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A APPENDIX A: UTILIZATION OF CO2 Heterogeneous photoreduction of CO2 requires presence of sacrificial hole traps (or electron donors) such as n-propanol, tertiary amines, or EDTA in order to get high yield. These compounds are more valuable than the CO2 reduction products. However, sulfide or sulfite ions are available as waste products. In the petrochemical and metallurgical industries and from fossil-burning fuel stations, huge amounts of H2S or SO2/SO3 are released. The oxidation of these compounds are beneficial environmentally. Hence, use of these as hole scavengers can lead to a high-yield photocatalytic process for CO2 reduction. High Energy Radiation Decomposition of CO2 Irradiation of CO2 with high energy radiation (gamma, electron, and other fission fragments) decomposes it to CO and O2. Further irradiation of CO reduces it to C3O4, which is a polymer and can be used as a building block for various organic compounds [25]. However, 12,400 MW(t) of nuclear power is estimated for a 1000 MW(e) coal- fired plant. This does not appear to be cost effective or practical. UV generation from a solar power plant can be used for photochemical decomposition of CO2 to CO and O2. For a 1000 MW(e) fossil-fuel plant, 180,000 MW(t) is required. Improvement in energy efficiency is needed before this becomes viable. Thermal decomposition of CO2 to CO and O2 is not considered viable due to the extremely high temperature (2500C) required. Synthesis of Chemicals from CO2 As discussed earlier, several chemicals can be synthesized using CO2 as a building block. Some examples are given below [25], [30]: • DMC synthesized from methanol and CO2 over zirconia catalysts with the addition of H3PO4 – DMC can be used as a fuel additive. • Utilization of CO2 for direct, selective conversion of methane to ethane and ethylene with Ca-based binary catalysts. Reaction for oxidation with CO2 – • Copolymerization of CO2 with epoxides (carboxylation) such as propylene oxide to yield poly-ether-carbonate, avoiding use of a more toxic compound such as phosgene. Since CO2 is relatively un-reactive, an effective catalyst is needed. The worldwide demand for polycarbonates is growing worldwide by >10% per year. Using these compounds instead of metals/cement for building materials will mitigate CO2 release to the atmosphere, since the metal and cement industry is highly energy intensive. • CO2 reduction by natural gas using multi-functional catalysts to yield methanol, ethanol, light olefins, gasoline. • Styrene produced by dehydrogenation of ethylbenzene over iron oxide catalysts in presence of large excess of steam is energetically wasteful. Dehydrogenation of ethylbenzene in excess CO2 yields styrene with considerably less energy. • Toluene reforming by CO2 to benzene, CO, and H2. • Decomposition of propane by CO2 on chromium oxide and ZnO catalyst to yield propene, CO, and water. 91PDF Image | Analysis for Recovering Energy from Industrial Waste Heat
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