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Beyond Oil and Gas: The Methanol Economy
23 Mar 2006-
TL;DR: In this paper, the authors present a history of the development and use of hydrogen in the past, present, and future of the hydrogen-powered vehicles and their use in the future.
Abstract: Chapter 1: Introduction. Chapter 2: Coal in the Industrial Revolution, and Beyond. Chapter 3: History of Oil and Natural Gas. Oil Extraction and Exploration. Natural Gas. Chapter 4: Fossil Fuel Resources and Uses. Coal. Oil. Tar Sands. Oil Shale. Natural Gas. Coalbed Methane. Tight Sands and Shales. Methane Hydrates. Outlook. Chapter 5: Diminishing Oil and Gas Reserves. Chapter 6: The Continuing Need for Hydrocarbons and their Products. Fractional Distillation. Thermal Cracking. Chapter 7: Fossil Fuels and Climate Change. Mitigation. Chapter 8: Renewable Energy Sources and Atomic Energy. Hydropower. Geothermal Energy. Wind Energy. Solar Energy: Photovoltaic and Thermal. Electricity from Photovoltaic Conversion. Solar Thermal Power for Electricity Production. Electric Power from Saline Solar Ponds. Solar Thermal Energy for Heating. Economic Limitations of Solar Energy. Biomass Energy. Electricity from Biomass. Liquid Biofuels. Ocean Energy: Thermal, Tidal, and Wave Power. Tidal Energy. Waves. Ocean Thermal Energy. Nuclear Energy. Energy from Nuclear Fission Reactions. Breeder Reactors. The Need for Nuclear Power. Economics. Safety. Radiation Hazards. Nuclear Byproducts and Waste. Emissions. Nuclear Power: An Energy Source for the Future. Nuclear Fusion. Future Outlook. Chapter 9: The Hydrogen Economy and its Limitations. The Discovery and Properties of Hydrogen. The Development of Hydrogen Energy. The Production and Uses of Hydrogen. Hydrogen from Fossil Fuels. Hydrogen from Biomass. Photobiological Water Cleavage. Water Electrolysis. Hydrogen Production Using Nuclear Energy. The Challenge of Hydrogen Storage. Liquid Hydrogen. Compressed Hydrogen. Metal Hydrides and Solid Absorbents. Other Means of Hydrogen Storage. Hydrogen: Centralized or Decentralized Distribution? Safety of Hydrogen. Hydrogen in Transportation. Fuel Cells. History. Fuel Cell Efficiency. Hydrogen-Based Fuel Cells. PEM Fuel Cells for Transportation. Regenerative Fuel Cells. Outlook. Chapter 10: The "Methanol Economy": General Aspects. Chapter 11: Methanol as a Fuel and Energy Carrier. Properties and Historical Background. Present Uses of Methanol. Use of Methanol and Dimethyl Ether as Transportation Fuels. Alcohol as a Transportation Fuel in the Past. Methanol as Fuel in Internal Combustion Engines (ICE). Methanol and Dimethyl Ether as Diesel Fuels Substitute in Compression Ignition Engines. Biodiesel Fuel. Advanced Methanol-Powered Vehicles. Hydrogen for Fuel Cells from Methanol Reforming. Direct Methanol Fuel Cell (DMFC). Fuel Cells Based on Other Fuels and Biofuel Cells. Regenerative Fuel Cell. Methanol for Static Power and Heat Generation. Methanol Storage and Distribution. Methanol Price. Methanol Safety. Emissions from Methanol-Powered Vehicles. Methanol and the Environment. Methanol and Issues of Climate Change. Chapter 12: Production of Methanol from Syn-Gas to Carbon Dioxide. Methanol from Fossil Fuels. Production via Syn-Gas. Syn-Gas from Natural Gas. Methane Steam Reforming. Partial Oxidation of Methane. Autothermal Reforming and Combination of Steam Reforming and Partial Oxidation. Syn-Gas from CO2 Reforming. Syn-Gas from Petroleum and Higher Hydrocarbons. Syn-Gas from Coal. Economics of Syn-Gas Generation. Methanol through Methyl Formate. Methanol from Methane Without Syn-Gas. Selective Oxidation of Methane to Methanol. Catalytic Gas-Phase Oxidation of Methane. Liquid-Phase Oxidation of Methane to Methanol. Methanol Production through Mono-Halogenated Methanes. Microbial or Photochemical Conversion of Methane to Methanol. Methanol from Biomass. Methanol from Biogas. Aquaculture. Water Plants. Algae. Methanol from Carbon Dioxide. Carbon Dioxide from Industrial Flue Gases. Carbon Dioxide from the Atmosphere. Chapter 13: Methanol-Based Chemicals, Synthetic Hydrocarbons and Materials. Methanol-Based Chemical Products and Materials. Methanol Conversion to Olefins and Synthetic Hydrocarbons. Methanol to Olefin (MTO) Process. Methanol to Gasoline (MTG) Process. Methanol-Based Proteins. Outlook. Chapter 14: Future Perspectives. The "Methanol Economy" and its Advantages. Further Reading and Information. References. Index.
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TL;DR: A unified theoretical framework highlights the need for catalyst design strategies that selectively stabilize distinct reaction intermediates relative to each other, and opens up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions.
Abstract: BACKGROUND With a rising global population, increasing energy demands, and impending climate change, major concerns have been raised over the security of our energy future. Developing sustainable, fossil-free pathways to produce fuels and chemicals of global importance could play a major role in reducing carbon dioxide emissions while providing the feedstocks needed to make the products we use on a daily basis. One prospective goal is to develop electrochemical conversion processes that can convert molecules in the atmosphere (e.g., water, carbon dioxide, and nitrogen) into higher-value products (e.g., hydrogen, hydrocarbons, oxygenates, and ammonia) by coupling to renewable energy. Electrocatalysts play a key role in these energy conversion technologies because they increase the rate, efficiency, and selectivity of the chemical transformations involved. Today’s electrocatalysts, however, are inadequate. The grand challenge is to develop advanced electrocatalysts with the enhanced performance needed to enable widespread penetration of clean energy technologies. ADVANCES Over the past decade, substantial progress has been made in understanding several key electrochemical transformations, particularly those that involve water, hydrogen, and oxygen. The combination of theoretical and experimental studies working in concert has proven to be a successful strategy in this respect, yielding a framework to understand catalytic trends that can ultimately provide rational guidance toward the development of improved catalysts. Catalyst design strategies that aim to increase the number of active sites and/or increase the intrinsic activity of each active site have been successfully developed. The field of hydrogen evolution, for example, has seen important breakthroughs over the years in the development of highly active non–precious metal catalysts in acid. Notable advancements have also been made in the design of oxygen reduction and evolution catalysts, although there remains substantial room for improvement. The combination of theory and experiment elucidates the remaining challenges in developing further improved catalysts, often involving scaling relations among reactive intermediates. This understanding serves as an initial platform to design strategies to circumvent technical obstacles, opening up opportunities and approaches to develop higher-performance electrocatalysts for a wide range of reactions. OUTLOOK A systematic framework of combining theory and experiment in electrocatalysis helps to uncover broader governing principles that can be used to understand a wide variety of electrochemical transformations. These principles can be applied to other emerging and promising clean energy reactions, including hydrogen peroxide production, carbon dioxide reduction, and nitrogen reduction, among others. Although current paradigms for catalyst development have been helpful to date, a number of challenges need to be successfully addressed in order to achieve major breakthroughs. One important frontier, for example, is the development of both experimental and computational methods that can rapidly elucidate reaction mechanisms on broad classes of materials and in a wide range of operating conditions (e.g., pH, solvent, electrolyte). Such efforts would build on current frameworks for understanding catalysis to provide the deeper insights needed to fine-tune catalyst properties in an optimal manner. The long-term goal is to continue improving the activity and selectivity of these catalysts in order to realize the prospects of using renewable energy to provide the fuels and chemicals that we need for a sustainable energy future.
7,062 citations
TL;DR: This Review will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities in a unifying manner.
Abstract: Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal–support interaction, and metal–reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results o...
2,700 citations
Pacific Northwest National Laboratory1, California Institute of Technology2, Princeton University3, Humboldt University of Berlin4, Pennsylvania State University5, Brookhaven National Laboratory6, University of California, Riverside7, University of Illinois at Urbana–Champaign8, University of California, Berkeley9, United States Department of Energy10, University of Toronto11, University of Michigan12, University of Amsterdam13, Utah State University14, Max Planck Society15, Louisiana State University16
TL;DR: Providing a future energy supply that is secure and CO_2-neutral will require switching to nonfossil energy sources such as wind, solar, nuclear, and geothermal energy and developing methods for transforming the energy produced by these new sources into forms that can be stored, transported, and used upon demand.
Abstract: Two major energy-related problems confront the world in the
next 50 years. First, increased worldwide competition for
gradually depleting fossil fuel reserves (derived from past
photosynthesis) will lead to higher costs, both monetarily and politically. Second, atmospheric CO_2 levels are at their highest recorded level since records began. Further increases are predicted to produce large and uncontrollable impacts on the world climate. These projected impacts extend beyond climate to ocean acidification, because the ocean is a major sink for atmospheric CO2.1 Providing a future energy supply that is secure and CO_2-neutral will require switching to nonfossil energy sources such as wind, solar, nuclear, and geothermal energy and developing methods for transforming the energy produced by these new sources into forms that can be stored, transported, and used upon demand.
1,651 citations
TL;DR: Fossil fuels have offered astounding opportunities during the 20th century in the rich countries of the western world, but now mankind has to face the challenges arising from fossil-fuel exploitation.
Abstract: Each generation is confronted with new challenges and new opportunities. In a restricted system like the Earth, however, opportunities discovered and exploited by a generation can cause challenges to the subsequent ones. Fossil fuels have offered astounding opportunities during the 20th century in the rich countries of the western world, but now mankind has to face the challenges arising from fossil-fuel exploitation. The proven reserves of fossil fuels are progressively decreasing, and their continued use produces harmful effects, such as pollution that threatens human health and greenhouse gases associated with global warming. Currently the world&s growing thirst for oil amounts to almost 1000 barrels a second, which means about 2 liters a day per each person living on the Earth (Figure 1). The current global energy consumption is equivalent to 13 terawatts (TW), that is, a steady 13 trillion watts of power demand. How long can we keep running this road?
1,532 citations
TL;DR: The synthesis of monomers as well as polymers from plant fats and oils has already found some industrial application and recent developments in this field offer promising new opportunities, as is shown within this contribution.
Abstract: The utilization of plant oil renewable resources as raw materials for monomers and polymers is discussed and reviewed. In an age of increasing oil prices, global warming and other environmental problems (e.g. waste) the change from fossil feedstock to renewable resources can considerably contribute to a sustainable development in the future. Especially plant derived fats and oils bear a large potential for the substitution of currently used petrochemicals, since monomers, fine chemicals and polymers can be derived from these resources in a straightforward fashion. The synthesis of monomers as well as polymers from plant fats and oils has already found some industrial application and recent developments in this field offer promising new opportunities, as is shown within this contribution. (138 references.)
1,299 citations
References
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10 Jul 1997
TL;DR: This paper presents a meta-modelling system that automates the very labor-intensive and therefore time-heavy and therefore expensive and expensive process of characterization and activation of Solid Catalysts.
Abstract: Preparation of Solid Catalysts. Characterization of Solid Catalysts. Model Systems. Elementary Steps and Mechanisms. Kinetics and Transport Processes. Deactivation and Regeneration. Special Catalytic Systems. Laboratory Reactors. Reaction Engineering. Environmental Catalysis. Inorganic Reactions. Energy-related Catalysis. Organic Reactions.
4,227 citations
TL;DR: In this paper, the occurrence, production, and origin of natural gas and methane are reviewed, and the physical properties, structure, and chemical reactivity of methane are also reviewed.
Abstract: As the simplest hydride of carbon and the major constituent of natural gas, methane has attracted increased attention in recent years. An important factor has been the recognition of the significance of world natural gas reserves to energy and chemicals production in the 21st century. This expectation is lined to the gradual depletion of oil reserves and to the possible influence of greenhouse global warming effect on energy policy. The combustion of fossil fuel has caused a rise in the CO{sub 2} level in the atmosphere from an estimated preindustrial level of 280 ppm to the current 360 ppm. If current climate models are correct, this may cause a global warming trend in the next few decades. If public resistance to nuclear energy remains strong, natural gas is likely to become a more important energy source. The low C:H ratio of CH{sub 4} means that on combustion it can furnish a much larger amount of energy per CO{sub 2} molecule released than can oil (approximate ratio, CH{sub 2}) or coal (approximate ratio, CH). This article reviews the occurrence, production, and origin of natural gas and methane. The physical properties, structure, and chemical reactivity of methane are also reviewed. 180 refs.
705 citations
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TL;DR: In this paper, Demirdoven et al. discuss the challenges of the transition from hydrogen to electric vehicles and the potential benefits of using hydrogen as a common currency for an energy economy.
Abstract: ### Contents
#### News
The Hydrogen Backlash
The Carbon Conundrum
Choosing a CO2 Separation Techology
Fire and ICE: Revving Up for H2
Will the Future Dawn in the North?
Can the Developing World Skip Petroleum?
#### Review
Stabilization Wedges: Solving the Climate Problem for the Next 50 Years with Current Techologies S. Pacala and R. Socolow
#### Viewpoints
Sustainable Hydrogen Production J. A. Turner
Hybrid Cars Now, Fuel Cell Cars Later N. Demirdoven and J. Deutch
See related Editorial.
S een up close, hydrogen looks like a recipe for success. Small and simple—one proton and one electron in its most common atomic form—hydrogen was the first element to assemble as the universe cooled off after the big bang, and it is still the most widespread. It accounts for 90% of the atoms in the universe, two-thirds of the atoms in water, and a fair proportion of the atoms in living organisms and their geologic legacy, fossil fuels.
To scientists and engineers, those atoms offer both promise and frustration. Highly electronegative, they are eager to bond, and they release energy generously when they do. That makes them potentially useful, if you can find them. On Earth, however, unattached hydrogen is vanishingly rare. It must be liberated by breaking chemical bonds, which requires energy. Once released, the atoms pair up into two-atom molecules, whose dumbbell-shaped electron clouds are so well balanced that fleeting charge differences can pull them into a liquid only at a frigid −252.89° Celsius, 20 kelvin above absolute zero. The result, at normal human-scale temperatures, is an invisible gas: light, jittery, and slippery; hard to store, transport, liquefy, and handle safely; and capable of releasing only as much energy as human beings first pump into it. All of which indicates that using hydrogen as a common currency for an energy economy will be far from simple. The papers and News stories in this special section explore some of its many facets.
Consider hydrogen's green image. As a manufactured product, hydrogen is only as clean or dirty as the processes that produce it in the first place. Turner (p. 972) describes various options for large-scale hydrogen production in his Viewpoint. Furthermore, as News writer Service points out (p. [958][1]), production is just one of many technologies that must mature and mesh for hydrogen power to become a reality, a fact that leads many experts to urge policymakers to cast as wide a net as possible.
In some places, the transition to hydrogen may be relatively straightforward. For her News story (p. 966), Vogel visited Iceland, whose abundant natural energy resources have given it a clear head start. Elsewhere, though, various technological detours and bridges may lie ahead. The Viewpoint by Demirdoven and Deutch (p. [974][2]) and Cho's News story (p. 964) describe different intermediate technologies that may shape the next generation of automobiles. Meanwhile, the fires of the fossil fuel-based “carbon economy” seem sure to burn intensely for at least another half-century or so [see the Editorial by Kennedy (p. [917][3])]. Service's News story on carbon sequestration (p. 962) and Pacala and Socolow's Review (p. [968][4]) explore strategies—including using hydrogen—for mitigating their effects.
Two generations down the line, the world may end up with a hydrogen economy completely different from the one it expected to develop. Perhaps the intermediate steps on the road to hydrogen will turn out to be the destination. The title we chose for this issue—Toward a Hydrogen Economy— reflects that basic uncertainty and the complexity of what is sure to be a long, scientifically engaging journey.
[1]: /lookup/doi/10.1126/science.305.5686.958
[2]: /lookup/doi/10.1126/science.1093965
[3]: /lookup/doi/10.1126/science.305.5686.917
[4]: /lookup/doi/10.1126/science.1100103
268 citations
TL;DR: This paper believes that methanol is the most versatile synthetic fuel available and its use could stretch or eventually substitute for, the disappearing reserves of low-cost petroleum resources, and it hopes that a practical meethanol fuel cell will be commercially available by the time that methnol becomes plentiful for fuel purposes.
Abstract: We believe that methanol is the most versatile synthetic fuel available and its use could stretch or eventually substitute for, the disappearing reserves of low-cost petroleum resources. Methanol could be used now as a means for marketing economically the natural gas that is otherwise going to waste in remote locations. If methanol were used as an additive to gasoline at a rate of 5 to 15 percent, for use in internal combustion engines, there would be an immediate reduction in atmospheric pollution, there would be less need for lead in fuel, and automobile performance would be improved. With increasing production of fuel-grade methanol from coal and other sources, we foresee the increasing use of methanol for electrical power plants, for heating, and for other fuel applications. We hope that a practical methanol fuel cell will be commercially available by the time that methanol becomes plentiful for fuel purposes. Methanol offers a particularly attractive form of solar-energy conservation, since agricultural and forest waste products can be used as the starting material. Indeed, at 1 percent conversion efficiency the forest lands could supply the entire present energy requirements of the United States.
192 citations
146 citations