Converting Power into Chemicals and Fuels

Martin Bajus, PhD is Professor of Chemical Technology at the Institute of Organic Chemistry, Catalysis, and Petrochemistry, Slovak University of Technology, Bratislava, Slovak Republic. He founded the Bratislava School of Pyrolysis at the Slovak University of Technology, and has published extensively on energy and petrochemical subjects.

• About the Book xviiPreface xixAcknowledgments xxiiiGeneral Literature xxvNomenclature xxxiAbbreviations and Acronyms xxxiii1 Power-to-Chemical Technology 11.1 Introduction 21.2 Power-to-Chemical Engineering 41.2.1 Carbon Dioxide Thermodynamics 41.2.2 Carbon Dioxide Aromatization Thermodynamics 121.2.3 Reaction Mechanism of Carbon Dioxide Methanation 141.2.4 Water Electrolysis Thermodynamics 181.2.5 Methane Pyrolysis Reaction Thermodynamic Consideration 201.2.5.1 The Carbon-Hydrogen System 201.2.6 Reaction Kinetics and Mechanism 271.2.7 Thermal Mechanism of Methane Pyrolysis into a Sustainable Hydrogen 281.2.8 Catalytic Mechanism Splitting of Methane into a Sustainable Hydrogen 301.2.9 Conversion of Methane over Metal Catalysts into a Sustainable Hydrogen 351.2.9.1 Nickel Catalysts 351.2.9.2 Iron Catalysts 371.2.9.3 Regeneration of Metal Catalysts 391.2.10 Conversion of Methane over Carbon Catalysts into Clean Hydrogen 401.2.10.1 Activity of Carbon Catalysts 401.2.10.2 Stability and Deactivation of Carbon Catalysts 421.2.10.3 Regeneration of Carbon Catalysts 431.2.10.4 Co-Feeding to Extend the Lifetime of Carbon Catalysts 441.2.11 Reactors 441.2.11.1 Conversion, Selectivity and Yields 441.2.11.2 Modelling Approach of the Structured Catalytic Reactors 451.2.11.3 Reactor Concept for Catalytic Carbon Dioxide Methanation 461.2.11.4 Monolithic Reactors 481.2.11.5 Mass Transfer in the Honeycomb and Slurry Bubble Column Reactor 491.2.11.6 Heat Transfer in Honeycomb and Slurry Bubble Column Reactors 501.2.11.7 Process Design 511.2.11.8 Comparison and Outlook 521.3 Potential Steps Towards Sustainable Hydrocarbon Technology: Vision and Trends 531.3.1 Technology Readiness Levels 541.3.2 A Vision for the Oil Refinery of 2030 591.3.3 The Transition from Fuels to Chemicals 601.3.3.1 Crude Oil to Chemicals Investments 661.3.3.2 Available Crude-to-Chemicals Routes 671.3.4 Business Trends: Petrochemicals 2025 671.3.4.1 Asia-Pacific 691.3.4.2 Middle East 701.3.4.3 United States 701.4 Digital Transformation 711.4.1 Benefits of Digital Transformation 711.4.2 A New Workforce and Workplace 721.4.3 Technology Investment 731.4.4 The Greening of the Downstream Industry 741.4.4.1 Sustainable Alkylation Technology 751.4.4.2 Ecofriendly Catalyst 751.5 RAM Modelling 761.5.1 RAM1 Site Model 771.5.2 RAM2 Plant Models 771.5.3 RAM3 Models 781.5.4 RAM Modelling Benefit 781.6 Conclusions 78Further Reading 802 The Green Shift in Power-to-Chemical Technology and Power-to-Chemical Engineering: A Framework for a Sustainable Future 852.1 Introduction 862.2 Eco-Friendly Catalyst 872.2.1 Development of Catalysts Supported on Carbons for Carbon Dioxide Hydrogenation 882.2.2 Properties of Carbon Supports 892.3 Hydrogen 912.3.1 Different Colours and Costs of Hydrogen 922.3.1.1 Blue Hydrogen 922.3.1.2 Green Hydrogen 922.3.1.3 Grey Hydrogen 932.3.1.4 Pink Hydrogen 932.3.1.5 Yellow Hydrogen 932.3.1.6 Multi-Coloured Hydrogen 932.3.1.7 Hydrogen Cost 932.4 Alternative Feedstocks 952.4.1 Carbon Dioxide-Derived Chemicals 952.5 Alternative Power-to-X-Technology 972.5.1 Power-to-X-Technology to Produce Electrochemicals and Electrofuels 972.6 Partial Oxidation of Methane 992.7 Biorefining 992.8 Sustainable Production to Advance the Circular Economy 1002.8.1 Introduction 1002.8.2 Circular Economy 1012.8.2.1 Sustainability 1012.8.2.2 Scope 1012.8.2.3 Background of the Circular Economy 1022.8.2.3.1 Emergence of the Idea 1022.8.2.3.2 Moving Away from the Linear Model 1032.8.2.3.3 Towards the Circular Economy 1032.8.3 Circular Business Models 1032.8.4 Industries Adopting a Circular Economy 1042.8.4.1 Minimizing Dependence on Fossil Fuels 1042.8.4.2 Minimizing the Impact of Chemical Synthesis and Manufacturing 1052.8.4.3 Future Research Needs in Developing a Circular Economy 1062.9 New Chemical Technologies 1062.9.1 Renewable Power 107Further Reading 1083 Storage Renewable Power-to-Chemicals 1133.1 Introduction 1133.2 Terminology 1183.3 Energy Storage Systems 1193.4 World Primary Energy Consumption 1263.4.1 2019 Briefly 1263.4.2 Energy in 2020 1283.4.2.1 Not Just Green but Greening 1283.4.2.2 For Energy, 2020 Was a Year Like No Other 1293.4.2.3 Glasgow Climate Pact 1293.4.2.4 Energy in 2020: What Happened and How Surprising Was It 1313.4.2.5 How Should We Think About These Reductions 1313.4.2.6 What Can We Learn from the COVID-induced Stress Test 1333.4.2.7 Progress Since Paris – How Is the World Doing 1343.5 Carbon Dioxide Emissions 1353.5.1 Carbon Footprint 1363.5.1.1 Climate-driven Warming 1373.5.2 Carbon Emissions in 2020 1383.6 Clean Fuels ‒ the Advancement to Zero Sulfur 1393.7 Renewables in 2019 1403.8 Hydroelectricity and Nuclear Energy 1413.9 Conclusion 141Further Reading 1424 Carbon Capture, Utilization and Storage Technologies 1454.1 Industrial Sources of Carbon Dioxide 1454.2 Carbon Capture, Utilization and Storage Technologies 1474.3 Carbon Dioxide Capture 1474.4 Developing and Deploying CCUS Technology in the Oil and Gas Industry 1554.5 Sustainable Steel/Chemicals Production: Capturing the Carbon in the Material Value Chain 1584.5.1 Valorisation of Steel Mill Gases 1584.5.2 Summary and Outlook 161Further Reading 1625 Integrated Refinery Petrochemical Complexes Including Power-to-X Technologies 1655.1 Introduction 1655.2 Synergies Between Refining and Petrochemical Assets 1675.2.1 Reaching Maximum Added Value – Integrated Refining Schemes 1685.2.1.1 Fluid Catalytic Cracking Alternates 1685.2.1.2 Hydrocracking Alternates 1705.2.2 Comparisons and Sensitivities to Product/Utility Pricing 1725.2.3 Options for Further Increasing the Petrochemical Value Chain 1745.3 Carbon Dioxide Emissions 1755.3.1 Effect of a Carbon Dioxide Tax 1765.3.2 Crude Oil Effects 1795.4 Summary 1805.5 Power- to-X Technology 1815.6 The Role of Nuclear Power 1855.6.1 Small Nuclear Power Reactors 1875.6.2 Conclusion 187Further Reading 1886 Power-to-Hydrogen Technology 1916.1 Introduction 1926.2 Traditional and Developing Technologies for Hydrogen Production 1936.3 Dry Reforming of Methane 1956.4 Tri-reforming of Methane 1976.5 Greenfield Technology Option → Low Carbon Emission Routes 1986.5.1 Water Electrolysis 2016.5.1.1 Alkaline Electrolysis 2026.5.1.2 Polymer Electrolyte Membrane Electrolysis 2036.5.1.3 Solid Oxide Electrolysis 2046.5.2 Methane Pyrolysis 2076.5.2.1 Process Concepts for Industrial Application 2086.5.2.2 Perspectives of the Carbon Coproduct 2116.5.3 Thermochemical Processes 2136.5.4 Photocatalytic Processes 2136.5.5 Biomass Electro-Reforming 2146.5.6 Microorganisms 2156.5.7 Hydrogen from Other Industrial Processes 2156.5.8 Hydrogen Production Cost 2156.5.9 Electrolysers 2156.5.10 Carbon Footprint 2166.6 Advances in Chemical Carriers for Hydrogen 2166.6.1 Demand Drivers 2176.6.2 Options for Hydrogen Deployment 2186.6.3 Advances in Hydrogen Storage/Transport Technology 2186.6.4 Global Supply Chain 2206.6.5 Power-to-Gas Demo 2206.6.5.1 Hydrogen Fuelling Stations 2216.6.5.2 Pathway to Commercialization 2216.6.5.3 Transportation Studies in North America 2216.6.6 Future Applications 2226.7 Ammonia Fuel Cells 2236.7.1 Proton-Conducting Fuel Cells 2236.7.2 Polymer Electrolyte Membrane Fuel Cells 2246.7.3 Proton-conducting Solid Oxide Fuel Cells 2246.7.4 Alkaline Fuel Cells 2256.7.5 Direct Ammonia Solid Oxide Fuel Cell 2266.7.6 Equilibrium Potential and Efficiency of the Ammonia-Fed SOFC 2276.8 Conclusions 228Further Reading 2287 Power-to-Fuels 2337.1 Introduction 2347.2 Selection of Fuel Candidates 2407.2.1 Fuel Production Processes 2417.3 Power-to-Methane Technology 2427.3.1 Carbon Dioxide Electrochemical Reduction 2427.3.2 Carbon Dioxide Hydrogenation 2447.4 Power-to-Methanol 2487.5 Power-to-Dimethyl Ether 2497.6 Chemical Conversion Efficiency 2507.6.1 Exergy 2507.6.2 Exergy Efficiency 2517.6.3 Economic and Environmental Evaluation 2517.6.4 Fuel Assessment 2527.6.5 Performance of Fuel Production Processes 2537.6.6 Process Chain Evaluation 2547.6.7 Fuel Cost 2557.7 Well-to-Wheel Greenhouse Gas Emissions 2577.7.1 Environmental Impact 2587.7.2 Infrastructure 2587.7.3 Efficiency 2597.7.4 Energy/Power Density 2597.7.5 Pollutant Emissions 2607.8 Gasoline Electrofuels 2607.9 Diesel Electrofuels 2617.10 Electrofuels and/or Electrochemicals 2637.10.1 Physico-Chemical Properties 2647.10.1.1 Density 2647.10.1.2 Tribological Properties 2647.10.1.3 Combustion Characteristics 2657.10.1.4 Combustion and Emissions 2677.10.2 Diesel Engine Efficiency 2697.10.3 Potential of Diesel Electrofuels 2697.11 Maturity, TRL, Production and Electrolysis Costs 2717.11.1 Summary 2737.12 Power-to-Liquid Technology 2747.12.1 Power-to-Jet Fuel 2757.12.2 Power-to-Diesel 2767.13 Conclusion and Outlook 276Further Reading 2788 Power-to-Light Alkenes 2838.1 Oxidative Dehydrogenation 2838.1.1 Carbon Dioxide as a Soft Oxidant for Catalytic Dehydrogenation 2838.1.2 Carbon Dioxide: Oxidative Coupling of Methane 2858.1.3 From Carbon Dioxide to Lower Olefins 2898.1.4 Low-Carbon Production of Ethylene and Propylene 2918.1.4.1 Energy Demand per Unit of Ethylene/Propylene Production via Methanol 2928.1.4.2 Carbon Dioxide Reduction per Unit of Ethylene/Propylene Production 2928.1.4.3 Economics of Low-Carbon Ethylene and Propylene Production 2938.2 Life Cycle Assessment 2938.2.1 Small-Scale Production of Ethylene 2938.3 Polymerization Reaction 2948.3.1 Carbon Dioxide-Based Polymers 2948.3.1.1 Perspective and Practical Applications 298Further Reading 2999 Power-to-BTX Aromatics 3019.1 Low-Carbon Production of Aromatics 3019.1.1 Methanol to Aromatics Process 3039.1.1.1 ZSM-5 Catalyst 3049.1.1.2 Process Variables 3059.1.1.3 Kinetic Modelling 3069.1.1.4 Aromatics via Hydrogen-Based Methanol (TRL7) 3079.1.1.5 Energy Demand per Unit of Low-Carbon BTX Production 3089.1.1.6 Carbon Dioxide Reduction 3089.1.1.7 Economics of Low-Carbon BTX Production 3089.2 Production of p-Xylene from 2,5-Dimethylfuran and Ethylene 3089.3 Carbon Dioxide Dehydrogenation of Ethylbenzene to Styrene 309Further Reading 31010 Power-to-C 1 Chemicals 31310.1 Introduction 31410.2 Carbon Dioxide Utilization into Chemical Technology 31710.3 Mechanism of Conversion of Carbon Dioxide 31810.4 Hydrogenation of Carbon Dioxide 31910.4.1 Heterogeneous Hydrogenation 31910.4.2 Homogeneous Hydrogenation 32310.5 Electrochemical Conversion of Carbon Dioxide into Valuable Chemicals 32410.5.1 Technologies Available for Carbon Dioxide Reduction 32510.6 Electrochemical Technologies 32610.6.1 Roles of Ionic Liquids on Electrochemical Carbon Dioxide Reduction Promotion 32810.6.2 Ionic Liquids as Absorbent for Carbon Dioxide Capture 32810.6.3 Classification of the Electrode Material 32810.6.4 High Hydrogen Evolution Overvoltage Metal 32910.6.5 Low Hydrogen Evolution Overvoltage Metals 32910.6.6 Copper Electrodes 32910.6.7 Other Electrodes for Carbon Dioxide Reduction 33010.7 Power-to-Methanol Technology 33110.7.1 Carbon Dioxide Electrochemical Reduction 33210.7.2 Direct Carbon Dioxide Hydrogenation into Methanol 33410.7.3 Low-Carbon Methanol Production 33610.7.4 Energy Demand 33710.8 Power-to-Formic Acid Technology 33710.8.1 Carbon Dioxide Electrochemical Reduction 33810.8.2 Carbon Dioxide Hydrogenation 33910.9 Power-to-Formaldehyde Technology 34110.9.1 Carbon Dioxide Electrochemical Reduction 34210.9.2 Carbon Dioxide Hydrogenation 34210.10 Selective Hydrogenation of Carbon Dioxide to Light Olefins 34310.10.1 Introduction 34310.10.2 Carbon Dioxide via FTS to Lower Olefins 34510.10.3 Methane via FTS to Lower Olefins 34710.10.4 Carbon Dioxide via FTS to Liquid iso-C 5 -C 13 -Alkanes 34910.10.4.1 Power-to-Liquids 35210.10.4.2 Energy Demand per Unit of Synthetic Fuel Production 35210.10.4.3 Carbon Dioxide Reduction per Unit of Synthetic Fuel Production 35310.10.4.4 Economics 35310.10.4.5 Comparison of the Hydrogen-Based Low-Carbon Synthesis Routes 35310.11 Electrochemical Reduction of Carbon Dioxide to Oxalic Acid 35410.11.1 Process Design and Modelling 35510.11.2 Carbon Dioxide Absorption in Propylene Carbonate 356Further Reading 35611 Power-to-Green Chemicals 36311.1 Introduction 36411.2 Biomethanol Production 36511.2.1 Biomethanol Production Process 36511.2.2 Energy and Feedstock Demand per Unit of Biomethanol Production 36611.2.3 Carbon Dioxide Reduction per Unit of Biomethanol Production 36711.2.4 Economics of Biomethanol Production 36711.3 Bioethanol Production 36711.3.1 Bioethanol Production Process 36811.3.2 Energy and Feedstock Demand per Unit of Bioethanol Production 36911.3.3 Carbon Dioxide Reduction per Unit of Bioethanol Production 37011.3.4 Carbon Dioxide Reduction for (Partially) Replacing Gasoline with Bioethanol 37011.3.5 Economics of Bioethanol Production 37011.4 Bioethylene Production 37111.4.1 Bioethylene Production Process 37111.4.2 Energy and Feedstock Demand per Unit of Bioethylene Production 37111.4.3 Carbon Dioxide Reduction per Unit of Bioethylene Production 37111.4.4 Economics of Bioethylene Production 37211.5 Biopropylene Production 37211.5.1 Biopropylene Production Processes 37211.5.2 Energy and Feedstock Demand per Unit of Biopropylene Production 37211.5.3 Carbon Dioxide Reduction per Unit of Biopropylene Production 37311.6 BTX Production from Biomass 37311.6.1 BTX Production Process 37311.6.2 Energy and Feedstock Demand per Unit of BTX Production from Biomass 37411.6.3 Carbon Dioxide Emissions per Unit of BTX Production from Biomass 37411.7 Comparison of the Biomass-Based Synthesis Routes 37411.8 Biofuels 37611.8.1 Biodiesel Production 37711.8.2 Purification of Glycerol 37911.8.3 Conversion of Glycerol into Valuable Products 38011.8.3.1 Solketal Synthesis Process 38211.8.3.2 Reaction Mechanism 38311.8.3.3 Kinetics of Reaction 38411.8.3.4 Catalyst Design 38511.8.3.5 Batch Process 38711.8.3.6 Continuous Process 38811.8.4 Current Issues and Challenges 38911.8.5 Future Recommendation 39111.8.6 Conclusion 39111.9 Higher Alcohols and Ether Biofuels 39211.9.1 Fuel Production Routes and Sustainability 39311.9.2 Lignin 39411.9.3 Fuel Properties 39411.9.4 Concluding Remarks 39611.10 Biofuels in the World: Biogasoline and Biodiesel 396Further Reading 39912 Industrial Small Reactors 40512.1 Introduction 40512.2 Thermochemical Water Splitting 40612.3 Small Modular Reactors 40712.4 Nuclear Process Heat for Industry 41012.4.1 High-temperature Reactors for Process Heat 41012.4.2 Recovery of Oil from Tar Sands 41312.4.3 Oil Refining 41412.4.4 Coal and Its Liquefaction 41412.4.5 Biomass-Based Ethanol Production 41512.4.6 District Heating 41612.5 Microchannel Reduction Cell 41612.6 Conversion of Carbon Dioxide to Graphene 41712.7 The Ammonia Synthesis Reactor-Development of Small-scale Plants 419Further Reading 42113 Recycling of Waste Plastics → Plastics Circularity 42313.1 Introduction 42413.2 Mechanism Aspects of Waste Plastic Pyrolysis 42613.2.1 Polyethylene and Polypropylene 42813.2.2 Polyethylene Terephthalate 42913.2.3 Polyvinyl Chloride 43013.2.4 Polystyrene 43113.2.5 Poly (Methyl Methacrylate) 43213.3 Kinetics 43313.4 Catalysts 43413.4.1 Zeolites 43413.4.2 Fluid Catalytic Cracking Catalysts 43413.5 Parameters Affecting Pyrolysis 43613.5.1 Type of Plastic Feed 43613.5.2 Temperature and Residence Time 43713.5.3 Pressure 43813.6 Type of Reactors 43813.6.1 Rotary Kiln Reactor 43813.6.2 Screw Feed (Auger) Reactor 43913.6.3 Fluid Catalytic Cracking Reactor 44013.6.4 Stirred-Tank Reactor 44013.6.5 Plasma Pyrolysis Reactor 44113.6.6 Batch Reactor 44213.6.7 Fixed Bed Reactor 44213.6.8 Fluidized Bed Reactor 44313.6.9 Conical Spouted Bed Reactor 44313.6.10 Microwave Reactor 44413.6.11 Pyrolysis in Supercritical Water 44513.7 Applications of Pyrolysis Products 44613.7.1 Pyrolysis Gases → Hydrogen and Methane 44613.7.2 Pyrolysis Oil → Aromatics and Diesel Fuels 44613.7.3 Pyrolysis Char → Nanotubes 449Further Reading 450Index 455