Completely revised and updated, the third edition of this bestseller discusses the concept and ongoing development of using methanol and derived dimethyl ether as a transportation fuel, energy storage medium, and as a chemical raw material to replace fossil fuels.
The contents have been expanded by 35% with new and up to date coverage on energy storage, methanol from biomass and waste products, as well as on carbon dioxide capture and recycling. Written by the late Nobel laureate George Olah, Alain Goeppert and G. K. Surya Prakash, this is an inspiring read for anyone concerned with the major challenge posed by environmental problems including global warming and ocean acidification due to massive increase in fossil fuel use. The book provides a comprehensive and sustainable solution to replace fossil fuels in the long run by chemical recycling of carbon dioxide through renewable methanol utilizing alternative energy sources such as solar, wind, hydro, geothermal and nuclear. The Methanol Economy is being progressively implemented in many parts of the world.
Preface xiii About the Authors xv Acronyms xvii 1 Introduction 1 2 Coal in the Industrial Revolution and Beyond 13 3 History of Petroleum Oil and Natural Gas 21 3.1 Oil Extraction and Exploration 26 3.2 Natural Gas 27 4 Fossil‐Fuel Resources and Their Use 31 4.1 Coal 32 4.2 Petroleum Oil 38 4.3 Unconventional Oil Sources 43 4.4 Tar Sands 44 4.5 Oil Shale 46 4.6 Light Tight Oil 47 4.7 Natural Gas 48 4.8 Coalbed Methane 56 4.9 Tight Sands and Shales 56 4.10 Methane Hydrates 57 4.11 Outlook 60 5 Oil and Natural Gas Reserves and Their Limits 63 6 The Continuing Need for Hydrocarbon Fuels and Products 73 6.1 Fractional Distillation of Oil 77 6.2 Thermal Cracking and Other Downstream Processes 78 6.3 Petroleum Products 79 7 Fossil Fuels and Climate Change 85 7.1 Mitigation 95 8 Renewable Energy Sources and Atomic Energy 101 8.1 Hydropower 104 8.2 Geothermal Energy 108 8.3 Wind Energy 113 8.4 Solar Energy: Photovoltaic and Thermal 117 8.4.1 Electricity from Photovoltaic Conversion 118 8.4.2 Solar Thermal Power for Electricity Production 121 8.4.3 Electric Power from Saline Solar Ponds 125 8.4.4 Solar Thermal Energy for Heating 125 8.4.5 Economics of Solar Energy 126 8.5 Bioenergy 127 8.5.1 Electricity from Biomass 128 8.5.2 Liquid Biofuels 130 8.5.2.1 Biomethanol 135 8.5.3 Advantages and Limitation of Biofuels 135 8.6 Ocean Energy: Thermal, Tidal, and Wave Power 136 8.6.1 Tidal Energy 136 8.6.2 Wave Power 138 8.6.3 Ocean Thermal Energy 139 8.7 Nuclear Energy 140 8.7.1 Energy from Nuclear Fission Reactions 142 8.7.2 Breeder Reactors 146 8.7.3 The Need for Nuclear Power 148 8.7.4 Economics 149 8.7.5 Safety 151 8.7.6 Radiation Hazards 153 8.7.7 Nuclear By‐products, Waste, and Their Management 154 8.7.8 Emissions 156 8.7.9 Nuclear Fusion 156 8.7.10 Nuclear Power: An Energy Source for the Future 160 8.8 Future Outlook 161 9 The Hydrogen Economy and Its Limitations 165 9.1 Hydrogen and Its Properties 166 9.2 The Development of Hydrogen Energy 168 9.3 Production and Uses of Hydrogen 171 9.3.1 Hydrogen from Fossil Fuels 172 9.3.2 Hydrogen from Biomass 174 9.3.3 Photobiological Water Cleavage and Fermentation 175 9.3.4 Water Electrolysis 175 9.3.4.1 Electrolyzer Types 176 9.3.4.2 Electricity Source 177 9.3.5 Hydrogen Production Using Nuclear Energy 179 9.4 The Challenge of Hydrogen Storage 180 9.4.1 Liquid Hydrogen 182 9.4.2 Compressed Hydrogen 182 9.4.3 Metal Hydrides and Solid Adsorbents 184 9.4.4 Chemical Hydrogen Storage 185 9.5 Centralized or Decentralized Distribution of Hydrogen? 186 9.6 Hydrogen Safety 188 9.7 Hydrogen as a Transportation Fuel 189 9.8 Fuel Cells 191 9.8.1 History 191 9.8.2 Fuel Cell Efficiency 192 9.8.3 Hydrogen‐based Fuel Cells 194 9.8.4 PEM Fuel Cells for Transportation 197 9.8.5 Regenerative Fuel Cells 200 9.9 Outlook 203 10 The “Methanol Economy”: General Aspects 205 11 Methanol and Dimethyl Ether as Fuels and Energy Carriers 211 11.1 Background and Properties of Methanol 211 11.1.1 Methanol in Nature 213 11.1.2 Methanol in Space 213 11.2 Chemical Uses of Methanol 214 11.3 Methanol as a Transportation Fuel 216 11.3.1 Development of Alcohols as Transportation Fuels 217 11.3.2 Methanol as a Fuel in Spark Ignition (SI) Engines 226 11.3.3 Methanol as a Fuel in Compression Ignition (Diesel) Engines and Methanol Engines 229 11.4 Dimethyl Ether as a Transportation Fuel 232 11.5 Biodiesel Fuel 238 11.6 Advanced Methanol‐powered Vehicles 238 11.6.1 Hydrogen for Fuel Cells Based on Methanol Reforming 239 11.7 Direct Methanol Fuel Cell (DMFC) 245 11.8 Fuel Cells Based on Other Methanol‐derived Fuels and Biofuel Cells 253 11.8.1 Regenerative Fuel Cell 253 11.9 Methanol and DME as Marine Fuels 253 11.10 Methanol for Locomotives and Heavy Equipment 261 11.11 Methanol as an Aviation Fuel 262 11.12 Methanol for Static Power, Heat Generation, and Cooking 263 11.13 DME for Electricity Generation and as a Household Gas 265 11.14 Methanol and DME Storage and Distribution 268 11.15 Price of Methanol and DME 271 11.16 Safety of Methanol and DME 273 11.17 Emissions from Methanol‐ and DME‐powered Vehicles and Other Sources 278 11.18 Environmental Effects of Methanol and DME 283 11.19 The Beneficial Effect of Chemical CO2 Recycling to Methanol on Climate Change 285 12 Production of Methanol from Still Available Fossil‐Fuel Resources 287 12.1 Methanol from Fossil Fuels 290 12.1.1 Production via Syngas 290 12.1.2 Syngas from Coal 294 12.1.3 Syngas from Natural Gas 295 12.1.3.1 Steam Reforming of Methane 295 12.1.3.2 Partial Oxidation of Methane 296 12.1.3.3 Autothermal Reforming and Combination of Steam Reforming with Partial Oxidation 296 12.1.3.4 Syngas from CO2 Reforming of Methane 297 12.1.4 Syngas from Petroleum Oil and Higher Hydrocarbons 297 12.1.5 Economics of Syngas Generation 298 12.1.6 Alternative Syngas Generation Methods 298 12.1.6.1 Tri‐reforming of Natural Gas 298 12.1.6.2 Bi‐reforming of Methane for Methanol Production 298 12.1.6.3 Oxidative Bi‐reforming of Methane for Methanol Production: Methane Oxygenation 300 12.1.7 Other High‐Temperature Processes Based on Methane to Convert Carbon Dioxide to Methanol 300 12.1.7.1 Carnol Process 300 12.1.7.2 Combination of Methane Decomposition with Dry Reforming or Steam Reforming 302 12.1.7.3 Addition of CO2 to Syngas from Methane Steam Reforming 303 12.1.8 Coal to Methanol Without CO2 Emissions 303 12.1.9 Methanol from Syngas Through Methyl Formate 305 12.1.10 Methanol from Methane Without Producing Syngas 306 12.1.10.1 Direct Oxidation of Methane to Methanol 306 12.1.10.2 Catalytic Gas‐Phase Oxidation of Methane 307 12.1.10.3 Liquid‐Phase Oxidation of Methane to Methanol 309 12.1.10.4 Methane to Methanol Conversion Through Monohalogenated Methanes 311 12.1.11 Microbial or Photochemical Conversion of Methane to Methanol 313 12.2 Dimethyl Ether Production from Syngas or Carbon Dioxide Using Fossil Fuels 314 13 Production of Renewable Methanol and DME from Biomass and Through Carbon Capture and Recycling 319 13.1 Biomass‐ and Waste‐Based Methanol and DME – Biomethanol and Bio‐DME 319 13.1.1 Gasification 321 13.1.1.1 Sources of Heat for the Gasification 322 13.1.2 Biocrude 322 13.1.3 Combination of Biomass and Coal 324 13.1.4 Excess CO2 in the Gas Mixture Derived from Biomass 324 13.1.5 Methanol from Biogas 329 13.1.6 Limitations of Biomass 332 13.1.7 Aquaculture 335 13.1.7.1 Water Plants 336 13.1.7.2 Algae 336 13.2 Chemical Recycling of Carbon Dioxide to Methanol 340 13.3 Heterogeneous Catalysts for the Production of Methanol from CO2 and H2 340 13.4 Production of DME from CO2 Hydrogenation over Heterogeneous Catalysts 342 13.5 Reduction of CO2 to Methanol with Homogeneous Catalysts 343 13.6 Practical Applications of CO2 to Methanol 344 13.7 Alternative Two‐Step Route for CO2 Hydrogenation to Methanol 346 13.8 Where Should the Needed Hydrogen Come From? 346 13.9 CO2 Reduction to CO Followed by Hydrogenation 347 13.10 Electrochemical Reduction of CO2 348 13.10.1 Direct Electrochemical CO2 Reduction to Methanol 349 13.10.2 Methods for High‐Rate Electrochemical CO2 Reduction 350 13.10.3 Syngas (Metgas) Production from Formic Acid Synthesized by Electrochemical Reduction of CO2 352 13.11 Thermochemical and Photochemical Routes to Methanol 352 13.11.1 Solar‐Driven Thermochemical Conversion of CO2 to CO for Methanol Synthesis 352 13.11.2 Direct Photochemical Reduction of CO2 to Methanol 354 13.12 Sources of CO2 355 13.12.1 Separating Carbon Dioxide from Industrial and Natural Sources for Chemical Recycling 356 13.12.2 CO2 Capture from Seawater 359 13.12.3 CO2 Capture from the Air 359 13.13 Atmospheric CO2 to Methanol 363 13.14 Cost of Producing Methanol from CO2 and Biomass 365 13.15 Advantages of Producing Methanol from CO2 and H2 369 13.16 Reduction in Greenhouse Gas Emissions 369 13.17 Anthropogenic Carbon Cycle 372 14 Methanol‐Based Chemicals, Synthetic Hydrocarbons, and Materials 375 14.1 Methanol‐Based Chemical Products and Materials 375 14.2 Methyl‐tert‐butyl Ether and DME 377 14.3 Methanol Conversion to Light Olefins and Synthetic Hydrocarbons 378 14.4 Methanol to Olefin (MTO) Processes 380 14.5 Methanol to Gasoline (MTG) Processes 383 14.6 Methanol‐Based Proteins 384 14.7 Plant Growth Promotion 385 14.8 Outlook 386 15 Conclusion and Outlook 387 15.1 Where Do We Stand? 387 15.2 The “Methanol Economy”: Progress and Solutions for the Future 390 Further Reading and Information 395 References 409 Index 459
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.
