C1: Principles and Processes

Description

Volatility of crude oil prices, depleting reservoirs and environmental concerns have stimulated worldwide research for alternative and sustainable sources of raw materials for chemicals and fuels. The idea of using single-carbon atom molecules as chemical building blocks is not new, and many such compounds have been techno-economically studied as raw materials for fuels. Nevertheless, unifying the scientific and technical issues under the topic of C1 chemistry is not as easy as it may appear. C1 Chemistry: Principles and Processes provides a comprehensive understanding of the chemical transformation from molecular to commercial plant scales and reviews the sources of C1 molecules, their conversion processes and the most recent achievements and research needs. This book: Describes the latest processes developments and introduces commercial technologies Covers a wide range of feedstocks, including greenhouse gases and organic wastes Details chemistry, thermodynamics, catalysis, kinetics and reactors for respective conversions Includes preparation and purification of C1 feedstocks, C1 molecule coupling reactions and process technologies for each C1 conversion reaction Considers environmental impacts and sustainability This book will be of interest to a wide range of researchers, academics, professionals and advanced students working in the chemical, environmental and energy sectors and offers readers insights into the challenges and opportunities in the active field of C1 chemistry. Cover Half Title Title Page Copyright Page Dedication Contents Preface Authors Chapter 1: C1 Chemistry: An Overview 1.1. Introduction 1.2. Definition 1.3. C1 Chemistry Developments and Drivers 1.4. Feedstocks 1.5. Overview of Conversion Technologies 1.6. Conclusions References Chapter 2: C1 Sources 2.1. Introduction 2.2. Natural Gas 2.2.1. Sources 2.2.2. Purification and Processing 2.3. Carbon Dioxide 2.3.1. Sources 2.3.2. CO2 Capture Options 2.3.2.1. Pre-Combustion Capture 2.3.2.2. Post-Combustion Capture 2.3.2.3. Oxy-Fuel Combustion 2.3.3. CO2 Separation Technologies 2.3.3.1. CO2 Separation from Stationary Points 2.3.3.2. CO2 Separation from Ambient Air 2.3.4. CO2 Storage Options 2.3.5. CO2 Utilization Options 2.3.6. Conclusions on Technologies for CO2 Capture 2.4. Coal 2.4.1. Chemical Composition 2.4.2. Gasification 2.4.2.1. Chemistry and Thermodynamics 2.4.2.2. Gasification Catalysts 2.4.2.3. Kinetics 2.4.2.4. Gasifiers 2.4.2.5. Commercial Technologies 2.5. Heavy Oil Residues 2.6. Biomass 2.6.1. Thermochemical Conversions 2.6.1.1. Gasification Models 2.6.1.2. Gasification Technologies for Biomass 2.6.2. Biochemical Conversion 2.7. Conclusions Nomenclature References Chapter 3: C1 Interconversions 3.1. Introduction 3.2. Methane Conversions 3.2.1. Reforming of Methane 3.2.1.1. Steam Reforming of Methane 3.2.1.2. Methane Dry Reforming 3.2.1.3. Partial Oxidation of Methane 3.2.1.4. Combined Reformings 3.2.2. Partial Oxidation to C1 Oxygenates 3.2.2.1. Methane to Formaldehyde 3.2.2.2. Methane to Methanol 3.2.3. Methane Halides 3.2.3.1. Oxidative Halogenation 3.2.3.2. Processes 3.2.4. Sulfurated Methanes 3.2.5. Methane to Hydrogen Cyanide 3.2.5.1. Chemistry of Reaction 3.2.5.2. Processes 3.3. Carbon Dioxide Conversions 3.3.1. Reverse WGS 3.3.1.1. Catalysts 3.3.2. Methanol Synthesis (Conventional) 3.3.2.1. Chemistry 3.3.2.2. Catalysts 3.3.2.3. Processes 3.3.3. Methanol from CO2 Hydrogenation 3.3.3.1. Catalysts 3.3.3.2. Mechanism 3.3.3.3. Commercial Plants 3.4. Concluding Remarks Nomenclature References Chapter 4: Methane Conversions 4.1. Introduction 4.2. Chemistry of Methane 4.3. Non-Oxidative Conversions 4.3.1. High-Temperature Self-Coupling 4.3.1.1. Mechanism 4.3.1.2. Industrial Processes 4.3.2. Two-Step Methane Homologation 4.3.2.1. Catalytic Effects 4.3.2.2. Mechanism 4.3.3. Methane Dehydroaromatization 4.3.3.1. Chemistry and Thermodynamic of Reactions 4.3.3.2. Catalytic Systems 4.3.3.3. Mechanism and Kinetics 4.3.3.4. Reactor Types and Operating Conditions 4.3.3.5. Surface Carbon Species 4.3.3.6. Catalyst Deactivation 4.3.3.7. Coaromatization of Methane 4.3.3.8. Processes 4.4. Oxidative Conversions 4.4.1. Oxidative Coupling of Methane 4.4.1.1. Chemistry of OCM 4.4.1.2. Catalysts 4.4.1.3. Mechanism 4.4.1.4. Reactor Options 4.4.1.5. Reactor Configuration 4.4.1.6. Process 4.4.1.7. Recent Developments 4.4.1.8. Integrating OCM Process with Other Ones 4.5. Concluding Remarks Nomenclature References Chapter 5: Synthesis Gas Chemistry 5.1. Introduction 5.2. Chemical Properties of Carbon Monoxide 5.3. Fischer–Tropsch Synthesis 5.3.1. Catalysts 5.3.1.1. Iron-Based Catalysts 5.3.1.2. Cobalt Catalysts 5.3.1.3. Ruthenium Catalysts 5.3.1.4. Support Effects 5.3.1.5. Comparison 5.3.2. Mechanism and Kinetics 5.3.3. Catalyst Deactivation 5.3.4. Reactor Options 5.3.5. Refining and Upgrading FT Products 5.3.6. Process Technologies 5.4. Modifications of FTS 5.4.1. Kölbel–Engelhardt Process 5.4.2. Isosynthesis 5.4.3. Synthesis of Nitrogen Compounds 5.5. Synthesis of Higher Alcohols 5.5.1. Chemistry and Thermodynamics 5.5.2. Catalysts 5.5.2.1. Modified Methanol Synthesis Catalysts 5.5.2.2. Modified FT Synthesis Catalyst 5.5.2.3. Mo-Based Catalysts 5.5.2.4. Rh-Based Catalysts 5.5.3. Mechanism 5.5.4. Processes 5.6. Synthesis of Ethylene Glycol 5.7. Hydroformylation 5.7.1. Chemistry of Reaction 5.7.2. Catalyst Systems 5.7.3. Reaction Mechanism 5.7.4. Commercial Processes 5.8. Conclusions Nomenclature References Chapter 6: Carbon Dioxide Conversions 6.1. Introduction 6.2. Chemical Utilization Options 6.3. Hydrogenation of Carbon Dioxide 6.3.1. Chemistry 6.3.2. Catalysts 6.3.2.1. Role of Active Site 6.3.2.2. Role of Support 6.3.2.3. Role of the Promoter 6.3.2.4. Role of Binder 6.3.3. Mechanisms 6.3.4. Effect of Reaction Conditions 6.3.4.1. Effect of Space Velocity 6.3.4.2. Effect of Temperature 6.3.4.3. Effect of Pressure 6.3.4.4. Role of the Reactor Type 6.3.5. Catalyst Deactivation 6.3.6. Processes 6.4. Coupling with Olefins 6.5. CO2 to Polymers 6.5.1. Introduction 6.5.2. Polymers Based on CO2-Direct Approach 6.5.2.1. Polycarbonates 6.5.2.2. Polyureas 6.5.2.3. Polyurethanes 6.5.2.4. Polyesters 6.5.2.5. Polyols 6.5.3. Polymers Based on CO2-Indirect Approach 6.5.4. Catalysts 6.5.5. Mechanisms 6.5.5.1. Ring-Opening Copolymerization 6.5.6. Industrial Examples 6.6. Challenges 6.7. Concluding Remarks Nomenclature References Chapter 7: Methanol Conversions 7.1. Introduction 7.2. Chemical Properties of Methanol 7.3. Methanol to Hydrocarbons 7.3.1. Chemistry of MTH 7.3.2. Catalysts 7.3.2.1. Aluminosilicates 7.3.2.2. Silicoaluminophosphates (SAPO) 7.3.3. Mechanisms 7.3.3.1. Oxonium Mechanism 7.3.3.2. Carbocation Mechanism 7.3.3.3. Carbene Mechanism 7.3.3.4. Radical Mechanism 7.3.3.5. Hydrocarbon Pool Mechanism 7.3.3.6. Dual-Cycle Mechanism 7.3.4. Kinetics 7.3.5. Catalyst Deactivation 7.3.6. Catalyst Modifications. 7.3.6.1. Metal Incorporation 7.3.6.2. Introducing Mesoporosity 7.3.6.3. Synthesis of Nanosized SAPO-34 7.3.7. Byproduct Upgrading 7.3.8. Processes 7.3.8.1. MTG Process 7.3.8.2. MTP Process 7.3.8.3. MTO Process 7.3.8.4. MOGD Process 7.3.8.5. GTO Process 7.3.8.6. DMTO Process 7.3.8.7. TIGAS Process 7.3.8.8. DTG Process 7.3.8.9. Others 7.4. Methanol Carbonylation 7.4.1. Reaction Chemistry 7.4.2. Homogeneous Catalytic Systems 7.4.2.1. Catalyst Components 7.4.2.2. Commercial Methanol Carbonylation Processes 7.4.3. Heterogeneous Carbonylation 7.5. Methanol-Based Chemical Industry and Methanol Economy Nomenclature Symbols Greek Symbols References Chapter 8: Methane Derivative Routes 8.1. Introduction 8.2. Hydrocarbons from Methyl Halides 8.2.1. Catalysts 8.2.2. Mechanisms 8.2.3. Catalyst Deactivation 8.2.4. Processes 8.3. Hydrocarbons from Sulfurated Methanes 8.3.1. Catalysts 8.3.2. Mechanism 8.3.3. Catalyst Deactivation 8.3.4. Challenges 8.4. Concluding Remarks Nomenclature References Chapter 9: Outlook and Perspective 9.1. Introduction 9.2. New Feedstocks 9.3. Energy Sources 9.4. Methanol Economy 9.5. Research Needs References Index