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Chapter 3. Sustainable Hydrocarbon Fuels by Recycling CO2 with Renewable/Nuclear Energy 53 Low-temp electrolysis, Photo(electro)lysis High temperature electrolysis Thermochemical cycles Thermolysis a) 300 250 200 150 100 50 0 0 500 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 H: CO2 = CO + 1⁄2O2 H:H2O=H2 +1⁄2O2 1000 1500 2000 2500 3000 3500 4000 T (°C) b) 30 20 10 0 -10 -20 -30 -40 -50 (WGS) CO+H2O CO2 +H2 (RWGS) CO2+H2 CO+H2O G H 0 500 1000 1500 T (°C) Figure 3-4. Thermodynamics of CO2 and H2O reduction reactions (a) and water-gas shift (b), using thermodynamic data from [1]. The electrochemical cell potential corresponding to the energy input is on the right vertical axis. The temperature ranges of the various methods of reducing CO2 and H2O are also labeled. Note that thermochemical cycles accomplish the reactions indirectly whereas the other methods all directly split the oxide. At temperatures higher than about 827 °C, the free energy of splitting CO2 is lower than that of H2O, and correspondingly the reverse water-gas shift (RWGS) reaction becomes favorable. 3.2.2.1. Thermolysis It is possible to split H2O and CO2 by thermolysis (by the direct use of heat) at extremely high temperatures. The thermodynamics of CO2 and H2O dissociation shows that thermolysis occurs fully only at temperatures exceeding 3000 and 4000 °C respectively (Figure 3-4). Literature mentions a temperature range of 2000-2500 °C for H2O thermolysis [58-60], although the equilibrium constant is only around 0.02 [1] and the product gases, H2 and O2, must be separated effectively at high temperature, or rapidly quenched to avoid recombination and then separated at lower temperature. Recombination reduces both the efficiency and Cell voltage kJ kJPDF Image | Electrolysis of CO2 and H2O
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