Beyond Oil and Gas E-Book

George A. Olah

• Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 973

Veröffentlichungsjahr: 2018

Beschreibung

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.

Leseprobe

Table of Contents

Cover

Dedication

Preface

About the Authors

Acronyms

Conversion of Units

Chapter 1: Introduction

Chapter 2: Coal in the Industrial Revolution and Beyond

Chapter 3: History of Petroleum Oil and Natural Gas

3.1 Oil Extraction and Exploration

3.2 Natural Gas

Chapter 4: Fossil‐Fuel Resources and Their Use

4.1 Coal

4.2 Petroleum Oil

4.3 Unconventional Oil Sources

4.4 Tar Sands

4.5 Oil Shale

4.6 Light Tight Oil

4.7 Natural Gas

4.8 Coalbed Methane

4.9 Tight Sands and Shales

4.10 Methane Hydrates

4.11 Outlook

Chapter 5: Oil and Natural Gas Reserves and Their Limits

Chapter 6: The Continuing Need for Hydrocarbon Fuels and Products

6.1 Fractional Distillation of Oil

6.2 Thermal Cracking and Other Downstream Processes

6.3 Petroleum Products

Chapter 7: Fossil Fuels and Climate Change

7.1 Mitigation

Chapter 8: Renewable Energy Sources and Atomic Energy

8.1 Hydropower

8.2 Geothermal Energy

8.3 Wind Energy

8.4 Solar Energy: Photovoltaic and Thermal

8.5 Bioenergy

8.6 Ocean Energy: Thermal, Tidal, and Wave Power

8.7 Nuclear Energy

8.8 Future Outlook

Chapter 9: The Hydrogen Economy and Its Limitations

9.1 Hydrogen and Its Properties

9.2 The Development of Hydrogen Energy

9.3 Production and Uses of Hydrogen

9.4 The Challenge of Hydrogen Storage

9.5 Centralized or Decentralized Distribution of Hydrogen?

9.6 Hydrogen Safety

9.7 Hydrogen as a Transportation Fuel

9.8 Fuel Cells

9.9 Outlook

Chapter 10: The “Methanol Economy”: General Aspects

Chapter 11: Methanol and Dimethyl Ether as Fuels and Energy Carriers

11.1 Background and Properties of Methanol

11.2 Chemical Uses of Methanol

11.3 Methanol as a Transportation Fuel

11.4 Dimethyl Ether as a Transportation Fuel

11.5 Biodiesel Fuel

11.6 Advanced Methanol‐powered Vehicles

11.7 Direct Methanol Fuel Cell (DMFC)

11.8 Fuel Cells Based on Other Methanol‐derived Fuels and Biofuel Cells

11.9 Methanol and DME as Marine Fuels

11.10 Methanol for Locomotives and Heavy Equipment

11.11 Methanol as an Aviation Fuel

11.12 Methanol for Static Power, Heat Generation, and Cooking

11.13 DME for Electricity Generation and as a Household Gas

11.14 Methanol and DME Storage and Distribution

11.15 Price of Methanol and DME

11.16 Safety of Methanol and DME

11.17 Emissions from Methanol‐ and DME‐powered Vehicles and Other Sources

11.18 Environmental Effects of Methanol and DME

11.19 The Beneficial Effect

of Chemical CO

2

Recycling to Methanol on Climate Change

Chapter 12: Production of Methanol from Still Available Fossil‐Fuel Resources

12.1 Methanol from Fossil Fuels

12.2 Dimethyl Ether Production from Syngas or Carbon Dioxide Using Fossil Fuels

Chapter 13: Production of Renewable Methanol and DME from Biomass and Through Carbon Capture and Recycling

13.1 Biomass‐ and Waste‐Based Methanol and DME – Biomethanol and Bio‐DME

13.2 Chemical Recycling of Carbon Dioxide to Methanol

13.3 Heterogeneous Catalysts for the Production of Methanol from CO

2

and H

2

13.4 Production of DME from CO

2

Hydrogenation over Heterogeneous Catalysts

13.5 Reduction of CO

2

to Methanol

with Homogeneous Catalysts

13.6 Practical Applications of CO

2

to Methanol

13.7 Alternative Two‐Step Route for CO

2

Hydrogenation to Methanol

13.8 Where Should the Needed Hydrogen Come From?

13.9 CO

2

Reduction to CO Followed by Hydrogenation

13.10 Electrochemical Reduction of CO

2

13.11 Thermochemical and Photochemical Routes to Methanol

13.12 Sources of CO

2

13.13 Atmospheric CO

2

to Methanol

13.14 Cost of Producing Methanol from CO

2

and Biomass

13.15 Advantages of Producing Methanol from CO

2

and H

2

13.16 Reduction in Greenhouse Gas Emissions

13.17 Anthropogenic Carbon Cycle

Chapter 14: Methanol‐Based Chemicals, Synthetic Hydrocarbons, and Materials

14.1 Methanol‐Based Chemical Products and Materials

14.2 Methyl‐

tert

‐butyl Ether and DME

14.3 Methanol Conversion to Light Olefins and Synthetic Hydrocarbons

14.4 Methanol to Olefin (MTO) Processes

14.5 Methanol to Gasoline (MTG) Processes

14.6 Methanol‐Based Proteins

14.7 Plant Growth Promotion

14.8 Outlook

Chapter 15: Conclusion and Outlook

15.1 Where Do We Stand?

15.2 The “Methanol Economy”: Progress and Solutions for the Future

Further Reading and Information

General information on energy

Coal

Petroleum oil and natural gas

Liquefied Natural Gas (LNG)

Unconventional oil and gas resources

Oil shale

Coal bed methane, tight gas sands and shale gas

Methane hydrates

Diminishing oil and natural gas resources, production peak and shortage

Hydrocarbons and their products

To learn more about plastics:

Climate change

CO

2

capture and storage

Renewable energies

Hydropower

Geothermal

Wind

Solar energy

Biomass

Ocean energy

Tidal, current and wave energy

Ocean thermal energy

Nuclear energy

Generation IV International Forum. https://www.gen‐4.org/ (accessed 31 January 2018).

Nuclear fusion

Hydrogen

Fuel cells

Methanol and the methanol economy®

Renewable methanol from biomass and CO

2

recycling

Methanol to hydrocarbons:

Direct methanol fuel cells (DMFC)

Dimethyl ether (DME)

Reference

Index

End User License Agreement

List of Tables

Chapter 1

Table 1.1 World population (in millions).

Table 1.2 United States energy consumption by fuel (%).

Table 1.3 Electricity generation in the United States by fuel (%).

Table 1.4 Electricity generated in selected industrialized countries by type of fuel (%, 2015).

Table 1.5 Composition of air.

Chapter 7

Table 7.1 Global warming potentials (GWPs) of some greenhouse gases.

Chapter 8

Table 8.1 Production of electricity from biomass and waste in 2014.

Table 8.2 Energy content of various fuels.

Table 8.3 Nuclear power reactors under construction.

Table 8.4 Radiation exposure (mSv/year) from different activities.

Table 8.5 Half‐life (years) of some radioactive elements.

Chapter 9

Table 9.1 Properties of hydrogen.

Table 9.2 Theoretical reversible cell potentials (

E

°

rev

) and maximum intrinsic efficiencies for fuel cell reactions under standard at 25 °C.

Chapter 11

Table 11.1 Properties of methanol.

Table 11.2 Properties of dimethyl ether (DME).

Table 11.3 Comparison of the physical properties of DME and diesel fuel.

Table 11.4 Comparison of the physical properties of oxymethylene ethers (OMEs)

, DME, and diesel fuel [395, 396, 398].

Table 11.5 Comparison of the physical properties of DME and liquified petroleum gas (LPG).

Table 11.6 Global warming potential of DME.

Chapter 13

Table 13.1 Standard potentials for

CO

2

reduction.

List of Illustrations

Chapter 1

Figure 1.1 World population over time

and in the future.

Figure 1.2 World primary energy consumption

, 1970–2040 in units of (a) petawatt‐hours; (b) Btu (British thermal units).

Figure 1.3 Proven oil and natural gas reserves

(in billion tonnes oil equivalent).

Chapter 2

Figure 2.1 Water removal in mines

during the middle ages. From an engraving by Georgius Agricola – De Re Metallica: book 6 ill. 36, 1556.

Figure 2.2 Watt's engine

, 1774..

Figure 2.3 Stephenson's locomotive,

The Rocket

, 1829..

Chapter 3

Figure 3.1 Edwin Drake

(right) in front of his well in Titusville, Pennsylvania, 1866.

Figure 3.2 Daimler and Maybach in their first four‐wheel automobile

.

Figure 3.3 Ford's first assembly line in 1913.

Figure 3.4 Oil supertanker

.

Figure 3.5 The Bunsen burner

. (a) The pure burner. (b) in action, burning with a blue flame.

Chapter 4

Figure 4.1 Total world primary energy supply (TPES)

in 2014.

Figure 4.2 World coal production

in 2013.

Figure 4.3 Coal production since 1981

for the current five largest producers.

Figure 4.4 Distribution of proven coal reserves

in 2015.

Figure 4.5 Oil production over time

. OPEC is the Organization of Petroleum Exporting Countries.

Figure 4.6 World oil consumption by sector in 2014

.

Figure 4.7 Regional distribution of world oil reserves in 2015.

Figure 4.8 Tar sand mining

in Alberta.

Figure 4.9 Suncor tar sand plant

in Alberta.

Figure 4.10 Crude oil production

in the U.S. with projections to 2040 (in million barrels per day).

Figure 4.11 World natural gas consumption

.

Figure 4.12 World natural gas proven reserves

by region.

Figure 4.13 Oil and natural gas reserve to production (R:P) ratio

.

Figure 4.14 Distribution of the world natural gas proven reserves in 2015

.

Figure 4.15 Liquid natural gas (LNG) tanker

for transportation of natural gas across the seas.

Figure 4.16 U.S. natural gas production by source.

Figure 4.17 Methane hydrate. A molecule of methane is trapped in a cage made out of water molecules.

Figure 4.18 Burning methane hydrate.

Figure 4.19 The distribution of methane hydrates, worldwide.

Figure 4.20 Distribution of organic carbon on Earth reservoirs (Gigatons).

Chapter 5

Figure 5.1 Predicted estimates of world oil ultimate recovery over time

.

Figure 5.2 Hubbert's original 1956 graph

showing crude oil production in the 48 Lower States of the United States based on the assumed initial reserves of 150 and 200 billion barrels. The bold, superimposed line indicates actual oil production up to 2015 following Hubbert's 200 billion barrels forecast until about 2004.

Figure 5.3 Hubbert's peak for world oil production

.

Chapter 6

Figure 6.1 Examples of hydrocarbons

.

Figure 6.2 Schematic representation of the structural groups and connecting bridges in bituminous coal

.

Figure 6.3 Crude oil distillation

.

Figure 6.4 Petroleum products and uses in the United States (% refinery yields of finished products in 1997).

Chapter 7

Figure 7.1 Annual global mean surface temperature anomalies

from 1850 to 2012 relative to the mean temperature of 1961–1990. Combined measurements from the latest version of the three combined

land surface air temperature

(

LSAT

) and

sea surface temperature

(

SST

) data sets (HadCRUT4, GISS, and NCDC MLOST).

Figure 7.2 Variations of Earth's surface temperature

for the past 1000 years in the Northern Hemisphere.

Figure 7.3 Atmospheric CO

2

concentration

measured at Mauna Loa, Hawaii.

Figure 7.4 Global carbon cycle

.

Figure 7.5 Global CO

2

emissions

from fossil fuel burning, cement production, and gas flaring for the period 1750 until 2013.

Figure 7.6 The world's largest energy‐related CO

2

emitters

in 2012.

Figure 7.7 Energy‐related CO

2

emissions

by selected region.

Figure 7.8 Relative contributions of greenhouse gases to the increased greenhouse effect induced by human activity. Total forcing change between 1750 and 2011 was 2.83 W m

−2

.

Figure 7.9 Radiative forcing from major well‐mixed greenhouse gases

from 1850 to 2011.

Figure 7.10 An overview of CO

2

sequestration technologies

.

Chapter 8

Figure 8.1 (a) Share of renewables in world's total primary energy supply (TPES) in 2014. (b) Share of renewables in world's electricity production in 2014. Other includes electricity from energy sources not defined above such as nonrenewable wastes, peat, oil shale, and chemical heat. Other renewables include geothermal, wind, solar, and tide.

Figure 8.2 Percentage of electricity produced from

hydropower in selected countries.

Figure 8.3 Hoover Dam

on the Colorado River in the United States.

Figure 8.4 Three Gorge dam

in China.

Figure 8.5 Geothermal electricity production

, 2015.

Figure 8.6 Worldwide development of geothermal electric power

until 2015.

Figure 8.7 The Geysers

, California.

Figure 8.8 World wind power installed capacity

.

Figure 8.9 Offshore wind farm

, Denmark.

Figure 8.10 First Solar thin‐film solar installation

.

Figure 8.11 Cumulative installed photovoltaic (PV) power in the world.

Figure 8.12 Compact linear Fresnel reflector power plant.

Figure 8.13 Ivanpah solar tower facility

in California.

Figure 8.14 Solar dish/Stirling engine systems

in New Mexico with a production capacity of 25 kW each.

Figure 8.15 Annual growth rates of electricity production between 1990 and 2014 in OECD countries.

Figure 8.16 Percentage of ethanol‐powered automobiles

produced in Brazil compared with the country's total automobile production.

Figure 8.17 Historic production of ethanol in the United States and Brazil.

Figure 8.18 Production of biodiesel

in Europe.

Figure 8.19 Share of nuclear energy in electricity production in 2015.

Figure 8.20 Nuclear fission chain reaction

.

Figure 8.21 Historical growth of nuclear energy (production capacity).

Figure 8.22 The nuclear fuel cycle in a once‐through reactor.

Figure 8.23 Uranium 238 fertilization by neutron capture.

Figure 8.24 U.S. electricity production costs from 1981 to 2014 (in 2014 cents/kWh). Costs include fuel, operation, and maintenance.

Figure 8.25 Average radiation dose to the public (in mSv/year).

Figure 8.26 ITER Fusion reactor

.

Figure 8.27 A typical fusion reaction.

Figure 8.28 Tri Alpha Energy experimental device to obtain high‐temperature stable plasma.

Figure 8.29 Compression system prototype at General Fusion using large pistons converging on a magnetized superheated plasma.

Chapter 9

Figure 9.1 The Sun is converting 600 million tonnes hydrogen to helium every second.

Figure 9.2 Zeppelin LZ‐129 “Hindenburg” flying over New York.

Figure 9.3 Space shuttle

launch at Cape Canaveral, Florida.

Figure 9.4 The main hydrogen‐consuming sectors in the world.

Figure 9.5 Sources for worldwide hydrogen production in 2014.

Figure 9.6 Alkaline electrolysis cell.

Figure 9.7 The sulfur–iodine thermochemical cycle for the production of hydrogen.

Figure 9.8 Different routes for the production of hydrogen.

Figure 9.9 Volumetric energy content of hydrogen compared with other fuels.

Figure 9.10 Hydrogen ICE car from BMW.

Figure 9.11 Fuel to energy conversions.

Figure 9.12 Theoretical efficiency change with temperature of a hydrogen fuel cell and a heat engine.

Figure 9.13

Proton‐exchange membrane (PEM) hydrogen fuel cell.

Figure 9.14 Alkaline fuel cell.

Figure 9.15 Molten carbonate fuel cell (MCFC).

Figure 9.16

Solid oxide fuel cell (SOFC).

Figure 9.17 Schematic of a polysulfide bromide battery.

Chapter 11

Figure 11.1 Methanol cloud in space.

Figure 11.2 The world demand for methanol in 2016 and 2007.

Figure 11.3 Distribution of methanol consumption by product over time.

Figure 11.4 Methanol‐fueled

vehicles in Germany from the mid‐1970s to beginning of 1980s. (a) Volkswagen and Audi fleet of methanol cars in 1975; (b) Volkswagen Golf running on methanol in 1975; (c) Porsche 924 and 928 filling M15 fuel at a station in 1980.

Figure 11.5 Methanol‐fueled vehicles operated by

Mercedes‐Benz in Germany at the end of the 1970s to beginning of 1980s. (a) Mercedes‐Benz 230; (b) Mercedes‐Benz 450 SL; (c) Mercedes‐Benz 208 van; (d) Mercedes‐Benz O‐305 city bus tested in regular service.

Figure 11.6 Methanol‐fueled vehicles in California

. (a) Ford Escorts methanol dedicated light‐duty vehicle (1981 (40 cars) and 1983 (500 cars)). (b) Flexible fuel vehicle (FFV) at a methanol filing station (1990).

Figure 11.7 Methanol

blending standards in Chinese provinces. The number after the “M” indicates the amount in methanol by volume in the fuel mixture with gasoline.

Figure 11.8 Buses refueling

with pure methanol in China (a). Trucks loading M15 for delivery to gas stations in Shaanxi province (b).

Figure 11.9 Fleet of methanol‐fueled taxis in

Guiyang city, Guizhou province, China.

Figure 11.10 Fleet of Geely Emgrand 7 cars operating in Iceland on 100% renewable methanol in front of the Carbon Recycling International (CRI) CO

2

‐to‐methanol production plant.

Figure 11.11 M15 and M70

demonstration cars in Israel.

Figure 11.12 Lotus Exige 270E tri‐fuel

able to run on any mixture of gasoline, ethanol, and methanol.

Figure 11.13 (a) Race car

powered with GEM fuel in Europe; (b) biomethanol fuel produced by BioMCN; (c) race cars powered by GEM fuels; (d) 2012 Holden Commodore SV6 running on GEM in Australia.

Figure 11.14 Methanol‐powered trucks in California in the 1980s–1990s. (a) Caterpillar 3306 methanol garbage truck. City of Glendale (1991). (b) City of Los Angeles dump truck equipped with a DDC 6V‐92TA methanol engine (M100, 1993). (c) Ford 6.6 l methanol arrowhead drinking water delivery truck.

Figure 11.15 Methanol‐powered regional transit bus in (a) Denver, Colorado; (b) Los Angeles, California; and (c) San Francisco (Golden Gate Transit 1984–1988). (d) Carpenter school bus using a DDC 6V‐92TA M85 engine (1993).

Figure 11.16 Examples of DME‐powered buses and trucks

. (a) DME‐fueled Volvo bus developed in Denmark. Source: Courtesy of Danish Road Safety and Transport Agency. (b–d) DME‐fueled Volvo Trucks in Europe and the United States (2010–2015).

Figure 11.17 (a) DME bus in

China [383]. (b) Isuzu DME‐fueled light‐duty truck in Japan (2007) [384]. (c) Isuzu DME‐fueled medium‐duty truck in Japan (2009) [382]. (d) Nissan DME heavy‐duty truck in Japan (2004) [384]. (e) DME‐fueled Jinggong Chutian refuse truck in Shanghai, China. (f) DME‐fueled Jinggong Chutian street sweeper in Shanghai, China.

Figure 11.18 Daimler's methanol‐fueled NECAR 5 fuel cell vehicle

(introduced in 2000).

Figure 11.19 Methanol fuel cell buses

developed at Georgetown University in front of the U.S. Capitol (2002).

Figure 11.20 Serenergy's 5 kW

high‐temperature PEMFC/methanol reformer system (front and back view).

Figure 11.21 (a) Fiat 500e electric

car equipped with a Serenergy reformer–PEMFC range extender fueled by methanol. (b) Methanol fueling station in Denmark besides regular gasoline and diesel fuel pumps. (c) QBEAK III vehicle from ECOmove with modular battery and reformer–PEMFC range extender (Serenergy) units. (d) EcoMotion gardening truck powered by Serenergy methanol reformer–PEMFC units.

Figure 11.22 Nissan e‐NV200 electric

car equipped with a Serenergy reformer–PEMFC range extender fueled by methanol. Source: Courtesy of Serenergy, with permission.

Figure 11.23 Palcan hybrid methanol reformer/PEMFC passenger bus

(a) and delivery truck (b) in China.

Figure 11.24 Theoretical energy density of batteries, H

2

–PEM fuel cells, and DMFCs.

Figure 11.25 The direct methanol fuel cell (DMFC).

Figure 11.26 Dynario DMFC‐based power supply

for charging electronic devices commercialized in limited quantities by Toshiba in 2009.

Figure 11.27 Function EFOY Pro fuel cell

of SFC energy (DMFC) for continuous power generation.

Figure 11.28 Daimler DMFC

go‐cart.

Figure 11.29 DMFC‐powered forklift

. (a) Developed at the Jülich Research Center. (b) Oorja Model 3 DMFC mounted on a Toyota forklift..

Figure 11.30 Yamaha FC‐me (a) and FC‐Dii

(b) two‐wheelers powered by a direct methanol fuel cell (DMFC).

Figure 11.31 SFC developed

EFOY DMFC‐powered Li‐ion hybrid system for a small electric car.

Figure 11.32 Regenerative fuel cell system based on CO

2

.

Figure 11.33 Wärtsilä 20‐kW SOFC.

Figure 11.34 Wallenius Wilhelmsen Logistics cargo ship

“Undine” in which the SOFC for the generation of auxiliary power was tested.

Figure 11.35 Passenger ship on lake Baldeney (Germany) powered by a hybrid fuel cell system fueled by renewable methanol. The power‐to‐methanol plant is located in the background (dark gray container on the right side of the picture on land).

Figure 11.36 SECAs

and

ECAs around the world.

Figure 11.37 Methanol‐powered Stena Germanica

50 000 MT ferry operating between Göteborg and Kiel.

Figure 11.38 MAN B&W ME‐LGI two‐stroke dual‐fuel engine (methanol/diesel) for 50 000 dead weight tonne cargo ship.

Figure 11.39 One of the world's first ocean‐going vessels powered by methanol using MAN ME‐LGI engines.

Figure 11.40 GreenPilot project

to convert a pilot boat to methanol operation.

Figure 11.41 Pratt and Whitney 50 MWe gas turbine in Eilat converted from diesel to methanol operation (background) and fuel‐handling system in the foreground.

Figure 11.42 Methanol 2 burner cookstove

from Cleancook AB (see also [481]).

Figure 11.43 Methanol fueling station and methanol pumps in China.

Figure 11.44 M15 dispensing pump alongside gasoline and diesel fuel dispensers in a refueling station in Israel. Source: Courtesy of Dor Chemicals, with permission.

Figure 11.45 DME filing station and pump in Shanghai, China.

Figure 11.46 Historic methanol sale prices.

Figure 11.47 The metabolism of methanol in the human body.

Figure 11.48 Spill‐free connection for refueling vehicles with methanol in Denmark.

Figure 11.49 Comparative fuel‐related fires, deaths, and injuries.

Figure 11.50 Pollutant emission from methanol‐powered fuel cell buses.

Figure 11.51 Emission regulation for diesel truck engines in the United States, Japan, and Europe compared with emission from DME truck.

Figure 11.52 DME truck NO

x

and particulate matter (PM) emission compared with emission regulations for diesel engines in the United States and Japan.

Figure 11.53 NO

x

, nonmethane hydrocarbons, CO, and PM emissions generated by DME engines compared with emission regulations in Japan.

Figure 11.54 Marine engine emissions with methanol compared with other fuels [512]. HFO: heavy fuel oil; MGO: marine gas oil. The percentage in parenthesis represents the sulfur content in the fuel.

Chapter 12

Figure 12.1 Methanol production

and demand by major region (estimate 2015).

Figure 12.2 Recent global

demand for methanol.

Figure 12.3 Market share of awarded methanol production capacity between 2003 and 2014.

Figure 12.4 Synthesis of methanol in the

LPMEOH slurry reactor developed by Air Products.

Figure 12.5 Atlas mega‐methanol plant in Trinidad

.

Figure 12.6 Schematic representation of KOGAS tri‐reforming process

.

Figure 12.7 Oxidative bi‐reforming for producing metgas exclusively for methanol synthesis.

Figure 12.8 Processes to convert methane to methanol using CO

2

.

Figure 12.9 Methane oxidation products

.

Figure 12.10 Methanol from fossil‐fuel resources.

Chapter 13

Figure 13.1 Simplified schematic illustrating the methanol production from biomass‐based feedstocks.

Figure 13.2 “Biocrude.”

Figure 13.3 Methanol/DME synthesis based on electrolysis‐assisted gasification of wood.

Figure 13.4 The carbon neutral cycle of biomethanol production and uses through syngas.

Figure 13.5 (a) Bio‐DME filling station in Sweden in 2011 and (b) Volvo DME‐fuelled truck in front of bioDME pilot plant in 2011.

Figure 13.6 Swedish car powered by a M56 mix with biomethanol from the LTU Green Fuels plant (in the background).

Figure 13.7 BioMCN biomethanol plant

in the Netherlands.

Figure 13.8 Enerkem's municipal solid waste

to biofuels (methanol and ethanol) plant in Alberta, Canada.

Figure 13.9 Methanol production concept from biogas and H

2

via SOEC using wind energy.

Figure 13.10 Oberon pilot plant for the production of DME

from biogas in California.

Figure 13.11 Small‐scale DME production with Oberon's technology.

Figure 13.12 The HotModule from MTU

: the first bi‐fuel molten carbonate fuel cell (MCFC) went into service at Vattenfall Europe AG in Berlin in September 2004. It is fuelled with natural gas or methanol or any mixture of these two. The methanol used is derived from waste generated locally.

Figure 13.13 Water hyacinth

infesting waterways in Langkawi, Malaysia.

Figure 13.14

Common (broad leaved) Cattail.

Figure 13.15 Kelp forest.

Figure 13.16 Microalgae Chlorella

.

Figure 13.17 Most common combinations of supports and additives used for Cu‐based heterogeneous catalysts for the hydrogenation of CO

2

to methanol.

Figure 13.18 The “George Olah Renewable CO

2

‐to‐Methanol Plant

” of Carbon Recycling International (CRI) in Iceland. Based on local renewable energy and CO

2

.

Figure 13.19 Simplified schematic of the CAMERE process.

Figure 13.20 Two‐electron reduction of CO

2

to CO with concomitant H

2

evolution for subsequent production of methanol.

Figure 13.21 Two‐electron reduction of CO

2

to formic acid with subsequent esterification to methyl formate and further hydrogenation to methanol.

Figure 13.22 Methanol production from CO

2

by sequential electrochemical reduction to FA, FA decomposition, and metgas conversion to methanol.

Figure 13.23 Solar thermochemical cycle

for metal‐oxide‐assisted reduction of CO

2

to CO. M

x

O

y

: metal oxide with the metal in its higher oxidation state, M

m

O

n

: metal oxide with the metal in its lower oxidation state.

Figure 13.24 Currently favored carbon capture and sequestration (CCS) processes from fossil‐fuel‐burning power plants.

Figure 13.25 CO

2

separation and capture technologies.

Figure 13.26 Examples of prototypes and proposed designs for the separation of CO

2

from the air. (a) Prototype for CO

2

capture from the air. (b) Solid amine‐based swing bed for CO

2

removal in human space flights. Currently undergoing tests in the International Space Station (ISS). (c) Artist rendering of an atmospheric CO

2

capture contactor. (d) Artist rendering of an array of atmospheric CO

2

capture units also known as Synthetic Trees. (e) Artist rendering of a prototype for CO

2

capture from the air using an anionic exchange resin and regeneration by moisture swing. (f) Construction of a prototype for CO

2

capture from the air in Alberta, Canada.

Figure 13.27 First commercial direct air capture plant built by Climeworks close to Zürich in Switzerland.

Figure 13.28 Methanol from atmospheric CO

2

and water in the Green Freedom process.

Figure 13.29 Production costs and production capacity of (bio‐)methanol for various feedstocks from the literature. Source: IRENA analysis [870]. Excludes cofeed setups; all costs converted to 2010 Euro values using national GDP deflators (World Bank); assumed Organisation for Economic Co‐operation and Development (OECD) average inflation if no specific region is mentioned; assumed 8000 operational hours per year (if necessary); for costs beyond 2010, 2.5% annual inflation was assumed (OECD average for 1995–2010). Based on references [308, 597, 609, 626, 629, 639, 640, 686, 871‐880, 882–889].

Figure 13.30 WTW GHG emissions of renewable methanol and comparative fossil and biofuel pathways (g CO

2

e/MJ).

Figure 13.31 Anthropogenic carbon cycle

within the Methanol Economy.

Figure 13.32 Possible transition to a sustainable fuel future including methanol and DME as key components.

Chapter 14

Figure 14.1 Methanol‐derived chemical products and materials.

Figure 14.2 DMTO commercial unit in Shenhua Baotou, Inner Mongolia.

Chapter 15

Figure 15.1 The Methanol Economy.

Guide

Cover

Table of Contents

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Beyond Oil and Gas: The Methanol Economy

George A. Olah, Alain Goeppert, and G. K. Surya Prakash

Third, Updated and Enlarged Edition

Copyright

The Authors

Prof. George A. Olah

University of Southern California

Loker Hydrocarbon Research Institute

837 Bloom Walk

Los Angeles, CA 90089

United States

Dr. Alain Goeppert

University of Southern California

Loker Hydrocarbon Research Institute

837 Bloom Walk

Los Angeles, CA 90089

United States

Prof. G. K. Surya Prakash

University of Southern California

Loker Hydrocarbon Research Institute

837 Bloom Walk

Los Angeles, CA 90089

United States

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de.

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN: 978-3-527-33803-0

ePDF ISBN:978-3-527-80565-5

ePub ISBN: 978-3-527-80567-9

oBook ISBN: 978-3-527-80566-2

Cover Design Grafik-Design Schulz, Fußgönheim, Germany

Dedication

Dedicated to the fond memory of a Giant of a Chemist and a great Human Being, the late Professor George A. Olah.

Preface

It is gratifying to see that our book centered on the “Methanol Economy,” after 12 years since its first publication and 9 years since the printing of the second updated edition, has received significant attention worldwide. Over the years, the book was translated into five other languages: Chinese, Hungarian, Japanese, Russian, and Swedish. The broad interest in the Methanol Economy and numerous developments related to methanol around the world over the past decade prompted us to write an updated version of the book. World methanol output is growing rapidly, having now surpassed 70 million metric tons per year, with a global production capacity in excess of 100 million metric tons. Methanol has been traditionally produced through steam reforming of natural gas and coal gasification. Currently, China is the leading nation in methanol production, with a yearly output of about 40 million metric tons, predominantly through coal gasification. More than 10% of transportation fuel in China is methanol based. China also uses methanol as a chemical feedstock to produce ethylene and propylene to make plastics. At the same time, China is blending dimethyl ether (DME) derived from methanol for use as a cooking fuel. In Sweden, methanol is being promoted as a major clean burning marine fuel, replacing highly polluting bunker and furnace oils. Israel is blending methanol with gasoline for the transportation sector. India has proposed using methanol not only as a transportation fuel to replace gasoline and diesel but also as a cooking fuel in clean burning methanol stoves. Although fossil fuels are still the source for most of the methanol produced today, biomass, biogas, and carbon dioxide are also emerging as feedstocks to produce renewable methanol and DME. Almost all energy on Earth, about 130 000 TW continuous, comes from the Sun, which is supposed to last at least for another 4.5 billion years. Therefore, humanity per se does not have an energy problem but rather an energy storage and energy carrier problem. All fossil fuels, which took nature eons to produce, can be classified as fossilized sunshine. The chemical recycling of natural and anthropogenic carbon dioxide sources using hydrogen derived from electrolysis of water using alternative energy sources such as solar, wind, geothermal, and nuclear will offer the ultimate solution for humankind to manage carbon and solve the deleterious effects of global warming. Since all living beings are tied to carbon, sensible carbon management has to be the solution for humankind in the long run. In fact, such a technology has been commercialized in Iceland, producing regenerative methanol from carbon dioxide and water using geothermal energy. The George Olah Renewable Methanol Plant, the first of its kind, aptly named after our late coauthor, produces 12 metric tons of renewable methanol a day! It is quite unfortunate that our distinguished coauthor, Professor George A. Olah, the major proponent of the Methanol Economy concept passed away on March 8, 2017. We dedicate this updated and enlarged edition of the book to his memory.

April 2018, Los Angeles

Alain Goeppert

G. K. Surya Prakash

About the Authors

Born in 1927 in Budapest, Hungary, George A. Olah obtained his doctorate at the Technical University of Budapest and was a distinguished professor and director of the Loker Hydrocarbon Institute at the University of Southern California (USC). During his life, he received numerous awards and recognitions worldwide, including memberships in various academies of science and 12 honorary degrees. He has some 1500 scientific papers, 20 books, and more than 140 patents to his name. In 1994, Prof. Olah was awarded the Nobel Prize in Chemistry for his work on long‐lived carbocations. He was a pioneer and a major proponent of the Methanol Economy concept. Unfortunately, Prof. Olah passed away in March 2017, before seeing the third edition of this book published.

Alain Goeppert was born in 1974 in Strasbourg, France. After obtaining his diploma in chemistry from the University Robert Schuman in Strasbourg, he received his engineering degree from the Fachhochschule Aalen, Germany. He then returned to Strasbourg to study the reactivity of alkanes in strong acid systems under the direction of Prof. Jean Sommer at the Université Louis Pasteur, earning his PhD in 2002. Subsequently, he joined the group of professors Olah and Prakash at the Loker Hydrocarbon Research Institute and is now a research scientist. Dr. Goeppert's current research is focused on the transformation of methane and CO2 into more valuable products as well as CO2 capture and recycling technologies.

Currently a professor and Olah Nobel Laureate Chair in Hydrocarbon Chemistry, director at the Loker Hydrocarbon Research Institute, and chair of chemistry at USC, G. K. Surya Prakash was born in 1953 in Bangalore, India. After receiving 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 more than 770 scientific papers, 14 books, and 90 patents to his name and has received many accolades, including three American Chemical Society National Awards. His primary research interests are in superacid, hydrocarbon, synthetic organic and organofluorine chemistry, energy, and catalysis areas. He is a co‐proponent of the Methanol Economy concept with late Professor Olah for which he co‐shared with him the 2013 Eric and Sheila Samson Prime Minister's Prize for Alternative Fuels to Transportation from the State of Israel.

Acronyms

AFC

Alkaline fuel cell

BP

British Petroleum

BWR

Boiling water reactor

CEA

Commissariat à l’Energie Atomique (France)

CEC

California Energy Commission

CI

Compression ignition

CIA

Central Intelligence Agency

DME

Dimethyl ether

DMFC

Direct methanol fuel cell

DOE

Department of Energy (United States)

EDF

Electricité de France

EIA

Energy Information Administration (DOE)

EPA

Environmental Protection Agency (United States)

EPRI

Electric Power Research Institute

EU

European Union

GDP

Gross Domestic Product

GHG

Greenhouse gas

IAEA

International Atomic Energy Agency

ICE

Internal combustion engine

IEA

International Energy Agency

IGCC

Integrated gasification combined cycle

IPCC

International Panel on Climate Change

ITER

International Thermonuclear Experimental Reactor

LNG

Liquefied natural gas

MCFC

Molten carbonate fuel cell

MTBE

Methyl‐

tert

‐butyl ether

NRC

National Research Council (United States)

NREL

National Renewable Energy Laboratory (United States)

OECD

Organization for Economic Cooperation and Development

OPEC

Organization of Petroleum Exporting Countries

ORNL

Oak Ridge National Laboratory

OTEC

Ocean thermal energy conversion

PAFC

Phosphoric acid fuel cell

PEMFC

Proton exchange membrane fuel cell

PFBC

Pressurized fluidized bed combustion

PV

Photovoltaics

PWR

Pressurized water reactor

R/P

Reserve:production ratio

SUV

Sport utility vehicle

TPES

Total primary energy supply

UNO

United Nations Organization

UNSCEAR

United Nations Scientific Committee on Effects of Atomic Radiation

URFC

Unitized regenerative fuel cell

USCB

United States Census Bureau

USGS

United States Geological Survey

WCD

World Commission on Dams

WCI

World Coal Institute

WEC

World Energy Council

ZEV

Zero‐emission vehicle

Units and Abbreviations

atm

Atmosphere

b and bbl

barrel

Btu

British thermal unit

°C

degree celsius

cal

calorie

g

gram

h

hour

ha

hectare

kWh

kilowatt‐hour

m

meter

Mb

megabarrel (10

6

barrels)

ppm

parts per million

s

second

Sv

Sievert

t

metric tonne

toe

tonne oil equivalent

W

watt

Prefixes

μ

micro 10

−6

m

milli 10

−3

k

kilo 10

3

M

mega 10

6

G

giga 10

9

T

tera 10

12

P

peta 10

15

E

exa 10

18

Conversion of Units

Volume

1 tonne of crude oil

 = 

7.33 barrels of oil

1 gallon

 = 

3.785 l

1 barrel of oil

 = 

42 U.S. gallons

 = 

159 l 1 m

3

 = 

1000 l

1 m

3

 = 

35.3 cubic feet (ft

3

)

Energy

1 kcal

 = 

4.1868 kJ

 = 

3.968 Btu

1 kJ

 = 

0.239 kcal

 = 

0.948 Btu

1 kWh

 = 

860 kcal

 = 

3600 kJ

1 toe

 = 

41.87 GJ

Quadrillion Btu, QBtu

 = 

1 × 10

15

Btu

1Introduction

Ever since our distant ancestors managed to light fire for providing heat, means for cooking and many other essential purposes, humankind’s life and survival are inherently linked with an ever‐increasing thirst for energy. From burning wood, vegetation, peat moss, and other sources to the use of fossil fuels such as coal, followed by petroleum oil and natural gas, humankind has thrived using Mother Nature’s resources[1]. Fossil fuels are all composed of hydrocarbons with varying ratios of carbon and hydrogen. These hydrocarbons derived from petroleum, natural gas, or coal are essential in many ways to modern life and its quality. A large quantity of the world’s hydrocarbons is used as fuel for propulsion, electrical power generation, and heating. The chemical, petrochemical, plastic, and rubber industries also depend on hydrocarbons as raw materials for their products. Indeed, most of the industrially significant synthetic chemicals are derived from petroleum sources. The overall use of oil in the world now exceeds 13 million metric tons per day (95 million barrels per day) [2]. The rapidly growing world population, which stood at 1.6 billion at the beginning of the twentieth century, has now exceeded 7 billion and is expected to reach 8–11 billion by the middle of the twenty‐first century and up to 16 billion by 2100 [3] (Table 1.1 and Figure 1.1). This increase in world population and energy consumption, compared with our finite nonrenewable fossil fuel resources, which are being increasingly depleted, are clearly on a collision course. New solutions are needed for the twenty‐first century and beyond to sustain the standard of living to which the industrialized world has become accustomed and the developing world is striving to achieve.

Table 1.1 World population (in millions).

Source: United Nations, Department of Economic and Social Affairs, Population Division.

1650

1750

1800

1850

1900

1920

1952

2000

2015

Projection 2050

545

728

906

1171

1608

1813

2409

6200

7400

8000–11 000

Figure 1.1 World population over time and in the future.

Source: United Nations, Department of Economic and Social Affairs, Population Division.

With an increasingly technological society, the world’s resources have difficulty in keeping up with the demands. Satisfying our society’s needs while safeguarding the environment and allowing future generations to continue to enjoy planet Earth as a hospitable home is one of the major challenges that we face today. Humans need not only food, water, shelter, clothing, and many other prerequisites but also huge and growing amounts of energy. In 2010, the world used about 1.33 × 1020 calories per year (154 PWh), equivalent to a continuous power consumption of about 18 TW, which is comparable to the production of 18 000 nuclear power plants each with a 1 GW output (Figure 1.2) [4]. With increasing world population, development, and higher standards of living, this demand for energy is expected to grow to 23 TW in 2025 and to about 30 TW in 2050.

Figure 1.2 World primary energy consumption, 1970–2040 in units of (a) petawatt‐hours; (b) Btu (British thermal units).

Source: Based on data from: Energy Information Administration (EIA), International Energy Outlook 2013.

Our early ancestors discovered fire and began to burn wood. The industrial revolution was fueled by coal, and the twentieth century added oil, natural gas, and introduced atomic energy.

When fossil fuels such as coal, oil, and natural gas (i.e. hydrocarbons) are burned to generate electricity in power plants, or to heat our houses, propel our cars, airplanes, and so on, they form carbon dioxide and water as their combustion products. They are thus used up and are nonrenewable on the human timescale.

Fossil Fuels:

Petroleum oil, natural gas, shale gas, tar sand, shale bitumen, tight oil, and coals

They are mixtures of hydrocarbons (i.e. compounds of the elements carbon and hydrogen). When oxidized (combusted), they form carbon dioxide (CO2) and water (H2O) and are thus not renewable on the human timescale.

Nature has given us a remarkable gift in the form of oil and natural gas. It has been determined that a single barrel of oil has the energy equivalent of 12 people working all year, or 25 000 man hours [5]. With each American consuming on average about 23 barrels of oil per year, this would be equivalent to each of them having almost 300 people working all year long to power the industries and providing the household in order to maintain the current standard of living. Considering the present cost of oil, this is truly a bargain. The fossil fuels that were created over the ages are, however, being consumed rather rapidly by humankind. Petroleum and natural gas are used on a massive scale to generate energy and as raw materials for diverse man‐made materials and products such as plastics, pharmaceuticals, and dyes that have been developed during the twentieth century. The United States’ energy consumption, for example, is heavily based on fossil fuels, with atomic energy and other sources (hydro, geothermal, solar, wind, etc.) representing only a modest 18% of the energy mix (Table 1.2) [6].

Table 1.2 United States energy consumption by fuel (%).

Source: U.S. Census Bureau, Statistical Abstract of the United States and U.S. Energy Information Administration.

Energy source

1960

1970

1980

1990

2000

2005

2010

2015

Oil

44.2

43.5

43.7

39.6

38.8

40.4

36.7

36.7

Natural gas

27.5

32.1

26.1

23.3

24.2

22.6

25.2

29.0

Coal

21.8

18.1

19.7

22.6

22.8

22.8

21.3

16.0

Nuclear energy

0.002

0.4

3.5

7.2

7.9

8.1

8.6

8.6

Hydro‐, geothermal, solar, wind, etc. energy

6.5

6.0

7.0

7.2

6.2

6.1

8.2

9.7

With regard to electricity generation in the United States, coal, which represented for a long while the largest portion of the fuels used, is now almost at parity with natural gas at about 33% each, followed by nuclear energy around 20% (Table 1.3). Due to considerable environmental issues, availability of cheap domestic shale gas, and decreasing costs of electricity from renewable sources, the role of coal has been diminishing rapidly during the last decade.

Table 1.3 Electricity generation in the United States by fuel (%).

Source: U.S. Census Bureau, Statistical Abstract of the United States and U.S. Energy Information Administration.

Energy source

1990

2000

2005

2010

2015

Coal

52.5

51.7

49.8

45.1

33.3

Petroleum

4.2

2.9

3.0

0.9

0.7

Natural gas

12.6

16.2

19.0

23.9

32.9

Nuclear

19.0

19.8

19.3

19.7

19.7

Hydroelectric

9.6

7.2

6.6

6.3

6.1

Geothermal

0.5

0.4

0.4

0.4

0.4

Wood

1.1

1.0

0.9

0.9

1.0

Waste

0.438

0.607

0.594

0.453

0.535

Wind

0.092

0.147

0.361

2.306

4.703

Solar

0.013

0.013

0.012

0.032

0.614

Other industrialized countries obtain between 15% and 95% of their electrical energy from nonfossil sources (Table 1.4) [7].

Table 1.4 Electricity generated in selected industrialized countries by type of fuel (%, 2015).

Source: International Energy Agency, Electricity Information 2016.

Country

Total electricity production (TWh)

Conventional thermal

Nuclear

Hydroelectric

Geothermal, solar, wind, biofuels and waste

Total nonfossil

France

568.2

6.0

77.0

10.5

6.5

94.0

Canada

631.6

17.9

16.5

60.1

5.6

82.1

United Kingdom

337.7

52.8

20.8

2.6

23.7

47.2

Germany

651.5

53.5

14.1

3.8

28.6

46.5

Italy

282.0

59.5

0.0

16.0

24.4

40.5

United States

4312.2

66.9

19.3

6.3

7.5

33.1

Korea

548.7

67.6

30.0

1.1

1.3

32.4

Japan

1014.9

81.7

0.9

9.0

8.4

18.3

Oil use has grown to the point, where the world in 2015 was consuming around 95 million barrels (1 barrel equals 42 gallons, i.e. some 160 l) a day, or about 13 million metric tons [2]. Fortunately, we still have significant worldwide reserves, including heavy oils, oil shale, tar sands, and even larger deposits of coal, a mixture of complex carbon compounds more deficient in hydrogen than in oil and gas. Our more plentiful coal reserves may last for 200 years or more, but at a higher socioeconomical and environmental cost. It is not suggested that our resources will run out in the near future, but it is clear that they will become scarcer, more expensive, and will not last for very long. With a world population exceeding 7 billion and still growing, the demand for oil and gas will only increase. It is also true that in the past, dire predictions of rapidly disappearing oil and gas reserves have proven incorrect (Figure 1.3). As a matter of fact, the proven reserves of oil and gas have been steadily growing over the years due to the discovery of new fields and the adoption of novel technologies allowing the extraction of fossil fuels from sources that could not be previously exploited economically. Proven oil reserves, instead of being depleted, have in fact almost quadrupled during the past 50 years and are now close to 250 billion tonnes (more than 1.5 trillion barrels) [2]. This seems so impressive that many people assume that there is no real oil shortage in sight.

Figure 1.3 Proven oil and natural gas reserves (in billion tonnes oil equivalent).

Source: For 1980–2016: BP statistical review of world energy 2016.

The question is, however also, what is meant by “depletion.” Increasing consumption due to improving standards of living, coupled with a growing world population, makes it more realistic to consider reserves on a per‐capita basis. If we do this, it becomes evident that our known reserves will last for a shorter period of time. Even if all other factors are taken into account (new findings, savings, alternate sources, etc.), our overall reserves will inevitably decrease and thus we will increasingly face a major shortage. Oil and gas are finite resources. Although they will not be depleted overnight, market forces of supply and demand will start to drive their prices up to levels that nobody even wants to contemplate presently. Therefore, if we do not find new solutions, we will eventually face a real crisis.

Humankind wants all the advantages that an industrial society can give to all its citizens. We essentially rely on energy, but the level of consumption varies vastly in different parts of the world (industrialized versus developing countries). At present, the annual oil consumption per capita in China is still only about 2.5 barrels, whereas it is about ten‐fold this level in the United States (23 barrels per capita per year) [2]. Oil use in China is expected to at least double during the next decade, and this alone equals more than the consumption of the United States – reminding us of the magnitude of the problem that we will face. Not only world population growth but also the increasing energy demands from China, India, and other fast developing countries are already putting great pressure on the world’s oil reserves, and this, in turn, will eventually contribute to price escalation. Large price fluctuations, with temporary sharp drops, can be expected, but the upward long‐term trend of increasing oil prices seems inevitable. We will need to get used to higher prices, not as a matter of any government policy but as a fact of market forces over which free societies have very little control.

As we continue to burn our hydrocarbon reserves to generate energy at an alarming rate, diminishing resources and sharp price increases will increasingly lead to a need to supplement or replace them by feasible alternatives. Although petroleum oil is one of the greatest bargains nature has given us, alternative energy and fuel sources and synthetic substitutes are generally costlier. However, with a barrel of oil priced between $30 and $150, within wide market fluctuations, some of these are already becoming economically viable.

Synthetic oil product and substitutes are feasible. Their production has been proven on an industrial scale via synthesis‐gas (syngas), a mixture of carbon monoxide and hydrogen obtained from the incomplete combustion of coal or natural gas, which, however, are themselves nonrenewable. Coal conversion was used in Germany during World War II and in South Africa during the boycott years of the Apartheid era [8]. Nevertheless, the size of these operations hardly amounted to 0.3% of the present United States consumption alone. This route – the so‐called Fischer–Tropsch synthesis – is also highly energy consuming, giving complex product mixtures and generating large amounts of carbon dioxide, thereby contributing to global warming. Thus, it can hardly be seen as the technology of the future. Nevertheless, to utilize still‐existing large coal and natural gas reserves, their conversion to liquid fuels through syngas is being applied on a large scale in China, the Middle East, and other locations. However, these plants can provide only a minor amount of the world’s consumption of transportation fuels, which, by itself, is in excess of 58 million barrels per day. This figure demonstrates the enormity of the problem we face. New and more efficient processes are clearly needed. Some of the required essential new basic science and technology to produce synthetic oil more efficiently are already being developed. Still, abundant natural gas could, for example, be directly converted to liquid hydrocarbon fuels and products, without passing through syngas. The use of our even larger coal resources to produce synthetic oil could also extend their availability. However, these would not solve the associated global climate change problems. Thus, new approaches based on renewable resources are essential for the future. The development of biofuels, primarily by the fermentative conversion of agricultural products (derived from sugar cane, corn, etc.) into bioethanol, is being pursued. Although ethanol can be used as a gasoline additive or alternative fuel, the enormous quantities of transportation fuel needed clearly limit the applicability to specific countries and situations. Plant‐based substitutes are also being developed as renewable equivalents of diesel fuel, although their role is also limited and their environmental impact and benefits are questionable. In addition, biofuels can affect food prices by competing for the same agricultural resources [9].

The advent of atomic energy opened up a fundamental new possibility, but also created dangers and concerns related to the safety of radioactive by‐products. It is regrettable that these considerations brought any further development of atomic energy almost to a standstill, at least in most parts of the Western world. On the other hand, concerns about the use of nuclear power especially after the accidents of Chernobyl and Fukushima are understandable. Nevertheless, if we want to be serious about the mitigation of carbon dioxide emission, atomic energy, albeit made safer and cleaner, is a leading alternative that does not produce CO2. Problems including those of safe storage and disposal of radioactive waste products must be solved. Pointing out difficulties and hazards as well as regulating them is necessary, and solutions to overcome them are essential and certainly feasible.

Even though the generation of energy by burning nonrenewable fossil fuels will last only for a relatively limited period in the future, it is generating serious environmental problems. When hydrocarbons are burned, as pointed out, they produce harmful carbon dioxide (CO2) and water (H2O). The very large amounts of CO2 released contribute to the so‐called “greenhouse warming effect” of our planet, which is causing grave environmental concerns. The relationship between the atmospheric CO2 content and temperature was first studied scientifically by Arrhenius as early as 1895 [10]. The climate change and warming/cooling trends of our Earth can be evaluated only over longer time periods, but there is clearly a relationship between the CO2 content in the atmosphere and Earth’s global temperature. Human activities have increased CO2 emissions, but the effect of these emissions is only superimposed on nature’s own variable cycles.

It is also a great challenge to reverse the combustion process and to chemically produce, both efficiently and economically, hydrocarbon fuels from CO2 and H2O. Nature, in its photosynthesis, achieves it by recycling CO2 with water into new plant life using the Sun’s energy. Although fermentation and other processes can convert plant life into biofuels and products, the natural formation of new fossil fuels takes a very long time, making them nonrenewable on the human timescale.

“The Methanol Economy®” – the specific subject of our book – elaborates a new approach of how humankind can decrease and eventually liberate itself from its dependence on diminishing oil and natural gas (and eventually coal) reserves while mitigating global warming caused by excessive carbon dioxide released from their combustion. The “Methanol Economy” is in part based on the more efficient conversion of still‐existing fossil‐fuel resources to methanol or dimethyl ether (DME) and, most importantly, on their production by chemical recycling of CO2 emissions from fossil‐fuel‐burning power plants as well as other industrial and natural sources. Eventually, even atmospheric CO2 itself will be captured and recycled by using catalytic or electrochemical methods. This represents a chemical regenerative carbon cycle alternative to natural photosynthesis [11–13].

Both methanol and DME are excellent transportation and industrial fuels on their own for internal combustion engines, electrical power generation, and household uses, replacing gasoline, diesel fuel, natural gas, etc. Methanol is also a suitable fuel for fuel cells, being capable of producing electric energy by reacting with atmospheric oxygen contained in the air. DME is readily obtained by dehydration of methanol.

It should be emphasized that the “Methanol Economy” itself does not produce energy. Methanol or DME only stores energy more conveniently and safely compared, for example, with extremely difficult to handle and highly volatile hydrogen gas, which is the basis of the so‐called “Hydrogen Economy” [14, 15]. Besides being most convenient energy storage materials and suitable transportation fuels, methanol and DME can also be easily converted into ethylene and/or propylene. These are essential building blocks in the petrochemical industry for the ready preparation of synthetic aliphatic and aromatic hydrocarbons and for the wide variety of derived products and materials. They are presently obtained from our diminishing oil and gas resources, on which we rely so much in our everyday life.

The far‐reaching implications of the new “Methanol Economy” have great significance and societal benefit for humankind. As mentioned, the world is presently consuming about 95 million barrels of oil each day, and about two‐thirds as much natural gas equivalent, both being derived from our declining and nonrenewable natural sources. Oil, natural gas, and coal were formed by nature over the eons in scattered and frequently increasingly difficult‐to‐access locations such as under deserts, in the depths of the seas, the inhabitable reaches of the polar regions, and so on. In contrast, recycling of CO2