2.1 Diffraction from Atoms and Arrangements of Atoms
6.2.2 Diffraction from Crystalline Materials
6.2.3 The Ewald Sphere
6.2.4 X-ray Generation and Synchrotrons
6.3 Single-crystal X-ray Diffraction (SCXRD)
6.3.1 Choosing a Good Crystal
6.3.2 Diffractometers
6.3.3 Initial Images and Calculation of the Orientation Matrix
6.3.4 Data Collection Strategies
6.3.5 Data Integration and Reduction
6.3.6 Solving the Structure – Getting around the Phase Problem
6.3.7 Refining the Structure
6.3.8 Residual Factors
6.3.9 Atomic Displacement Parameters and Occupancy Factors
6.3.10 Constraints and Restraints
6.3.11 Publication (CIFs and cifcheck)
6.4 Powder X-ray Diffraction
6.4.1 The Rietveld Method
6.4.2 Restraints
6.5 Pair Distribution Function (PDF) Analysis
6.5.1 Disorder and Crystallographically Challenging Materials
6.5.2 Total Scattering and Relation to the Functions S(Q), F(Q), and G(r)
6.5.3 The Pair Distribution Function, g(r), G(r), and R(r)
6.5.4 Data Collection
6.5.5 Data Processing
6.5.6 Interpretation and Modelling
6.6 Solid-state NMR
6.6.1 Interactions in NMR Spectroscopy
6.6.2 Important NMR Experiments
6.7 Gas Adsorption Measurements
6.7.1 Surface Area and Porosity Measurements
References
Chapter 7 Spectroscopy of Zeolites
7.1 Introduction
7.2 Routine Characterization Techniques
7.3 Zeolite Synthesis
7.3.1 Simultaneous Synchrotron-based Spectroscopy
7.3.2 NMR Spectroscopy
7.3.3 Raman Spectroscopy
7.4 Zeolite Modification
7.4.1 Fluorescence and UV-Vis Microscopy
7.4.2 Integrated Light and Electron Microscopy
7.4.3 NMR and X-ray Fluorescence
7.4.4 X-ray Microscopy and Tomography
7.4.5 Positron Annihilation Spectroscopy
7.5 Zeolite Catalysis
7.5.1 UV-Vis Spectroscopy
7.5.2 Single Molecule Fluorescence Microscopy
7.5.3 IR Spectroscopy
7.5.4 Raman Spectroscopy
7.5.5 NMR Spectroscopy
7.5.6 X-ray Absorption, Emission, and Diffraction
7.6 Zeolite Deactivation and Regeneration
7.6.1 IR, NMR, Raman and UV-Vis Spectroscopy
7.6.2 NMR and EPR Spectroscopy
7.6.3 Micro-spectroscopy and Fluorescence Microscopy
7.6.4 X-ray Microscopy and Tomography
7.6.5 IR Spectroscopy
7.6.6 NMR and UV-Vis Spectroscopy
7.7 Conclusions
List of Abbreviations
Acknowledgements
References
Chapter 8 Electron Microscopy of Zeolites
8.1 Introduction
8.2 Highlights of the Techniques
8.2.1 Electron Gun
8.2.2 Scanning Electron Microscopy
8.2.3 Transmission Electron Microscopy
8.2.4 Scanning Transmission Electron Microscopy
8.2.5 Energy Dispersive X-ray Spectroscopy
8.2.6 Electron Tomography
8.3 Electron Microscopic Imaging of Zeolites
8.3.1 Crystal Size and Morphology
8.3.2 Zeolite Structures
8.3.3 Defects in Zeolites
8.3.4 Catalytic Metal Nanoparticles in Zeolites
8.4 Summary
Acknowledgements
References
Chapter 9 Zeolites in Industrial Catalysis
9.1 Introduction
9.2 Economic Impact: Market Volumes and Sales
9.3 Overview of the Rich Variety of Synthetic Zeolite Applications
9.4 Catalytic Applications
9.5 Critical Properties for Catalysis
9.6 Common Secondary Synthesis and Stabilization Methods
9.6.1 Framework Stabilization
9.6.2 Acidity Control
9.6.3 Porosity Modification
9.7 Recap of Important Properties
9.8 Refining & Petrochemical Applications
9.8.1 Overview
9.8.2 FCC
9.8.3 Hydrocracking
9.8.4 Dewaxing and Hydroisomerization
9.8.5 Olefin Oligomerization and Conversion Technologies
9.8.6 Light Naphtha Isomerization
9.8.7 Aromatic Alkylation and Transalkylation
9.8.8 Paraffin Conversion into Aromatics
9.8.9 Methanol-to-Olefins (MTO)
9.8.10 NOx Selective Catalytic Reduction (SCR) – Acid Catalyst with Redox Active Metal
9.9 Remaining Challenges and Conclusions
References
Chapter 10 Application of Zeolites in the Production of Light Olefins and BTX Petrochemical Intermediates
10.1 Introduction
10.2 Production of Light Olefins
10.2.1 Catalytic Cracking
10.2.2 Methanol-to-olefins (MTO)
10.2.3 Oxidative Dehydrogenation (ODH) of Short-chain Alkanes
10.3 Production of BTX Aromatics
10.3.1 Aromatization of LPG
10.3.2 Catalytic Reforming of Naphtha
10.3.3 Non-oxidative Methane Dehydroaromatization (MDA)
10.4 Production of para-Xylene
10.4.1 Isomerization of C8-alkylaromatics
10.4.2 Disproportionation/Transalkylation of Toluene
10.4.3 Alkylation of Toluene with Methanol
10.5 Concluding Remarks
Acknowledgements
References
Chapter 11 Zeolites for Fine Chemistry
11.1 Introduction
11.2 Features of Zeolites as Catalysts – General Aspects
11.3 Electrophilic Aromatic Substitution
11.3.1 Acylation of Monocyclic Aromatic Hydrocarbons
11.3.2 Acylation of Monocyclic Arenes Containing Hydroxyl-/Alkoxy-groups
11.3.3 Acylation of Polycyclic Arenes
11.3.4 Alkylation of Aromatic Compounds
11.4 Reactions of Carbonyl Compounds
11.4.1 Acetalization
11.4.2 Hydroxyalkylation
11.4.3 Aldol Condensation
11.5 Cyclization and Cycloaddition
11.5.1 Diels–Alder Reaction
11.5.2 Other Cyclization Reactions
11.6 Isomerization
11.6.1 Terpenes
11.6.2 Carbohydrates
11.7 Red-ox Reactions
11.7.1 Epoxidation
11.7.2 Baeyer–Villiger Reaction
11.7.3 Oppenauer–Meerwein–Ponndorf–Verley Oxidation–Reduction
11.8 Concluding Remarks
References
Chapter 12 Biomass Conversion over Zeolite Catalysts
12.1 Introduction
12.2 Valorization of Oleaginous Feedstock over Zeolite Catalysts
12.2.1 Catalytic Cracking of Triglycerides
12.2.2 Hydrocracking/Hydroisomerization of Triglycerides
12.3 Thermocatalytic Valorization of Lignocellulosic Feedstock over Zeolites
12.3.1 Catalytic Pyrolysis
12.3.2 Catalytic Upgrading of Pyrolysis Bio-oil
12.4 Chemocatalytic Valorization of Lignocellulosic Biomass over Zeolites
12.4.1 From Sugars to Platform Molecules
12.4.2 From Platform Molecules to Valuable Chemicals
12.4.3 Cascade Reactions: Multifunctional Zeolites
12.5 Concluding Remarks
Acknowledgements
References
Chapter 13 Zeolite Membranes in Catalysis
13.1 Introduction
13.2 Zeolite Membranes
13.2.1 Synthesis
13.2.2 Supports
13.2.3 Characterization
13.3 Zeolite Membrane Reactors
13.3.1 Reactor Level
13.3.2 Particle Level
13.3.3 Crystal Level
13.4 Conclusion and Outlook

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