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Chapter 3. Sustainable Hydrocarbon Fuels by Recycling CO2 with Renewable/Nuclear Energy 55 the other method of electrically-driven dissociation, electrolysis. Givotov et al [63] reported an electricity-to-fuel energy efficiency of 80% for non-thermal plasma decomposition of CO2, however CO2 conversion was only 20%, which would require more energy to be spent on subsequent gas phase separation of CO, O2 and CO2. Much higher (>90%) CO2 conversion has been demonstrated using plasma micro-reactors, at the expense of reduced efficiency [64, 65]. For plasma decomposition of H2O, Givotov et al [63] reported a lower efficiency (<40%) than for CO2 plasmolysis, with lower conversion as well (<6%). At present, electrolysis is superior to plasma based dissociation because it provides a higher efficiency conversion with the products automatically separated (see section 3.2.2.3). However, it is not impossible that plasma based dissociation could become feasible if the efficiency and rates can be improved and if the cost of the reactors is relatively lower than that of electrolyzers. 3.2.2.2. Thermochemical cycles Thermochemical cycles split H2O or CO2 through a series of thermally driven chemical reactions at lower temperatures than thermolysis. Product separation is simpler and often inherent in the cycle’s reaction steps; one step will yield the H2 (or CO) and a separate one will yield the O2. Such cycles can be driven by nuclear reactor heat [66, 67] or concentrated sunlight [59, 60, 68]. Two-step cycles are most often based on reducing a metal oxide while evolving the O2 in the first step and in the second step oxidizing the metal or lower-valence metal oxide by reaction with H2O (or CO2) thereby producing H2 (or CO): MxOy MxOy-1 + 1⁄2 O2 (g) MxOy-1 + H2O(g) MxOy + H2 (g) The first step requires temperatures up to 2000 °C depending on the cycle. Fewer steps results in lower losses associated with products separation, heat transfer, and transfer of materials between each step. However, there are cycles with 3 or more steps with a maximum temperature below 1000 °C. The high temperature (usually 2-step) cycles are considered with concentrated solar heat because concentrated sunlight can provide high temperature heat. The high temperature step places thermal demands on materials, and may require difficult product separation. Both of these disadvantages are shared with direct thermolysis, because both processes operate at extreme temperatures. The most well known of this type of cycle is the ZnO/Zn cycle: ZnO(s) Zn(g) + 1⁄2O2(g) 1600-2000 °C Zn(s) + H2O(l) ZnO(s) + H2(g) 300-400 °C The ΔGr of the first step is zero at 1982 °C [59]. In the high temperature step, a gaseous phase of the reduced Zn metal is produced. The gaseous Zn and O2 require quenching to avoidPDF Image | Electrolysis of CO2 and H2O
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