Anthropogenic Chemical Carbon Cycle for a Sustainable Future

Review: 595 refs.

Starting with coal, followed by petroleum oil and natural gas, the utilization of fossil fuels has allowed the fast and unprecedented development of human society. However, the burning of these resources in ever increasing pace is accompanied by large amounts of anthropogenic CO2 emissions, which are outpacing the natural carbon cycle, causing adverse global environmental changes, the full extent of which is still unclear. Even through fossil fuels are still abundant, they are nevertheless limited and will, in time, be depleted. Chemical recycling of CO2 to renewable fuels and materials, primarily methanol, offers a powerful alternative to tackle both issues, that is, global climate change and fossil fuel depletion. The energy needed for the reduction of CO2 can come from any renewable energy source such as solar and wind. Methanol, the simplest C1 liquid product that can be easily obtained from any carbon source, including biomass and CO2, has been proposed as a key component of such an anthropogenic carbon cycle in the framework of a "Methanol Economy". Methanol itself is an excellent fuel for internal combustion engines, fuel cells, stoves, etc. It's dehydration product, dimethyl ether, is a diesel fuel and liquefied petroleum gas (LPG) substitute. Furthermore, methanol can be transformed to ethylene, propylene and most of the petrochemical products currently obtained from fossil fuels. The conversion of CO2 to methanol is discussed in detail in this review.

Preface. Part I Climate Physics. 1 The Effect. On the Temperatures of the Terrestrial Sphere and Interplanetary Space (Jean-Baptiste Joseph Fourier (1824)). 2 Wagging the Dog. On the Absorption and Radiation of Heat by Gases and Vapours, and on the Physical Connexion of Radiation, Absorption, and Conduction (John Tyndall (1861)). 3 By the Light of the Silvery Moon. On the Influence of Carbonic Acid in the Air upon the Temperature of the Ground (Svante Arrhenius (1896)). 4 Radiative Transfer. The Influence of the 15 m Carbon-dioxide Band on the Atmospheric Infra-red Cooling Rate (G. N. Plass (1956)). 5 The Balance of Energy. Thermal Equilibrium of the Atmosphere with a Given Distribution of Relative Humidity (Syukuro Manabe and Richard T. Wetherald (1967)). The Effect of Solar Radiation Variations on the Climate of the Earth (M. I. Budyko (1968)). A Global Climatic Model Based on the Energy Balance of the Earth-Atmosphere System (William D. Sellers (1968)). 6 The Birth of the General Circulation Climate Model. The Effects of Doubling the CO2Concentration on the Climate of a General Circulation Model (Syukuro Manabe and Richard T. Wetherald (1975)). Climate Sensitivity: Analysis of Feedback Mechanisms (J. Hansen, A. Lacis, D. Rind, G. Russell, P. Stone, I. Fung, R. Ruedy, and J. Lerner (1984)). 7 Aerosols. Climate Response to Increasing Levels of Gases and Sulphate Aerosols (J. F. B. Mitchell, T. C. Johns, J. M. Gregory and S. F. B. Tett (1995)). 8 Ocean Heat Uptake and Committed Warming. Earth's Energy Imbalance: Confirmation and Implications (James Hansen, Larissa Nazarenko, Reto Ruedy, Makiko Sato, Josh Willis, Anthony Del Genio, Dorothy Koch, Andrew Lacis, Ken Lo, Surabi Menon, Tica Novakov, Judith Perlwitz, Gary Russell, Gavin A. Schmidt and Nicholas Tausnev (2005)). 9 Taking Earth's Temperature. Global Temperature Variations Between 1861 and 1984 (P. D. Jones, T. M. L. Wigley and P. B. Wright (1986)). Contribution of Stratospheric Cooling to Satellite-Inferred Troposphoric Temperature Trends (Qiang Fu, Celeste M. Johanson, Stephen G. Warren and Dian J. Seidel (2004)). Northern Hemisphere Temperatures During the Past Millennium: Inferences, Uncertainties, and Limitations (Michael E. Mann, Raymond S. Bradley and Malcolm K. Hughes (1999)). 10 Ice Sheets and Sea Level. Surface Melt-Induced Acceleration of Greenland Ice-Sheet Flow (H. Jay Zwally, Waleed Abdalati, Tom Herring, Kristine Larson, Jack Saba and Konrad Steffen (2002)). 11 The Public Statement. Man-Made Carbon Dioxide and the Greenhouse Effect (J. S. Sawyer (1972)). Carbon Dioxide and Climate: A Scientific Assessment (Jule G. Charney, Akio Arakawa, D. James Baker, Bert Bolin, Robert E. Dickinson, Richard M. Goody, Cecil E. Leith, Henry M. Stommel and Carl I. Wunsch (1979)). Part II The Carbon Cycle. 12 The Sky is Rising! The Artificial Production of Carbon Dioxide and its Influence on Temperature (G. S. Callendar (1938)). 13 Denial and Acceptance. Carbon Dioxide Exchange Between Atmosphere and Ocean and the Question of an Increase of Atmospheric CO2during the Past Decades (Roger Revelle and Hans E. Suess (1957)). Distribution of Matter in the Sea and Atmosphere: Changes in the Carbon Dioxide Content of the Atmosphere and Sea due to Fossil Fuel Combustion (Bert Bolin and Erik Eriksson (1958)). 14 Bookends. The Concentration and Isotopic Abundances of Carbon Dioxide in the Atmosphere (Charles D. Keeling (1960)). Is Carbon Dioxide from Fossil Fuel Changing Man's Environment? (Charles D. Keeling (1970)). 15 One If by Land. Changes of Land Biota and Their Importance for the Carbon Cycle (Bert Bolin (1977)). Observational Constraints on the Global Atmospheric CO2 Budget (Pieter P. Tans, Inez Y. Fung and Taro Takahashi (1990)). Acceleration of Global Warming Due to Carbon-Cycle Feedbacks in a Coupled Climate Model (Peter M. Cox, Richard A. Betts, Chris D. Jones, Steven A. Spall and Ian J. Totterdell (2000)). 16 Two If by Sea. Neutralization of Fossil Fuel CO2 by Marine Calcium Carbonate (W. S. Broecker and T. Takahashi (1977)). Effects of Fuel and Forest Conservation on Future Levels of Atmospheric Carbon Dioxide (James C. G. Walker and James F. Kasting (1992)). Abrupt Deep-Sea Warming, Palaeoceanographic Changes and Benthic Extinctions at the End of the Palaeocene (J. P. Kennett and L. D. Stott (1991)). 17 On Ocean pH. Anthropogenic Carbon and Ocean pH (Ken Caldeira and Michael E. Wickett (2003)). Reduced Calcification of Marine Plankton in Response to Increased Atmospheric CO2 (Ulf Riebesell, Ingrid Zondervan, Bjorn Rost, Philippe D. Tortell, Richard E. Zeebe and Francois M. M. Morel (2000)). 18 Tiny Bubbles. Evidence From Polar Ice Cores for the Increase in Atmospheric CO2 in the Past Two Centuries (A. Neftel, E. Moor, H. Oeschger and B. Stauffer (1985)). Vostok Ice Core Provides 160,000-Year Record of Atmospheric CO2(J. M. Barnola, D. Raynaud, Y. S. Korotkevich and C. Lorius (1987)). Index.

Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. In contrast, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products can be achieved via its capture and subsequent reductive hydrogenative conversion. The present Perspective reviews this new approach and our research in the field over the last 15 years. Carbon recycling represents a significant aspect of our proposed Methanol Economy. Any available energy source (alternative energies such as solar, wind, geothermal, and atomic energy) can be used for the production of needed hydrogen and chemical conversion of CO(2). Improved new methods for the efficient reductive conversion of CO(2) to methanol and/or DME that we have developed include bireforming with methane and ways of catalytic or electrochemical conversions. Liquid methanol is preferable to highly volatile and potentially explosive hydrogen for energy storage and transportation. Together with the derived DME, they are excellent transportation fuels for internal combustion engines (ICE) and fuel cells as well as convenient starting materials for synthetic hydrocarbons and their varied products. Carbon dioxide thus can be chemically transformed from a detrimental greenhouse gas causing global warming into a valuable, renewable and inexhaustible carbon source of the future allowing environmentally neutral use of carbon fuels and derived hydrocarbon products.

Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. Today, anthropogenic CO2 emissions, mainly from the burning of fossil fuels, also far outpace nature's CO2 recycling capabilities, contributing significantly to the current global warming problem. To supplement and dramatically accelerate the natural CO2 recycling process, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products including hydrocarbons can be achieved via its capture and subsequent reductive conversion in the framework of the Methanol Economy.

Our small planet is now vulnerable to the cumulative effects of our normal activities. There are two specific grand challenges associated with sustainability that are worth our attention—the global carbon cycle and the global nitrogen cycle. Human beings are disrupting the carbon cycle by releasing carbon, dug out of coalmines and oil fields, into the atmosphere. Mainly due to human beings’ activities, the concentration of carbon dioxide in the atmosphere has increased by more than 30% over the last 250 years, with an annual increase of about 0.5%. Two-thirds of the rise has occurred during the past 50 years. Fossil fuel accounts for 85% of the world’s energy system, and has been the principle agent of interference with the natural cycle for carbon. Such a disrupted carbon cycle, with a high carbon dioxide concentration, is posing tremendous challenges, including wide-spread global warming, rising sea level, significant threats to human health, more frequent extreme weather, and harmful disrupted ecological systems, and so on. Unless there is a change, the world will see much higher concentration of carbon dioxide, and it is thus a must for the world to redesign its energy system to become much less dependent on fossil fuels and less harmful to the carbon cycle. Besides the carbon cycle, the nitrogen cycle is another fundamental feature of life on the planet. The nitrogen cycle is also being disrupted by human beings. Organisms on this planet require nitrogen to survive, but the nitrogen in the atmosphere must be modified to be useful. The nitrogen needed by life is produced by “nitrogen-fixing bacteria” that break the triple bond of atmospheric nitrogen (N2, or N≡N) and produce “available” nitrogen. Only a few bacteria can act as “nitrogen-fixing bacteria.” Additional nitrogen fixation is accomplished by lightning. However, for the past hundred years, human beings have been able to produce available nitrogen from atmospheric nitrogen industrially, using the Haber-Bosch process. The most important product, globally, is nitrogen fertilizer, which has enabled a great expansion of the world’s food supply. The world is now more and more dependent on fertilizers to fix nitrogen. And now, more nitrogen is fixed in fertilizer factories than by the bacteria of the world. Another new source of available nitrogen comes from combustion of fossil fuels, which produces nitrogen oxides (“NOx,” which subsumes NO, NO2, N2O5, and other oxides of nitrogen). Significant increases in NOx emissions could occur over the next several decades due to both population growth and per capita increases in fossil-fuel use, although there are many technologies that can reduce NOx emissions. The extra nitrogen fixation today will seriously affect many environment systems—changing the balance of species, producing unwanted biological growth (eutrophication) in aqueous systems, and increasing the emissions of nitrous oxide (N2O, a greenhouse gas) to the atmosphere. International attention to the nitrogen cycle has gradually increased and focuses on the complexity of human alteration of the nitrogen cycle. Coordinated management of the nitrogen and carbon cycles is desirable. Engineering can provide remedies to disrupted ecosystems and has managed to achieve partial successes. There are many reasons to be optimistic that much can be accomplished, the world still has a terribly inefficient system for using carbon and nitrogen, and there is so much room to improve our energy system, food system, and agricultural system. The word “smart” is a key word to describe what engineers can contribute—smart buildings, appliances, infrastructure, vehicles, and food systems, with a core aim to achieve better efficiency. In order to achieve that, we can use a carbon price and a nitrogen price to promote efficient use. Also, we have an enormous amount of global infrastructure still to build, especially in the developing world (Table 1). Crucially, young scientists and engineers now find the challenges of carbon and nitrogen management exciting. As a main engineering method to protect the carbon cycle, carbon dioxide can be captured at a coal plant, then compressed and sent into porous rocks deep below ground. Someday all coal plants may separate the burning of coal from the emission of carbon dioxide. The already existing network of carbon dioxide pipelines in the USA shows that such a route for a low-carbon future

CO2 Capture via Crystalline Hydrogen-Bonded Bicarbonate Dimers

Limits to Paris compatibility of CO2 capture and utilization

’s (2012) conclusion that observed climate change is comparableto projections, and in some cases exceeds projections, allows further inferences ifwe can quantify changing climate forcings and compare those with projections.The largest climate forcing is caused by well-mixed long-lived greenhouse gases.Here we illustrate trends of these gases and their climate forcings, and we discussimplications. We focus on quantities that are accurately measured, and we includecomparison with fixed scenarios, which helps reduce common misimpressionsabout how climate forcings are changing.Annual fossil fuel CO

Our way of life is on a collision course with geological limitations. Ever since petroleum geologist M. King Hubbard correctly predicted in l956 that U.S. oil production would reach a peak in l973 and then decline (1), scientists and engineers have known that worldwide oil production would follow a similar trend. Today, the only question is when the world peak will occur.The U.S. transportation system depends almost entirely (∼97%) on oil (2), and foreign imports have risen steadily since l973 as the demand increased and domestic supplies decreased. Today, more than 60% of U.S. oil consumption is imported and the dependence on foreign oil is bound to increase. There is no question that once the world peak is reached and oil production begins to drop, either alternative fuels will have to be supplied to make up the difference between demand and supply, or the cost of fuel will increase precipitously and create an unprecedented social and economic crisis for our entire transportation system.Among energy analysts the above scenario is not in dispute. There is, however, uncertainty about the timing. Bartlett (3) has developed a predictive model based on a Gaussian curve similar in shape to the data used by Hubbard as shown in Fig. 1. The predictive peak in world oil production depends only on the assumed total amount of recoverable reserves. According to a recent analysis by the Energy Information Agency (4), world ultimately recoverable oil reserves are between 2.2×1012 barrels (bbl) and 3.9×1012bbl with a mean estimate of the USGS at 3×1012bbl. But changing the total available reserve from 3×1012bbl to 4×1012bbl increases the predicted time of peak production by merely 11yr, from 2019 to 2030. The present trend of yearly increases in oil consumption, especially in China and India, shortens the window of opportunity for a managed transition to alternative fuels even further. Hence, irrespective of the actual amount of oil remaining in the ground, peak production will occur soon and the need for starting to supplement oil as the primary transportation fuel is urgent because an orderly transition to develop petroleum substitutes will take time and careful planning.Some analysts claim that hydrogen can take the place of petroleum in a future transportation system (56). But in previous publications, the authors have shown that hydrogen is inferior as an energy carrier to electricity (7) and that the energy efficiency of hydrogen vehicles, especially if the hydrogen were produced by the electrolysis of water, is considerably less than the efficiency of hybrid electric vehicles or fully electric battery vehicles (7). The results of these analyses have subsequently been confirmed by other studies, particularly those by Hammererschlag and Mazza (8) and Mazza and Hammerschlag (9).Before hydrogen could become a useful automotive fuel, an entirely new system of energy production and distribution on twice the scale of today’s electric power generating stations and distribution grid would have to be built. It has been estimated that a hydrogen transmission and storage system to fuel only 50% of the automotive fleet by the year 2020 would cost at least $600 billion (10) and that to make the hydrogen by electrolysis would require doubling the electric power generation rate (11). There is no question that a paradigm shift in fuel for worldwide transportation is imperative, and before embarking on such a huge investment, it is prudent to compare the hydrogen option with alternative ways to provide the energy and/or fuel needed by the transportation system.This paper presents and analyzes two generic approaches to meet the future demand of the U.S. ground transportation systems that do not require hydrogen, can use existing transmission infrastructure, and can eventually reduce CO2 emission drastically with a renewable energy system. Both these pathways are examined from an energetic and environmental perspective and are shown to be superior to the hydrogen economy on both these criteria. The first approach is a demand-side strategy based on the use of electric hybrid vehicles, an energy-efficient vehicle configuration, combined with a liquid fuel. This approach could use the existing liquid-fuel distribution system, but would need an expanded and robust electric-transmission system, albeit on a smaller and much more economical scale than a hydrogen fuel-cell infrastructure. The second approach is a supply-side strategy, based on synthetic fuel generation that can use initially coal or natural gas as the energy source, but can eventually transition to renewable biomass sources. The two pathways are not mutually exclusive, but can be combined into a secure and efficient future transportation system as will be shown in this paper.Cradle-to-grave energy efficiency is an important criterion for comparing energy-source utilization pathways because if a pathway is less efficient than another pathway that accomplishes the same final goal from the same amount of primary energy, then the less efficient pathway requires more primary energy to accomplish the same end. Hence, if the primary energy source is nonrenewable, then the less efficient pathway leaves less of the energy source for the future. It also means that more pollution is produced and the cost for the final end use is likely higher. However, if the primary energy source is renewable, then the efficiency does not change the amount of primary energy available in the future and energy efficiency does not have the same significance for renewable energy sources as for nonrenewable sources. Efficiency is, of course, important because the cost of delivering the energy is usually strongly influenced by the system efficiency. But a comparison between renewable and nonrenewable pathways should be based on economic and environmental criteria, such as cost and CO2 generation.In order to demonstrate the urgency for initiating a plan to supplement oil as soon as possible, we have made calculations to predict the potential gasoline savings based on the very optimistic scenario that, at an arbitrary starting time, all new light vehicles sold in the U.S. would be either hybrid or electric vehicles. The term “light vehicles” as used here includes all automobiles, family vans, sports utility vehicles, motorcycles, and pickup trucks. This scenario is an extreme case to show that because of the slow turnover of the light-vehicle fleet, it takes a long time for a significant impact on gasoline consumption to occur. The following cases are considered: (i) All new vehicles sold are gasoline-electric hybrid vehicles (HEV); (ii) all new vehicles sold are plug-in, gasoline-electric hybrids with a 20mil electric-only range (PHEV20); (iii) all new vehicles are diesel-electric hybrids (DHEV) with diesel fuel from coal or biomass; (iv) all new vehicles are plug-in, diesel hybrids with a 20mil all-electric range (PDHEV20); or (v) all new vehicles are all-electric vehicles (EV).The calculations use a rate of new vehicle sales of 7% of the fleet per year, a retirement rate of 5%/y, and a resulting net increase in total vehicles of 2%/y. These numbers represent an approximate fit to the light-vehicle sales and total number data for the years 1966 to 2003 reported by the U.S. government (12). All calculated results are presented in percentages and are therefore independent of the time at which all new vehicle sales switch to hybrids or EVs. When new car sales begin to be all hybrids or all EVs, it is assumed that the future rate of retirement of vehicles from the all-gasoline fleet is 5%/y of the remaining gasoline vehicles. The all-gasoline fleet is therefore completely retired 20 years later. The yearly rate of retirement of hybrid or EV vehicles is then 5% of the total number of vehicles at the beginning of that year, less 5% of the number of gasoline vehicles at the beginning of year zero. Thus, in year zero, no hybrid or EVs are retired.The following average vehicle mileage values were used: gasoline fleet, 21mpg (miles per gallon); gasoline HEV, 41mpg; gasoline PHEV 20, 56mpg of gasoline (13). A mileage is not needed for the EVs, or the diesels, since neither use gasoline, and we assume that the diesel fuel will be derived from nonpetroleum sources, as discussed in Secs. 34.The results of these calculations are presented in Figs. 234. Figure 2 shows the ratio of the total number of vehicles in the fleet, the number of all-gasoline vehicles in the fleet, and the number of hybrid or EV vehicles in the fleet to the total number in the fleet as a function of time. The total number of vehicles increases by over 60% in 25 years at the assumed 2%/y net increase while the number of all-gasoline vehicles decreases linearly from 100% initially to 0% after 20y. The number of hybrid or EV vehicles increases from 0% initially to 58% in 10y and 100% in 20y. This graph emphasizes how long it takes for the introduction of a new vehicle type to show a significant impact on the composition of the vehicle fleet, even when only the new vehicle types are sold after a starting point. This slow turnover of the fleet is the fundamental reason that the effects on gasoline consumption show up so slowly.Figure 3 shows the annual reduction in gasoline consumption as a function of time. Note that for HEVs the annual savings in gas consumption is 29% of the gasoline consumption for a conventional fleet in the tenth year and becomes constant at 49% in the twentieth year. Figure 3 also shows that the plug-in gasoline hybrid scenario saves 41% of the usage in the tenth year and increasing to 64% in the twentieth year and thereafter. Clearly, 10y after starting to sell only hybrid or EV vehicles, the impact of the HEV or PHEV20 scenarios on gasoline consumption is still rather small. After 20yr, the impact becomes significant, but gasoline consumption still remains high for gasoline hybrids. The total number of vehicles and the consumption (with the assumption of no efficiency improvement) by an all-gasoline fleet will have increased by more than 60%, but even the PHEV20 savings is only 40% of the zero-time annual-rate of gasoline consumption. The DHEV, DPHEV20, and EV scenarios show 59% annual savings in the tenth year and 100% in the twentieth year and thereafter. As would be expected, the nongasoline vehicles have a much greater impact on gasoline usage than gasoline-using HEVs, and the impact occurs more rapidly.Figure 4 gives the cumulative gasoline savings for the various scenarios compared to an all-gasoline fleet. HEVs save cumulatively 16% after 10yr and 20% after 20 years. Because of the cumulative savings, HEVs would use in 28yr the same amount of gasoline as an all-gasoline fleet would use in 20yr. PHEV20s save 21% after 10yr and 38% after 20yr. These results emphasize the relatively small effect on gasoline consumption that these highly optimistic scenarios have in the first decade after implementation. DHEVs, DPHEV20s, and EVs, the options without any gasoline use, save cumulatively as much as 32% after 10yr and 59% after 20yr.A 2004 report of the Committee on Alternatives and Strategies for Future Hydrogen Production and Use (14), prepared under the auspices of the National Research Council (NRC), concluded that the vision of a hydrogen economy is based on the expectation that hydrogen can be produced from domestic energy sources in a manner that is “both affordable and environmentally benign.” An analysis of currently available technologies for achieving this goal (7) showed that irrespective of whether fossil fuels, nuclear fuels or renewable technologies are used as the primary energy source, hydrogen is inefficient compared to using the electric power or heat from any of these sources directly. Given these facts, it is important to note that the NRC report also stated that “If battery technology improves dramatically, all-electric vehicles might become the preferred alternative (to fuel cell electric vehicles).” The report also noted that “Hybrid vehicle technology is commercially available today and can therefore be realized immediately.” If synthetic fuels made from coal, natural gas, or biomass were used in place of gasoline in hybrid vehicles, the consumption of oil could be reduced immediately and eventually eliminated. In the light of these observations, it is therefore important to examine what the current state of battery technology is, what can be expected in the near future, and how these developments affect the potential of hybrid vehicle performance and economics.To assess the performance of a battery for electric vehicles, the following characteristics have to be considered: Specific energy, a measure of the battery weight in units of watt hours per kilogramEnergy density, a measure of the space the battery occupies in watt hours per cubic meterCapacity, the total quantity of energy a battery can store and later deliver in watt hoursEfficiency, the ratio of energy that can be extracted from the battery to the initial energy input to change the batterySpecific power, the rate at which the battery can deliver the stored energy per unit weight of battery in watts per kilogramBattery lifecycle, the number of charge and discharge cycles that a battery can sustain during its lifeA significant effort to replace oil as a transportation fuel was undertaken ten years ago in California, when the California Air Resources Board [CARB] mandated that a certain percentage of all vehicles sold in California had to have zero tailpipe emissions (15). At that time the only technology available to meet the mandate was the all battery electric vehicle [BEV], which required no gasoline for its operation. The experiment to mandate the use of BEVs in California failed because the technology was not ready for commercialization. The best battery available in 1995 (fluted-tubular lead acid) had an energy storage density of 35Wh∕kg, a specific power of 100W∕kg, and a life cycle of 600-1000cycles. With these battery characteristics, the maximum range of a BEV was only 50mil, and the battery pack required replacement every 25,000mil at a cost of between $7000 and $8000 for an average BEV (16). Since that time, new batteries have been developed by Panasonic, VARTA, and SAFT, that have twice the energy-storage density, three times the specific power, and two or three times the cycle life of the lead acid batteries sold in California, as shown in Table 1 (13).In addition to the advanced batteries, a new concept has been developed that combines the best qualities of hybrid and battery vehicle technologies. This “plug-in hybrid vehicle” can recharge vehicle batteries during off-peak hours, and since most cars are parked 90% of the time, there are plenty of charging opportunities at both home and the workplace. Furthermore, a large portion of the electric generation infrastructure is only needed for peak demands and lays idle much of the time. Hence, if charging automobile batteries occurred during off-peak hours, they would level out the load of the electric production system and reduce the average cost of electricity (17). Moreover, plug-in hybrid vehicles are not range limited because they have an engine that can refuel at existing gas stations to use when the batteries are low.The efficiency of a PHEV depends on the number of miles the vehicle travels on liquid fuel and electricity, respectively, as well as on the efficiency of the prime movers according to1η=energytowheelsenergyfromprimarysource=f1η1η2+f2η3η4where η1 is the efficiency of the primary source of electricity, η2 is the efficiency of transmitting electricity to the wheels, f1 is the fraction of energy supplied by electricity, f2 is the fraction of energy supplied by fuel =(1−f1), η3 is the efficiency of primary source to fuel, and η4 is the efficiency of fuel to wheels.PHEVs can be designed with different all-electric ranges. The distance, in miles, that a PHEV can travel on batteries alone is denoted by a number after PHEV. Thus, a PHEV20 can travel 20mil on fully charged batteries without using the gasoline engine. According to a study by EPRI (13), on average 1/3 of the annual mileage of a PHEV20 is supplied by electricity and 2/3 by gasoline. The percentage depends, of course, on the vehicle design and the capacity of the batteries on the vehicle. A PHEV60 can travel 60mil on batteries alone, and the percentage of electric miles will be greater as will the battery capacity.The tank-to-wheel (more appropriately, battery-to-wheel) efficiency for a battery all-electric vehicle according to EPRI (13) is 0.82. In a previous analysis by the authors (18), the efficiency in 1993 was only 0.49. Comparing these results shows the enormous improvements in the electric component efficiency (controller 87%, battery 90%, charger 90%, drivetrain 90%;). When these numbers are multiplied by a hybrid-weight-times-idle factor of 1.3 (19), the overall efficiency of an electric hybrid is 82%, the same as that used in the EPRI study (13). It is important to note that currently all-electric vehicles can be nearly twice as efficient as when (18) was published.Given the potentials for plug-in hybrid vehicles, the Electric Power Research Institute (13) conducted a large-scale analysis of the cost, the battery requirements, and the economic competitiveness of plug in vehicles today and within the near term future. Table 2 presents the net present value of life-cycle costs over ten years for a midsized combustion vehicle [CV], hybrid vehicle [HEV] and a plug in electric vehicle with a 20mil electric-only range [PHEV20]. The battery module cost in dollars per kilowatt is the cost at which the total life-cycle costs of all three vehicles would be the Figure presents cost for battery as a function of number of units produced per year. According to this a production of about units per year units would the cost reduction to make both hybrid electric vehicles and plug in electric vehicles 3 presents the electric and plug-in hybrid vehicle battery that would be to make electric vehicles cost for vehicles according to EPRI (13). As shown in Table the characteristics of batteries, and batteries are to meet the required cost and performance The battery characteristics shown in Table 1 and Fig. are years and it is likely that more from would show Furthermore, the EPRI study assumed a current gasoline cost of A of the analysis based on a gasoline cost of that the battery at which the net present values of conventional combustion vehicles and battery vehicles are would up from to for an HEV and from to for a PHEV Figure shows the cost for batteries production for Hence, it that the cost of HEVs and with available batteries is with that of engine The EPRI analysis is because it compared the performance of all battery electric and plug in hybrid vehicles only to currently available combustion as shown in the use of diesel in a hybrid would increase the efficiency of compared to a hybrid with engine and the amount of fuel Hence, it be concluded that the EPRI analysis is it includes advanced batteries, it does not the increased efficiency by using diesel of combustion Furthermore, diesel fuel, as will be shown in can be produced from coal or renewable sources as can the electric power required for charging the The introduction of to the energy is the of this it is and can be as renewable technologies become more cost and fossil fuels more natural gas and biomass can be into liquid the most fossil fuel in the is used almost to In order to make coal into a vehicle fuel, it first be to a gas by a of The of this then be to of that can be used as vehicle fuel. biomass and natural gas can be used of coal or combined with coal to make these and are discussed gas can be used as a vehicle fuel, or it can be with to make gas, which can be used to fuels in the same manner as for The technology is well developed as shown by the recent of of which will natural gas, which is currently to liquid fuel. These and a in of which is diesel in With a with an estimated billion and a diesel with the of with an estimated at The of natural gas to make vehicle fuels was discussed in an paper by the authors (18), and of those results are presented later for comparison with coal as the fuel It should also be noted that biomass can be either alone or in with coal and to liquid fuels by the same as coal, or it can also be and then into vehicle fuels as in is a that is a in the production of synthetic liquid fuels from coal for transportation The coal is shown in Fig. It a such as coal or with to and This gas can be to hydrogen or to make or can be used as a transportation fuel in but this study on diesel fuel because are more the first of the coal is with limited to and The in the coal is to hydrogen gas, and are as In the shift is with to and The and hydrogen are from the and to the or into The that is in this is from the in a for Thus, it can be from the and are the costs when liquid fuel is produced from The estimated time of for a is to years. The depends on the production capacity of the the cost of a with a capacity to barrels of liquid fuel per is estimated to be of the order billion of coal claim that there will be gas pollution from the However, in the future vehicle emissions of can be reduced those of vehicles, by the use of plug-in hybrid electric vehicles and by of the from the fuel production is a synthetic diesel fuel that can be made from coal by of The is first to make which can then be to The is to the and the gas is to electricity for the as shown in Fig. is a gas at but can be under and then can be to other liquid of make it an fuel for It is similar to but has a number The number to the of a fuel to With combustion of the fuel occurs after and emissions are as a of combustion The combustion also in by the need for to the shown in Fig. coal into liquid fuel. The was by scientists before and is used today in by to make diesel fuel gas to make a liquid fuel of synthetic diesel fuel, which is similar to and which is used to make synthetic gasoline (7). The is from the liquid diesel and to the The gas resulting from is to electricity for the can be made from coal by by gas After the hydrogen gas and are from the gas, and hydrogen are The hydrogen can be stored and the can be for electricity and/or to the shift as shown in Fig. store and the hydrogen, it is either to it to or to it at a The efficiency of the first option is while the second is efficient (7). Both and hydrogen have been for fuel storage in a of hydrogen fuel-cell vehicles is in the of coal or natural gas into a vehicle fuel. The energy efficiency of these is important in the overall well to efficiency of these alternative Table 4 presents or efficiency for various fuels from coal or natural and have reported the and energy for with of the and values are used (18) presented for natural gas without and estimated that of CO2 the efficiency of by about two percentage Since natural gas only about as much per unit of energy as coal, it has been assumed that will reduce the efficiency of to fuels by percentage point. Thus, percentage has been from values reported by (18) to the values shown in Table In the of data for the of natural gas to the authors assumed that the ratio of the for natural gas is the same as that for coal to estimate this efficiency as shown in Table 4 that the production of liquid fuels from natural gas is more efficient than from But is in and the technology is not a It is however, for the that is currently into the in gasoline The of of these has been But production is the more for the term and does not require hydrogen as a fuel or energy Today, the of fuel from coal, at the only in The of supplies of such fuels as gasoline, and The economic and of coal have been U.S. and for a fuel in using technology and are to the that will have a capacity to of diesel fuel. has in recent NRC study other technologies that could synthetic fuels from biomass and presents a comparison of the energy on energy for production from and These significant in synthetic But the for synthetic fuel production need to be multiplied before synthetic fuels can make up for the between demand and of gasoline after the peak in oil production is on the analysis presented in this we the following and oil production is expected to peak within the and as is liquid fuel are expected to increase This could lead to a crisis in the U.S. transportation system that on 60% of which is options for a transportation crisis by and/or liquid fuels derived from petroleum with synthetic fuels from natural gas, or coal and by demand by increasing the efficiency and mileage of options to have impact they be at least before hybrid vehicles are a option to reduce the liquid fuel consumption of future transportation hybrid vehicles can the existing infrastructure for electric power transmission by charging batteries during peak hours and use liquid fuels only for a fraction of overall power hybrid vehicles can diesel that can be by synthetic fuels derived from coal, natural gas, or use efficiency is increased efficiency alone will not be to the transportation without the production of large of synthetic liquid number of technologies for synthetic diesel that can be used in diesel and reduce emission of that lead to scale of effort required to provide synthetic fuels will require years to and should therefore be as soon as hybrid or all-electric vehicles with available battery technology in an are compared to gasoline of the of the transportation it is that be by government such as for the of synthetic fuels and CO2 high liquid fuel mileage for automobiles, and for efficient plug-in hybrid scenario in this paper for a secure transportation system can be immediately with available technologies and without hydrogen or authors to for as of an independent study for the of at the of

Alcohol Production from Carbon Dioxide: Methanol as a Fuel and Chemical Feedstock

Making synthetic fuels for the road transportation sector via solid oxide electrolysis and catalytic upgrade using recovered carbon dioxide and residual biomass

Rapidly increasing levels of atmospheric carbon dioxide and their damaging impact on the global climate system raise doubts about the sustainability of the fossil resource based energy system. Meanwhile, raising living standards and increasing global population lead to an ever growing need for energy. Renewable energy sources are believed to present a solution to these problems with the sheer abundance of solar energy showing particular promise to fulfill the world's energy needs. However, for large scale application of solar energy to be possible, the problem of its storage has to be addressed. The insufficient flexibility of present-day storage technologies has led to the quest for producing solar fuels, centering on hydrogen as a fuel in a prospective hydrogen economy. Nevertheless, the gaseous state, low volumetric energy density and explosive nature of hydrogen makes it a challenging fuel for practical applications. Using solar energy to produce carbon-based liquid fuels solves these challenges, closes the anthropogenic carbon cycle and allows for the continued utilization of existing infrastructures. A promising method for the production of such fuels consists in the photoelectrochemical and electrochemical conversion of carbon dioxide. In this thesis, both methods are investigated using molecular homogeneous catalysts and heterogeneous systems. The photoelectrochemical reduction of carbon dioxide on TiO2-protected Cu2O photocathodes was investigated using a rhenium bipyridyl catalyst in solution. Important charge transport limitations were encountered, which could be overcome by the addition of protic additives to the electrolyte. Improving on this result, the molecular catalyst was covalently immobilized on the TiO2 surface of the photocathode by modifying the bipyridyl ligand with a phosphonate binding group. A nanostructure of TiO2 was needed to support sufficient catalyst to sustain the photocurrent generated by the Cu2O photoelectrode. The complete device showed photocurrents exceeding 2.5 mA cm-2 and large faradaic efficiency for the production of CO. Moving toward heterogeneous catalysis, the promotion of the CO2 to CO conversion reaction on silver surfaces by imidazolium cations was investigated. Replacing the imidazolium C2 proton with a phenyl substituent led to an enhancement of the co-catalytic effect. Replacing the C4 and C5 protons with methyl groups, however, suppressed the catalysis-promoting effect of the imidazolium salt for different C2 substituents and led to new insights into the role of imidazolium. The unassisted solar-driven splitting of CO2 into CO and O2 was demonstrated using water as electron source. This was achieved by the use of a porous gold cathode and an IrO2 anode, driven by three methylammonium lead iodide perovskite solar cells in series. Extended operation over 18 h was shown, achieving a solar to CO efficiency exceeding 6.5 %. Atomic layer deposition (ALD) modification of CuO nanowire cathodes with SnO2 was investigated, leading to striking impacts on the catalytic selectivity of this system. In an aqueous electrolyte, bare CuO led to the production of a wide spectrum of products, which was modified to the production of CO with high selectivity upon ALD modification. By exploiting the oxygen evolving activity of SnO2-coated CuO, a low cost bifunctional system was constructed, achieving sustained solar-driven production of CO with up to 13.4% efficiency.

Chapter 3.26 - Toward a Sustainable Carbon Cycle: The Methanol Economy

Understanding the mechanisms governing the evolution of the ocean’s anthropogenic carbon reservoir is critical for assessing its role in the global carbon cycle and susceptibility of the ocean carbon sink to climate change. Anthropogenic carbon, primarily from fossil fuel burning, interacts with and alters the natural carbon cycle, increasing the vulnerability of surface waters to natural carbon leaks. To address these dynamics, we quantify the mechanisms affecting oceanic anthropogenic carbon, including ocean circulation, biological production, and carbonate chemistry, using the Max Planck Institute Earth System Model. By disentangling the multi-factors through separating the evolutions of natural carbon—pre-industrial oceanic carbon pools—and anthropogenic carbon, we aim to develop a clearer and more comprehensive understanding of the ocean carbon cycle. Utilizing idealized emissions-driven simulations, we assess the sensitivity of the ocean carbon sink under varying emission pathways, such as increasing and decreasing CO2 emissions. This mechanistic understanding is crucial to understanding the vulnerability of the ocean carbon sink and monitoring the carbon budget. By linking these insights to the Transient Climate Response to cumulative CO2 Emissions (TCRE), this study contributes to a framework for evaluating carbon cycle feedback under diverse emission pathways.