Beyond Oil and Gas

George A. Olah obtained his doctorate at the Technical University of Budapest in 1949 and was the Donald P. and Katherine B. Loker Distinguished Professor of Organic Chemistry and Director of the Loker Hydrocarbon Institute at the University of Southern California, USA. He passed away on March 8, 2017. Olah received numerous awards and recognitions worldwide, including memberships in various academies of science and 12 honorary degrees. He had some 1,400 scientific papers, 20 books and more than 140 patents to his name. Professor Olah's research spanned a wide range of synthetic and mechanistic organic chemistry. But most notably, his work on the chemistry of carbocations earned him the 1994 Nobel Prize in Chemistry. Alain Goeppert is a research associate in the groups of Profs. George A. Olah and G. K. Surya Prakash at the Loker Hydrocarbon Research Institute at the University of Southern California, USA, since 2002. After obtaining his diploma in chemistry from the University Robert Schuman in Strasbourg, France, he received his engineering degree from the Fachhochschule Aalen, Germany. He then returned to Strasbourg to obtain his PhD in 2002 under the direction of Prof. Jean Sommer at the Université Louis Pasteur. Dr. Goeppert's current research is focused on the transformation of methane and CO2 into more valuable products and CO2 capture technologies. G. K. Surya Prakash is currently a Professor and Olah Nobel Laureate Chair in Hydrocarbon Chemistry and Scientific Co-Director at the Loker Hydrocarbon Research Institute at University of Southern California, USA. After gaining his bachelor and master degrees from India, he obtained his PhD from the University of Southern California under the direction of Prof. Olah in 1978. Professor Prakash has close to 600 scientific papers, 9 books and 25 patents to his name, and has received many accolades, including two American Chemical Society National Awards. His primary research interests are in superacid, hydrocarbon, synthetic organic & organofluorine chemistry, energy and catalysis areas.

• Preface xiiiAbout the Authors xvAcronyms xvii1 Introduction 12 Coal in the Industrial Revolution and Beyond 133 History of Petroleum Oil and Natural Gas 213.1 Oil Extraction and Exploration 263.2 Natural Gas 27           4 Fossil‐Fuel Resources and Their Use 314.1 Coal 324.2 Petroleum Oil 384.3 Unconventional Oil Sources 434.4 Tar Sands 444.5 Oil Shale 464.6 Light Tight Oil 474.7 Natural Gas 484.8 Coalbed Methane 564.9 Tight Sands and Shales 564.10 Methane Hydrates 574.11 Outlook 605 Oil and Natural Gas Reserves and Their Limits 636 The Continuing Need for Hydrocarbon Fuels and Products 736.1 Fractional Distillation of Oil 776.2 Thermal Cracking and Other Downstream Processes 786.3 Petroleum Products 797 Fossil Fuels and Climate Change 857.1 Mitigation 958 Renewable Energy Sources and Atomic Energy 1018.1 Hydropower 1048.2 Geothermal Energy 1088.3 Wind Energy 1138.4 Solar Energy: Photovoltaic and Thermal 1178.4.1 Electricity from Photovoltaic Conversion 1188.4.2 Solar Thermal Power for Electricity Production 1218.4.3 Electric Power from Saline Solar Ponds 1258.4.4 Solar Thermal Energy for Heating 1258.4.5 Economics of Solar Energy 1268.5 Bioenergy 1278.5.1 Electricity from Biomass 1288.5.2 Liquid Biofuels 1308.5.2.1 Biomethanol 1358.5.3 Advantages and Limitation of Biofuels 1358.6 Ocean Energy: Thermal, Tidal, and Wave Power 1368.6.1 Tidal Energy 1368.6.2 Wave Power 1388.6.3 Ocean Thermal Energy 1398.7 Nuclear Energy 1408.7.1 Energy from Nuclear Fission Reactions 1428.7.2 Breeder Reactors 1468.7.3 The Need for Nuclear Power 1488.7.4 Economics 1498.7.5 Safety 1518.7.6 Radiation Hazards 1538.7.7 Nuclear By‐products, Waste, and Their Management 1548.7.8 Emissions 1568.7.9 Nuclear Fusion 1568.7.10 Nuclear Power: An Energy Source for the Future 1608.8 Future Outlook 1619 The Hydrogen Economy and Its Limitations 1659.1 Hydrogen and Its Properties 1669.2 The Development of Hydrogen Energy 1689.3 Production and Uses of Hydrogen 1719.3.1 Hydrogen from Fossil Fuels 1729.3.2 Hydrogen from Biomass 1749.3.3 Photobiological Water Cleavage and Fermentation 1759.3.4 Water Electrolysis 1759.3.4.1 Electrolyzer Types 1769.3.4.2 Electricity Source 1779.3.5 Hydrogen Production Using Nuclear Energy 1799.4 The Challenge of Hydrogen Storage 1809.4.1 Liquid Hydrogen 1829.4.2 Compressed Hydrogen 1829.4.3 Metal Hydrides and Solid Adsorbents 1849.4.4 Chemical Hydrogen Storage 1859.5 Centralized or Decentralized Distribution of Hydrogen? 1869.6 Hydrogen Safety 1889.7 Hydrogen as a Transportation Fuel 1899.8 Fuel Cells 1919.8.1 History 1919.8.2 Fuel Cell Efficiency 1929.8.3 Hydrogen‐based Fuel Cells 1949.8.4 PEM Fuel Cells for Transportation 1979.8.5 Regenerative Fuel Cells 2009.9 Outlook 20310 The “Methanol Economy”: General Aspects 20511 Methanol and Dimethyl Ether as Fuels and Energy Carriers 21111.1 Background and Properties of Methanol 21111.1.1 Methanol in Nature 21311.1.2 Methanol in Space 21311.2 Chemical Uses of Methanol 21411.3 Methanol as a Transportation Fuel 21611.3.1 Development of Alcohols as Transportation Fuels 21711.3.2 Methanol as a Fuel in Spark Ignition (SI) Engines 22611.3.3 Methanol as a Fuel in Compression Ignition (Diesel) Engines and Methanol Engines 22911.4 Dimethyl Ether as a Transportation Fuel 23211.5 Biodiesel Fuel 23811.6 Advanced Methanol‐powered Vehicles 23811.6.1 Hydrogen for Fuel Cells Based on Methanol Reforming 23911.7 Direct Methanol Fuel Cell (DMFC) 24511.8 Fuel Cells Based on Other Methanol‐derived Fuels and Biofuel Cells 25311.8.1 Regenerative Fuel Cell 25311.9 Methanol and DME as Marine Fuels 25311.10 Methanol for Locomotives and Heavy Equipment 26111.11 Methanol as an Aviation Fuel 26211.12 Methanol for Static Power, Heat Generation, and Cooking 26311.13 DME for Electricity Generation and as a Household Gas 26511.14 Methanol and DME Storage and Distribution 26811.15 Price of Methanol and DME 27111.16 Safety of Methanol and DME 27311.17 Emissions from Methanol‐ and DME‐powered Vehicles and Other Sources 27811.18 Environmental Effects of Methanol and DME 28311.19 The Beneficial Effect of Chemical CO2 Recycling to Methanol on Climate Change 28512 Production of Methanol from Still Available Fossil‐Fuel Resources 28712.1 Methanol from Fossil Fuels 29012.1.1 Production via Syngas 29012.1.2 Syngas from Coal 29412.1.3 Syngas from Natural Gas 29512.1.3.1 Steam Reforming of Methane 29512.1.3.2 Partial Oxidation of Methane 29612.1.3.3 Autothermal Reforming and Combination of Steam Reforming with Partial Oxidation 29612.1.3.4 Syngas from CO2 Reforming of Methane 29712.1.4 Syngas from Petroleum Oil and Higher Hydrocarbons 29712.1.5 Economics of Syngas Generation 29812.1.6 Alternative Syngas Generation Methods 29812.1.6.1 Tri‐reforming of Natural Gas 29812.1.6.2 Bi‐reforming of Methane for Methanol Production 29812.1.6.3 Oxidative Bi‐reforming of Methane for Methanol Production: Methane Oxygenation 30012.1.7 Other High‐Temperature Processes Based on Methane to Convert Carbon Dioxide to Methanol 30012.1.7.1 Carnol Process 30012.1.7.2 Combination of Methane Decomposition with Dry Reforming or Steam Reforming 30212.1.7.3 Addition of CO2 to Syngas from Methane Steam Reforming 30312.1.8 Coal to Methanol Without CO2 Emissions 30312.1.9 Methanol from Syngas Through Methyl Formate 30512.1.10 Methanol from Methane Without Producing Syngas 30612.1.10.1 Direct Oxidation of Methane to Methanol 30612.1.10.2 Catalytic Gas‐Phase Oxidation of Methane 30712.1.10.3 Liquid‐Phase Oxidation of Methane to Methanol 30912.1.10.4 Methane to Methanol Conversion Through Monohalogenated Methanes 31112.1.11 Microbial or Photochemical Conversion of Methane to Methanol 31312.2 Dimethyl Ether Production from Syngas or Carbon Dioxide Using Fossil Fuels 31413 Production of Renewable Methanol and DME from Biomass and Through Carbon Capture and Recycling 31913.1 Biomass‐ and Waste‐Based Methanol and DME – Biomethanol and Bio‐DME 31913.1.1 Gasification 32113.1.1.1 Sources of Heat for the Gasification 32213.1.2 Biocrude 32213.1.3 Combination of Biomass and Coal 32413.1.4 Excess CO2 in the Gas Mixture Derived from Biomass 32413.1.5 Methanol from Biogas 32913.1.6 Limitations of Biomass 33213.1.7 Aquaculture 33513.1.7.1 Water Plants 33613.1.7.2 Algae 33613.2 Chemical Recycling of Carbon Dioxide to Methanol 34013.3 Heterogeneous Catalysts for the Production of Methanol from CO2 and H2 34013.4 Production of DME from CO2 Hydrogenation over Heterogeneous Catalysts 34213.5 Reduction of CO2 to Methanol with Homogeneous Catalysts 34313.6 Practical Applications of CO2 to Methanol 34413.7 Alternative Two‐Step Route for CO2 Hydrogenation to Methanol 34613.8 Where Should the Needed Hydrogen Come From? 34613.9 CO2 Reduction to CO Followed by Hydrogenation 34713.10 Electrochemical Reduction of CO2 34813.10.1 Direct Electrochemical CO2 Reduction to Methanol 34913.10.2 Methods for High‐Rate Electrochemical CO2 Reduction 35013.10.3 Syngas (Metgas) Production from Formic Acid Synthesized by Electrochemical Reduction of CO2 35213.11 Thermochemical and Photochemical Routes to Methanol 35213.11.1 Solar‐Driven Thermochemical Conversion of CO2 to CO for Methanol Synthesis 35213.11.2 Direct Photochemical Reduction of CO2 to Methanol 35413.12 Sources of CO2 35513.12.1 Separating Carbon Dioxide from Industrial and Natural Sources for Chemical Recycling 35613.12.2 CO2 Capture from Seawater 35913.12.3 CO2 Capture from the Air 35913.13 Atmospheric CO2 to Methanol 36313.14 Cost of Producing Methanol from CO2 and Biomass 36513.15 Advantages of Producing Methanol from CO2 and H2 36913.16 Reduction in Greenhouse Gas Emissions 36913.17 Anthropogenic Carbon Cycle 37214 Methanol‐Based Chemicals, Synthetic Hydrocarbons, and Materials 37514.1 Methanol‐Based Chemical Products and Materials 37514.2 Methyl‐tert‐butyl Ether and DME 37714.3 Methanol Conversion to Light Olefins and Synthetic Hydrocarbons 37814.4 Methanol to Olefin (MTO) Processes 38014.5 Methanol to Gasoline (MTG) Processes 38314.6 Methanol‐Based Proteins 38414.7 Plant Growth Promotion 38514.8 Outlook 38615 Conclusion and Outlook 38715.1 Where Do We Stand? 38715.2 The “Methanol Economy”: Progress and Solutions for the Future 390Further Reading and Information 395References 409Index 459