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Chapter 3. Sustainable Hydrocarbon Fuels by Recycling CO2 with Renewable/Nuclear Energy 54 fraction of H2O or CO2 converted. 2500 °C is a reasonable upper limit because high- temperature ceramics such as zirconia begin to decompose at higher temperatures. Such high temperature heat could be supplied by combustion of fuels in an oxygen or chlorine atmosphere, but for thermolytic fuel production this would be self-defeating since more fuel would be consumed for heat generation than could be produced by thermolysis using the generated heat. Concentrated solar furnaces and a variety of electric furnaces are the two other methods that can provide high temperature heat for CO2/H2O thermolysis. Jensen et al have developed a CO2 thermolysis chamber driven by concentrated sunlight. CO2 thermolysis could be carried out at lower temperature than H2O thermolysis according to the thermodynamics (Figure 3-4). In addition, the absorption spectrum of CO2 is shifted at higher temperatures such that in their chamber the CO2 is in part photolyzed by the solar irradiation [22]. The observed peak conversion of solar energy to chemical energy was 5%, with expectation of 20% for a mature system [23]. While the demonstrated yield is low, the system also produced unutilized high temperature heat which could be used to drive a steam turbine, giving an additional 25% efficiency for electrical energy [23] (which could be used to produce more CO or H2 via electrolysisiv, see section 3.2.2.3). If these goals could be met, the total conversion efficiency would be nearly 50%, suggesting a very promising process. However, the majority of energy output from the system is not in the form of thermolysis products but rather electricity, which could have been produced more cheaply. The expensive materials required and complicated gas handling and separations, and heat management, may outweigh the savings from high efficiency. The concentrated sunlight reached ca. 2400 °C in the chamber, indicated by the partially melted zirconia rod at the focal point [23]. The stability of materials can also be strained by thermal shocks due to intermittency of the solar heat source (e.g. rapid transients in sunlight due to clouds). Despite some promising results, because the temperature, materials, and separation requirements for direct solar thermolysis are so severe, development of an economically viable process is unlikely in the near future [59]. An electromagnetic field can be used to excite gaseous H2O or CO2 (or at least the electrons in gaseous H2O or CO2) to extremely high temperatures (thousands to tens of thousands degrees), which results in plasma based decomposition. In so-called thermal plasmas, the electron temperatures are close to that of the discharge gas, whereas in non-thermal plasmas (also called non-equilibrium or cold plasmas), the electron temperature is far above that of the discharge gas [62]. An advantage of plasma based dissociation over direct solar thermolysis is that the high temperature zone is not in contact with any surfaces, so less expensive materials are needed. However, since plasma based dissociation is driven by electricity, it competes with iv Indeed, a study by Baykara et al [61] concluded that H2 production by solar H2O thermolysis is less economical and less efficient than H2 production by processes in which solar H2O thermolysis is combined with H2O electrolysis.PDF Image | Electrolysis of CO2 and H2O
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