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Chapter 3. Sustainable Hydrocarbon Fuels by Recycling CO2 with Renewable/Nuclear Energy 57 e.g. Fe3O4/Fe2O3 as the reduced and oxidized metal oxides respectively [86]. The introduction of hydroxides is motivated by their higher reactivity compared to that of water which should result in faster reaction rates. The corrosive nature of NaOH, the need to separate liquid NaOH/Mn2O3 mixtures and the reduced efficiency due to having three steps can each present difficulties. In all of these high-temperature cycles, thermal management is extremely important to attain an efficient and economical process. With this in mind, research in solar thermochemical cycles also includes the design and development of efficient heat recuperating solar collectors. Diver et al [24, 73] have developed a counter-rotating ring system to optimize heat exchange between the oxidation and reduction steps, and have demonstrated its use for H2O and CO2 dissociation cycles using modified ferrites supported on YSZ or ceria-doped zirconia with a reduction temperature of 1400 °C. Lower temperature cycles can be suitable for use with heat from nuclear reactors. The 3-step sulfur-iodine (SI) cycle, invented by General Atomics in the 1970s, operates below 1000 °C and has received much attention for integration with heat from high-temperature nuclear reactors [67]. The 4-step calcium–bromine–iron (UT-3) cycle has similarly low operating temperature. The corrosive nature of the chemicals presents material problems. Copper- chloride and magnesium-chloride cycles aim to lessen the corrosion problems of the higher temperature cycles by operating at around 500 °C [66, 67]. These cycles have also been proposed as hybrid electrochemical-thermochemical cycles with electrolysis driving one of the reactions in the cycle in order to lower the maximum cycle temperature by enabling a non- spontaneous step [66, 67]. While a greater number of steps lowers the maximum temperature needed, each additional step lowers the efficiency as more materials must be handled and more heat must be managed, and multi-step cycles often involve corrosive chemicals. The above mentioned cycles are just a few possibilities. Hundreds of possible cycles have been identified for hydrogen production with a variety of maximum operating temperatures [87]. Despite detailed studies of a number of these cycles, they face a number of obstacles: (1) expensive materials (or equivalently, short material lifetimes) associated with high temperatures, rapid temperature transients and/or corrosive chemical intermediates, (2) difficult separations of the chemical intermediates, (3) energy losses across multiple steps from heat exchange, and (4) undesired side reactions. The solar-to-heat conversion efficiency is limited by re-radiation losses and the heat-to-chemicals conversion efficiency is limited by thermodynamics [87, 88], with further energy losses from heat recuperation and from separation and quench steps. Practical efficiencies for the net solar-to-chemicals conversion have been estimated in the range of 16-25%, depending on the process [59]. This is in the same range as what can be attained using solar thermal electric or photovoltaic devices coupled to electrolyzers. The economic benefits from the slightly higher efficiency of a thermochemical process may easily be outweighed by the economic cost of exotic materials. An economicPDF Image | Electrolysis of CO2 and H2O
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