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Dowson and Styring CO2 Butanol with large silicone oil bubbler, under an atmosphere of dry nitro- gen was cooled in an ice-water bath. Methylmagnesium chloride (50 mL, 3.0 M solution in THF, 150 mmol) was added under a flow of dry nitrogen. A further 100 mL of dry THF was added to maintain solubility of Grignard reagent throughout the reac- tion. After liquid additions were complete and the reaction vessel sealed, the nitrogen flow was stopped. Dry synthetic flue gas (12% CO2, 88% N2) was admitted at a slow flow rate that maintained positive overall pressure through a needle adapter and sparging needle inserted as deeply as possible into the liquid layer. Flow was monitored using the oil bubbler. Maintaining low gas flow rates and the use of a reflux condenser was important to limit the evaporative loss of solvent and formation of a gel-like solid within the reaction vessel, indicative of poor initial solubility or inverse solubility of the magnesium chloride acetate salt intermediate product in THF. The latter effect can become pronounced, par- ticularly if temperatures become elevated. Complete reaction was indicated by a stable internal pressure when gas flow was paused (monitored by oil bubbler) or by the reaction remaining cold or cooling even when the ice bath was temporarily removed. The resulting product, magnesium acetate chloride, was used directly in solution without isolation. ethyl acetate by Direct esterification of Magnesium acetate chloride The Grignard reaction mixture was quenched by the very slow addition of a small excess of sulfuric acid (30 mL, 166 mmol) dissolved in ethanol (100 mL). The resulting mixture was then fractionally distilled, using a long fractionating column due to the relatively close boiling points of THF and the ethyl acetate/ ethanol azeotrope (66 and 71.8°C). The resulting product was dried using anhydrous magnesium sulfate and stored over molecular sieves. Crude product yield was 13.62 g, indicating an ethyl acetate yield of approximately 9.41 g (71% overall yield from the starting Grignard agent) with an azeotropic composi- tion of 71.8% ethyl acetate. Separation of the azeotrope was not attempted as neither ethanol nor trace THF would adversely affect subsequent reaction stages. ethyl acetoacetate A Claisen condensation was carried out using a previously published procedure which emphasized the importance of ensuring the alkoxide salt was of highest purity possible to achieve maximum yield (Fisher and McElvain, 1934). Therefore, freshly prepared sodium ethoxide (1.3 g, 19 mmol) was added to the azeotropic mixture from the previous reaction and heated under reflux for 24 h. The mixture was then cooled and aqueous acetic acid added slowly to quench the base. The product, ethyl acetoacetate was extracted using diethylether, with additional distilled water added to the reaction mixture to limit ethanol contamination of product yield. 4.80 g of very pale yellow ethyl acetoacetate (69% yield from ethyl acetate) was isolated and characterized by 1H NMR spectrometry, com- paring the resulting spectrum to reference spectra: δH (ppm) 400 MHz, CDCl3: 1.30 (t, 3 H), 2.28 (S, 3 H), 3.45 (S, 2 H), and 4.20 (q, 2 H). hYDrOgenaTiOn caTalYsT (cu/ZnO) PreParaTiOn ZnO (32.55 g, 400 mmol) was added to a 1 M aqueous solution of Cu(NO3)2 (100 mL, 100 mmol) and stirred to form a well- dispersed slurry. The suspension was dried under vacuum using a rotary evaporator and the moist solid further dried using the same method with the addition of 2-propanol to drive off mois- ture by azeotropic evaporation. The resulting solid was placed in a furnace at 500°C for 16 h to yield a gray-black powder of CuO supported on ZnO. 2 g of the resulting powder was placed in a 250-mL Parr autoclave and heated to 200°C under 10 bar H2 for 4 h. During cooling, the autoclave was evacuated to remove any generated water, yielding a copper-orange powder of Cu on ZnO with a loading of 20 wt% Cu determined by the initial molar ratio of the reactants. hYDrOgenaTiOn anD hYDrOgenOlYsis Ethyl acetoacetate (4.80 g, 36.9 mmol) and ethanol (5 mL) were added to the catalyst contained in the 250-mL Parr autoclave which was then sealed and purged using H2 to a pressure of 20 bar. Reaction was continued for 16 h. The reaction mixture was cooled and filtered, then dried over anhydrous magnesium sulfate to yield 10.5 mL of mixed alcohols, which were analyzed by 1H NMR spectroscopy (Table 1) with quantitative analyses carried out using mesitylene [δH(ppm) 400 MHz, CDCl3: 2.25 (s, 9 H), 6.75 (m, 3 H)] as an internal standard. The branched methyl group on the 2-butanol appears as a doublet at a shift of 1.12 ppm was cleanly away from the bulk of the signals. The com- bined integral of the terminal CH3 groups (at δH 0.7–0.8 ppm) where the 1- and 2-butanol signals overlap was determined and the amount of 1-butanol was determined by subtracting the amount of 2-butanol based on the amount determined from the 1.12 ppm doublet. A small doublet was observed next to the 2-butanol doublet which did not fit with being a carbon satellite and fitted the reference spectrum for 1,3-butane diol (the terminal CH3), which was used to calculate the butanediol concentration. The combined butanol isomers, butanediol and acetone were isolated in 98% conversion from ethyl acetoacetate with 95% selectivity to the butanol isomers. The overall four-step conversion from methyl magnesium chloride (chloromethane) to butanol isomers is 44%. resUlTs anD DiscUssiOn Producing butanol entirely and directly from CO2 using the Grignard process would not be possible without additional steps TaBle 1 | Composition of total product mixture, determined by 1H NMR, 400 MHz, CDCl3. composition 1-butanol 2-butanol ethanol 1,3-butanediol acetone Mass (%) 69 26 4 1 <1 Volume (%) 70 25 4 1 <1 Frontiers in Energy Research | www.frontiersin.org 6 October 2017 | Volume 5 | Article 26PDF Image | Demonstration of CO2 Conversion to Synthetic Transport Fuel
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