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Dowson and Styring CO2 Butanol FigUre 7 | Reaction enthalpy profile for the synthesis of butanol from methanol in a carbon dioxide utilization process (NIST, 2017). the Claisen condensation has a slightly positive overall enthalpy of reaction. This, in combination with the reaction entropy, renders this step of the reaction non-spontaneous without consumption of one equivalent of base by use of acid work-up (Davis and Garratt, 1991). However, given the exothermic nature of the overall reaction pathway, a broad estimation of the overall energy cost of the reaction, starting from methanol or methane, can be calculated from the energy requirements of magnesium regeneration, hydrogen production, and Claisen base/acid. Note that this calculation does not include energy costs associated with the drying of the carbon dioxide source and assumes 100% reaction yield. Simultaneously, potential energy recovery of the 15.26 MJ/L exotherm from the reaction process shown in Figure 7, has not been included, which would make the overall process more favorable. While the drying costs will be small in comparison with the other energy requirements such as magnesium electrolysis, reaction yields may be limited. In fact, magnesium electrolysis costs can be minimized by real- izing that the process operates commercially at large scale and so it would be economically more favorable to batch process the regeneration of magnesium as part of that process rather than using dedicated electrolysers. At this stage, energy costs associated with the process alone are considered. A full life-cycle analysis is being carried out to account for all impacts, including the impact of methanol production and transport of the by-product to the electrolysis site. However, a full scope three LCA falls outside the scope of this paper due to the complexity of the analysis. TaBle 2 | Minimum energy cost per liter of butanol fuel produced from methanol and methane. reaction component Magnesium electrolysisa Hydrogen productionb Claisen base/acidc Total energy cost Increase in fuel energyd Energy efficiency required amount 531.2 g/L 88.1 and 66.1 g/L 437.1 g/L – – – alcohol route 13.37 MJ/L 16.80 MJ/L 1.53 MJ/L 31.7 MJ/L 15.4 MJ/L 48.6% hydrocarbon route 13.37 MJ/L 12.60 MJ/L 1.53 MJ/L 27.5 MJ/L 9.74 MJ/L 35.4% aCalculated using magnesium electrolysis cost of 25.2 MJ/kg (Demirci and Karakaya, 2012). bHydrogen electrolysis efficiency of 75% used. c Chloralkali process for base (NaOH) production (Thannimalay et al., 2013). dCalculated by difference in energy density of butanol compared to 2 M equivalent quantities of methanol and methane, respectively. By comparison of the specific energy of the starting materials (methanol and methane, respectively) with the energy density of the butanol product, and then comparing this difference with a reasonable minimum overall energy cost of conversion (includ- ing magnesium regeneration, hydrogen generation, and the stoichiometric acid and base required to complete the Claisen condensation) a calculation of the efficiency of the transforma- tion via this route, with the assumptions listed above, can be made (Table 2). It should be emphasized that Table 2 represents the minimum energy cost of butanol production calculated with the assumptions Frontiers in Energy Research | www.frontiersin.org 8 October 2017 | Volume 5 | Article 26PDF Image | Demonstration of CO2 Conversion to Synthetic Transport Fuel
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