The past several decades have seen a significant rise in atmospheric carbon dioxide levels resulting from the combustion of hydrocarbon fuels. A solar energy based technology to recycle carbon dioxide into readily transportable hydrocarbon fuel (i.e., a solar fuel) would help reduce atmospheric CO2 levels and partly fulfill energy demands within the present hydrocarbon based fuel infrastructure. We review the present status of carbon dioxide conversion techniques, with particular attention to a recently developed photocatalytic process to convert carbon dioxide and water vapor into hydrocarbon fuels using sunlight.

Toward Solar Fuels: Photocatalytic Conversion of Carbon Dioxide to Hydrocarbons

Solar thermochemical production of hydrogen--a review

Thermal energy storage technologies and systems for concentrating solar power plants

To improve the sustainability of transportation, a major goal is the replacement of conventional petroleum-based fuels with more sustainable fuels that can be used in the existing infrastructure (fuel distribution and vehicles). While fossil-derived synthetic fuels (e.g. coal derived liquid fuels) and biofuels have received the most attention, similar hydrocarbons can be produced without using fossil fuels or biomass. Using renewable and/or nuclear energy, carbon dioxide and water can be recycled into liquid hydrocarbon fuels in non-biological processes which remove oxygen from CO2 and H2O (the reverse of fuel combustion). Capture of CO2 from the atmosphere would enable a closed-loop carbon-neutral fuel cycle. This article critically reviews the many possible technological pathways for recycling CO2 into fuels using renewable or nuclear energy, considering three stages—CO2 capture, H2O and CO2 dissociation, and fuel synthesis. Dissociation methods include thermolysis, thermochemical cycles, electrolysis, and photoelectrolysis of CO2 and/or H2O. High temperature co-electrolysis of H2O and CO2 makes very efficient use of electricity and heat (near-100% electricity-to-syngas efficiency), provides high reaction rates, and directly produces syngas (CO/H2 mixture) for use in conventional catalytic fuel synthesis reactors. Capturing CO2 from the atmosphere using a solid sorbent, electrolyzing H2O and CO2 in solid oxide electrolysis cells to yield syngas, and converting the syngas to gasoline or diesel by Fischer–Tropsch synthesis is identified as one of the most promising, feasible routes. An analysis of the energy balance and economics of this CO2 recycling process is presented. We estimate that the full system can feasibly operate at 70% electricity-to-liquid fuel efficiency (higher heating value basis) and the price of electricity needed to produce synthetic gasoline at U.S.D$ 2/gal ($ 0.53/L) is 2–3 U.S. cents/kWh. For $ 3/gal ($ 0.78/L) gasoline, electricity at 4–5 cents/kWh is needed. In some regions that have inexpensive renewable electricity, such as Iceland, fuel production may already be economical. The dominant costs of the process are the electricity cost and the capital cost of the electrolyzer, and this capital cost is significantly increased when operating intermittently (on renewable power sources such as solar and wind). The potential of this CO2 recycling process is assessed, in terms of what technological progress is needed to achieve large-scale, economically competitive production of sustainable fuels by this method.

Sustainable hydrocarbon fuels by recycling CO2 and H2O with renewable or nuclear energy

Carbon dioxide reforming of methane produces synthesis gas with a low hydrogen to carbon monoxide ratio, which is desirable for many industrial synthesis processes. This reaction also has very important environmental implications since both methane and carbon dioxide contribute to the greenhouse effect. Converting these gases into a valuable feedstock may significantly reduce the atmospheric emissions of CO2 and CH4. In this paper, we present a comprehensive review on the thermodynamics, catalyst selection and activity, reaction mechanism, and kinetics of this important reaction. Recently, research has centered on the development of catalysts and the feasible applications of this reaction in industry. Group VIII metals supported on oxides are found to be effective for this reason. However, carbon deposition causing catalyst deactivation is the major problem inhibiting the industrial application of the CO2/CH4 reaction. Ni-based catalysts impregnated on certain supports show carbon-free operation and thus attract much attention. To develop an effective catalyst for CO2 reforming of CH4 and accelerate the commercial application of the reaction, the following are identified to be the most important areas for future work: (1) selection of metal and support and studying the effect of their interaction on catalyst activity; (2) the effect of different promoter on catalyst activity; (3) the reaction mechanism and kinetics; and (4) pilot reactor performance and scale-up operation.

Carbon Dioxide Reforming of Methane To Produce Synthesis Gas over Metal-Supported Catalysts: State of the Art

Thermochemical cycles are a type of heat engine that utilize high-temperature heat to produce chemical work. Like their mechanical work producing counterparts, their efficiency depends on the operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxide (ferrites) working materials. The design concepts utilize two sets of moving beds of ferrite reactant materials in close proximity and moving in opposite directions to overcome a major impediment to achieving high efficiency-thermal recuperation between solids in efficient countercurrent arrangements. They also provide an inherent separation of the product hydrogen and oxygen and are an excellent match with a high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this paper, the counter-rotating-ring receiver/reactor/ recuperator solar thermochemical heat engine concept is introduced, and its basic operating principles are described. Preliminary thermal efficiency estimates are presented and discussed. Our results and development approach are also outlined.

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Roy E. Hogan

Papers

Solar Thermochemical Water-Splitting Ferrite-Cycle Heat Engines

Carbon Dioxide Reforming of Methane in a Solar Volumetric Receiver-Reactor: The CAESAR Project.

Solar reforming of methane in a direct absorption catalytic reactor on a parabolic dish. 2: Modeling and analysis

Solar reforming of methane in a direct absorption catalytic reactor on a parabolic dish: I—Test and analysis

Solar Thermochemical Water-Splitting Ferrite-Cycle Heat Engines