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Dowson and Styring CO2 Butanol be vigorously dried. While this would normally represent a considerable energy penalty for the process in terms of more standard capture approaches, compared with the electrolysis of one molecular equivalent of magnesium salt per molecule of CO2 captured, the energy cost is relatively small. Furthermore, there is the possibility that the drying process could be carried out using the otherwise non-recoverable portion of the exothermic heat (waste heat) from the reaction process to thermally cycle drying agents. In any case, the flue gas will need to be dried irrespective of the capture process, either post-capture in the case of amines or pre-capture for membranes or direct CDU. Trace levels of water that are carried through to the Grignard reaction will cause the formation of methane and Mg(OH)X. The methane could potentially be recycled to increase the CO2:O2 ratio in the flue stream or otherwise utilized/reclaimed. The other product, Mg(OH)X, would be converted to the standard MgX2 by-product after the general Grignard quench with HX. Some care would have to be taken to avoid the formation of MgO, which is not typically reduced by electrolysis in the same way as MgX2, although this too is relatively easily converted back to MgX2. Overall, the presence of small quantities of water would primarily serve to only reduce reaction yield. Previous work car- ried out by our group has indicated that the reaction of Grignard reagents with oxygen is relatively slow compared to its reaction with CO2, although flue gas streams with very high oxygen levels may see trace amounts of the oxygen products, MgO, methanol, and possibly dimethyl ether (Goebel and Marvel, 1933; Dowson et al., 2015). Without these undesirable reactions, the post-quench products of the reaction of Grignard reagents with CO2 are carboxylic acids, which are not typically used as liquid fuels, although they can be used to generate biodiesel esters. Further conversion steps are therefore required for the generation of a more conventional advanced fuel. One potential advanced fuel target would be butanol. Butanol is well recognized to be a potential drop-in replacement for petrol in road vehicles as well as a suitable blending agent for diesel engines (Yao et al., 2010). Unlike ethanol, which can only be blended with hydrocarbon fuels up to certain limits due to its corrosivity and hydrophilicity, butanol is lipophilic and non-corrosive (New Zealand Ministry of Transport and SGS Industrial, Penrose 2009). Furthermore, it has a slightly higher energy density (36.0 MJ/L) than gasoline (34.2 MJ/L), and similar burn rate and octane number, allowing completely unmodified vehicles to run on both butanol alone and butanol/petrol fuel blends (Szulczyk, 2010; Xu and Avedisian, 2015). Butanol further allows higher ethanol concentrations to be used within blended fuels, as it solubilizes ethanol in the bulk petrol and prevents ethanol volatilization (Yanowitz et al., 2011). As a CDU fuel, butanol is also attractive as it requires significantly less hydrogen to produce it from CO2 than the proposed synthetic hydrocarbons suitable for petrol engines. This is due to its relatively high density, partial oxidation, and shorter chain length. Simple stoichiometric calculations show that 15% less hydrogen per liter and 26% less hydrogen per kilogram is required in the product fuel than for synthetic octanes. Given the limitations in energy efficiency of hydrogen generation from water electrolysis, this presents a potentially significant energy advantage for butanol production (Dincer and Acar, 2015). Furthermore, as a single-component fuel, it does not encounter issues with the absence of branched and aromatic compounds in synthetic hydrocarbons that reduce the octane numbers of methanol-to-gasoline and Fisher–Tropsch products to unsuitable levels (Dry, 2002). The fact that it can be used as a single-component fuel potentially allows for higher general engine efficiency to be achieved even than conventional petrol as the combustion characteristics are entirely uniform and not disrupted by variations in low-octane components, when the butanol is being used alone (Irimescu, 2012). The other advantage is that mixtures of butanol isomers can be directly used as drop-in fuels, meaning that isomer mixtures do not need to be separated prior to use. However, the production of butanol from carbon dioxide, other than via biological processes or syngas, has previously only been reported as trace production in the high temperature/ pressure hydrogenation of CO2 in water by platinum/cobalt catalysts (He et al., 2016). Here, we report a route to produce butanol-based fuel that is suitable for petrol-based applications in a multi-step-moderate-yield process. This has the potential to become a moderate-to-high yield process from CO2 once fully optimized. The reported process is demonstrated under near- ambient conditions for the major synthesis steps. eXPeriMenTal MeThODs All reagents and deuterated solvents were purchased from Sigma-Aldrich at the highest available purity and were used without further purification. Schlenk-line techniques, used where indicated, were carried out using furnace-dried glassware under a dry nitrogen atmosphere. The apparatus was purged at least three times prior to handling of air-sensitive Grignard reagents. All solvents were purchased from VWR at HPLC grade or higher and were used without further purification. H2, CO2, N2, O2, and dry synthetic flue gas (12% CO2, 88% N2) were sup- plied by BOC-Linde. Catalyst pre-treatment and hydrogenation experiments were carried out in a 250-mL stainless steel Parr autoclave with heating mantle and glass insert and were stirred magnetically using an IKE stirrer hot-plate. 1H NMR spectra were recorded on a Bruker Avance 400 spectrometer operating at 400 MHz. All samples were dis- solved in deuterochloroform and TMS added as the internal standard. Quantitative analysis of the butanol mixtures was performed by 1H NMR using mesitylene (10 μL) as an internal standard against 0.2 mL of reaction products diluted with deuterochloroform. BUTanOl sYnThesis: grignarD reacTiOn anD esTeriFicaTiOn Magnesium acetate chloride (ch3cOOMgcl) A 250-mL two-necked, round bottom flask with magnetic stirrer bar attached to a reflux condenser and Schlenk-line apparatus Frontiers in Energy Research | www.frontiersin.org 5 October 2017 | Volume 5 | Article 26PDF Image | Demonstration of CO2 Conversion to Synthetic Transport Fuel
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