Direct Natural Gas Conversion to Value-Added Chemicals

Cover
Half Title
Title Page
Copyright Page
Table of Contents
Preface
Editors
List of Contributors
Chapter 1 Electrochemical Conversion of Natural Gas to Value Added Chemicals
1.1 Introduction
1.2 Electrochemical Direct Conversion of Methane
1.2.1 Electrochemical Methane Coupling to Produce Ethylene
1.2.1.1 Electrochemical Oxidative Methane Coupling (EOMC)
1.2.1.2 Electrochemical Nonoxidative Methane Coupling (ENMC)
1.2.2 Electrochemical Methane Dehydro-Aromatization (EDMA)
1.3 Electrochemical Direct Conversion of Ethane
1.3.1 Electrochemical Oxidative Dehydrogenation (EODH)
1.3.2 Electrochemical Nonoxidative Dehydrogenation (ENDH)
1.4 Electrochemical Direct Conversion of Propane
1.5 Challenges and Opportunities
Acknowledgments
References
Chapter 2 Microwaves in Nonoxidative Conversion of Natural Gas to Value-Added Products
2.1 Introduction
2.2 Basic Microwave Heating Theory
2.2.1 Electromagnetic Waves
2.2.2 Interaction between Electromagnetic Fields and Dielectric Materials
2.2.3 Measurement of Electromagnetic Properties
2.2.4 Transmission-Reflection Line Method
2.2.5 Cavity Perturbation Method
2.2.6 Advantages of Microwave over Conventional Heating
2.2.6.1 Internal Heating, Rapid Heating, and Selective Heating
2.2.6.2 Controllable Field Distributions
2.3 Microwave Reactor Designs
2.3.1 Microwave Source
2.3.2 E-H Tuners
2.3.3 Waveguide Cavity
2.3.4 Sliding Short
2.3.5 Temperature Measurement
2.4 Microwave-Assisted Dry Methane Reforming (DMR)
2.4.1 Background
2.4.2 Reaction Chemistry
2.5 Microwave-Assisted Dehydroaromatization of Natural Gas
2.6 Microwave-Assisted Ammonia Synthesis from Methane and Nitrogen
2.6.1 Background
2.6.2 Reaction Chemistry of Ammonia Synthesis from Methane and Nitrogen
2.6.2.1 Reaction in Thermally Heated Fixed-Bed Reactor
2.6.2.2 Reaction under Microwave Plasma without Catalyst
2.6.2.3 Reaction in Microwave-Heated Fixed-Bed Reactor
2.7 Numerical Modeling of Microwave–Material Interaction: Microwave-Assisted Methane Decomposition Example
2.8 Conclusions
References
Chapter 3 Nonthermal Plasma Conversion of Natural Gas to Oxygenates
3.1 Introduction
3.2 Methane Reforming
3.2.1 Direct Synthesis of Methanol from Methane
3.2.2 Conventional Methane Reforming
3.3 Plasmas for Fuel Conversion
3.3.1 General
3.3.2 Dielectric Barrier Discharge
3.3.3 Thermal Catalysis versus Nonthermal Plasma Catalysis of Methane
3.4 Methane Conversion Using Microplasma
3.5 Results and Discussion
3.5.1 Effect of Reaction Temperature on Methanol Selectivity
3.5.2 Syngas Generation via Direct Route
3.5.3 Methane Conversion and Product Selectivity
3.6 Reaction Mechanism
3.6.1 Interaction of DBD and Liquid
3.6.2 Mechanism of Low-Temperature Methane Oxidation
3.6.3 Gas Phase Reaction Model
3.7 Conclusions
References
Chapter 4 Natural Gas Conversion to Olefins via Chemical Looping
4.1 Introduction
4.2 Chemical Looping – The General Approach
4.3 Chemical Looping Conversion of Shale Gas to Light Olefins
4.3.1 Methane-Based Olefin Production
4.3.1.1 Chemical Looping – Oxidative Coupling of Methane
4.3.1.2 Chemical Looping – Partial Oxidation or Reforming of Methane
4.3.2 Ethane- and Propane-Based Olefin Production via Chemical Looping
4.3.2.1 Chemical Looping Oxidative Dehydrogenation of Ethane
4.3.2.2 Chemical Looping Oxidative Dehydrogenation of Propane
4.3.3 Naphtha-Based Ethylene Production
4.4 Chemical Looping Light Olefin Production – Advantages and Potential Opportunities
4.5 Summary
References
Chapter 5 Oxidative Coupling of Methane
Abbreviations
5.1 Introduction
5.1.1 Natural Gas and Methane as Feedstocks for Ethylene Production
5.1.2 Evolution of Understanding of Oxidative Coupling of Methane
5.1.2.1 Reactions, Important Aspects, and Performance Indicators
5.1.2.2 Limitations of Catalysts, Reactors, and Process Performance
5.1.2.3 Highest Impact Parameters in a Practically Relevant Analysis Context
5.1.3 Remarks and Conclusions for Structuring This Chapter
5.2 Catalyst Research
5.2.1 Selecting Active Components for OCM Catalysts
5.2.2 Selecting Dopants and Promotors for OCM Catalysts
5.2.3 Impacts of Support on the Performance of OCM Catalysts
5.2.4 Interactive Effects on the Performance of OCM Catalysts
5.2.5 Efficient Characterizations Strategy for Systematic Analysis of the OCM Catalyst Performance
5.2.5.1 Comprehensive Analysis of an Mn-Na2WO4/SiO2 Catalyst
5.2.5.2 General Conclusions Based on Catalyst Material-Chemical-Structural Characteristics
5.2.6 OCM Kinetic Analysis
5.3 Reactor Research
5.3.1 Fixed-Bed Reactor
5.3.2 Membrane Reactor
5.3.3 Fluidized-Bed Reactor
5.3.4 Other Types of OCM Reactors and General Design and Control Aspects
5.4 Interaction of the Catalyst and Reactor Research
5.4.1 Operating Parameters
5.4.1.1 Critical Importance of Pressure
5.4.1.2 Methane-to-Oxygen Ratio
5.4.1.3 Reactor Temperature
5.4.1.4 Feed Flow or Gas Hourly Space Velocity (GHSV)
5.4.1.5 Gas Dilution/Inert
5.4.2 Thermal-Reaction Analysis
5.4.2.1 Stable, Transient, and Dynamic Behavior of OCM Reactors
5.5 Process and Reactor Integration, Environmental, and Industrial Prospects
5.5.1 Integration Potentials of OCM Reactors and other Reaction Systems
5.5.2 Process Integration via Downstream Units
5.5.3 Techno-Economic Analysis of Stand-Alone and Integrated OCM Processes
5.5.4 Priorities for Future Research
Acknowledgments
References
Chapter 6 Direct Natural Gas Conversion to Oxygenates
6.1 Introduction
6.2 Challenges in Methane Activation and Functionalization
6.3 Direct Methane Oxidation to C1-Oxygenates
6.3.1 Criteria to Classify the Direct Methane Oxidation Processes
6.3.2 Nature of Oxidants
6.4 Noncatalyzed and Catalyzed Direct Partial Oxidation of Methane to Oxygenates
6.4.1 Homogeneous (Noncatalyzed) Direct Partial Oxidation of Methane to Oxygenates
6.4.1.1 Reactor Wall Material
6.4.1.2 Reaction Conditions
6.4.1.3 Additives (Reaction Initiators)
6.4.2 Catalyzed Direct Oxidation of Methane to C1-Oxygenates
6.4.2.1 Homogeneous (Nonsolid) Catalyzed Direct Oxidation
6.4.2.2 Solid-Catalyzed Direct Oxidation
6.5 Direct Methane Oxidation to Higher Oxygenates
6.6 Conclusions and Outlook
References
Chapter 7 Hydrogen and Solid Carbon Products from Natural Gas: A Review of Process Requirements, Current Technologies, Market Analysis, and Preliminary Techno Economic Assessment
7.1 Introduction
7.1.1 Steam-Methane Reforming
7.1.2 Steam-Methane Reforming with Carbon Capture
7.1.3 Methane Pyrolysis
7.2 Engineering Review
7.2.1 Thermal (Noncatalytic) Reactions
7.2.2 Catalytic Reactions
7.2.2.1 Catalytic Reactors Types
7.2.2.2 Catalysts
7.2.2.3 Catalyst Regeneration
7.2.3 Plasma Reactions
7.2.4 Separations Required
7.3 Process Technologies
7.3.1 Thermal Catalytic Processes
7.3.2 Concentrated Solar Power
7.3.3 Plasma Processes
7.3.4 Chemical Processes for Decomposing Methane
7.4 Market – Current and New Opportunities
7.4.1 Current Markets
7.4.1.1 Natural Gas
7.4.1.2 Hydrogen
7.4.1.3 Carbon
7.4.2 New Market Opportunities for Methane Conversion to Carbon and Hydrogen
7.4.2.1 Graphite/Graphene
7.4.2.2 Carbon Fibers
7.4.2.3 Carbon Nanotubes
7.4.2.4 Needle Coke
7.5 Techno-Economic Assessment
7.5.1 Break-Even Price of Carbon Products versus the Cost of Methane
7.5.2 ASPEN Process Modeling and Economic Analysis
7.6 Technology Barriers to Commercial Implementation and R&D Opportunities
7.7 Conclusions
Acknowledgments
References
Chapter 8 Methane Conversion on Single-Atom Catalysts
8.1 Introduction
8.2 Methane to Methanol over the SACs by Thermal Catalysis
8.2.1 Base Metal SACs
8.2.1.1 Zeolite-Supported Base Metal SACs
8.2.1.2 MOF-Supported Base Metal SACs
8.2.1.3 Two-Dimensional Materials Supported Base Metal SACs
8.2.1.4 Other Supports
8.2.2 Precious Metal SACs
8.2.2.1 Rh SACs
8.2.2.2 Other Precious Metal SACs
8.3 Methane to Methanol over the SACs by Nonthermal Catalysis
8.4 Conclusions
Acknowledgements
References
Chapter 9 Active Sites in Mo/HZSM-5 Catalysts for Nonoxidative Methane Dehydroaromatization
9.1 Introduction
9.2 Thermodynamics and Reactivity
9.3 Generation of the Active Sites
9.4 Nature of the Active Sites
9.5 Conclusions
References
Chapter 10 Natural Gas Dehydroaromatization
10.1 Introduction
10.2 Thermodynamics of Methane Activation
10.3 Structure and Properties of Zeolites Used for Methane Activation
10.4 Dehydroaromatization of Methane
10.4.1 Nonoxidative Conversion of Methane over Metal-Based Catalyst
10.4.1.1 Mo-Based Catalysts
10.4.1.2 Zn-Based Catalysts
10.4.1.3 Transitional Metal Catalysts
10.4.1.4 Effect of Promoters
10.4.1.5 Addition of Other Hydrocarbons
10.4.2 Interaction of Methane with Different Catalyst Supports (Silica, Alumina, and H-ZSM-5)
10.4.3 Formation and Nature of Active Sites
10.4.4 Induction Period of Methane Dehydroaromatization Reaction
10.4.5 The Role of Brønsted Acid Sites
10.4.6 The Nature of the Carbonaceous Deposit and Its Role in the Reaction
10.4.7 Plasma Catalysis for Methane Activation
10.5 Conclusions
References
Chapter 11 Multifunctional Reactors for Direct Nonoxidative Methane Conversion
11.1 Introduction
11.1.1 Natural Gas as an Alternative to Crude Oil
11.1.2 Gas-to-Liquid Conversion Pathways in Natural Gas Upgrading
11.1.3 Challenges in Direct Nonoxidative Methane Conversion
11.2 Membrane Reactor for Nonoxidative Methane Conversion
11.2.1 Hydrogen-Permeable Membrane Reactor
11.2.1.1 DNMC in Pd-Based Membrane Reactors
11.2.1.2 DNMC in Ceramic Membrane Reactors
11.2.2 Oxygen-Permeable Membrane Reactors
11.2.3 Membrane Reactor Coupled with External Circuit
11.3 Catalytic Wall Reactor for Direct Nonoxidative Methane Conversion
11.3.1 Catalytic Wall Reactor for Autothermal Operation
11.3.2 Direct Nonoxidative Methane Conversion in Catalytic Wall Reactor
11.4 Summary
References
Chapter 12 Homogeneous Methane Functionalization
12.1 Introduction
12.2 Organization Structure
12.2.1 Organization Based on Practical Considerations
12.2.2 Organization Based on Mechanistic Considerations
12.2.2.1 Classification Details of Mechanistic Considerations
12.3 H2SO4/SO3 Systems for Methane Oxidation
12.4 CHA1 Catalytic Systems That Utilize O2/O2-Regenerable Oxidants and Operate by Nonchain, CH Activation Reactions
12.4.1 Platinum Systems
12.4.2 Mercury Systems
12.4.3 Palladium Systems
12.4.4 Rhodium Systems
12.4.5 Iodine Systems
12.5 CHA2 Stoichiometric Systems That Utilize O2/O2-Regenerable Oxidants and Operate by Nonchain, CH Activation Reactions
12.5.1 Mercury Systems
12.5.2 Palladium Systems
12.5.3 Antimony Systems
12.6 CHO1 Catalytic Systems That Utilize O2/O2-Regenerable Oxidants and Operate by Nonchain, CH Oxidation Reactions
12.6.1 Europium Systems
12.6.2 Ruthenium Systems
12.7 CHO2 Stoichiometric Systems That Utilize O2/O2-Regenerable Oxidants and Operate by Nonchain, CH Oxidation Reactions
12.8 Summary and Conclusions
Acknowledgments
Associated Content
References
Chapter 13 3D Printed Immobilized Biocatalysts for Conversion of Methane
13.1 Introduction
13.2 Current Limitations of Gas-to-Liquid Biocatalysis
13.3 Biocatalyst Immobilization
13.3.1 Surface Immobilization Techniques
13.3.2 Entrapment or Encapsulation
13.4 Additive Manufacturing for Bioreactor Design
13.4.1 Types of 3D Bioprinting
13.4.1.1 Photostereolithography
13.4.1.2 Extrusion-Based Bioprinting
13.4.1.3 Droplet-Based Bioprinting
13.4.2 3D Printing Reactors for Biocatalysis
13.5 Conclusions and Future Perspectives
Acknowledgments
References
Chapter 14 Biological Conversion of Natural Gas
14.1 Introduction
14.2 Methanotrophs and Their Biocatalytic Properties
14.3 Methanotrophic Resilience to Toxic Compounds
14.4 Culture Conditions for Natural Gas Bioconversion
14.5 Current Applications
14.6 Final Remarks
Acknowledgments
References
Chapter 15 System Integration Approaches in Natural Gas Conversion
15.1 Introduction
15.2 Flowsheet Synthesis and Analysis
15.3 Process Integration and Multicriteria Decision Making
15.4 Modular Process Integration
15.5 Integration of Shale-Gas Monetization into Industrial Symbiosis
15.6 Synergism between Systems Integration and Experimental Work
15.7 Conclusions
References
Chapter 16 Techno-Economic Analysis of Microwave-Assisted Conversion Processes: Application to a Direct Natural Gas-to-Aromatics Process
16.1 Introduction
16.2 Design of MW Reactors
16.3 MW Scale-Up Challenges and Alternatives
16.4 Natural Gas Conversion to Hydrocarbons
16.5 Direct Nonoxidative Conversion of Natural Gas to Aromatics: Plant-Wide Modeling and Techno-Economic Analysis
16.6 Conclusions
References
Index