Isobutanol-methanol mixtures from synthesis gas. Quarterly technical progress report, 1 April--30 June 30 1996

A series of CuMgCeO{sub x} catalysts have been prepared by coprecipitating the corresponding metal nitrates with a mixed solution of potassium carbonate and potassium hydroxide. Kinetic studies of methanol and ethanol coupling reactions on K-Cu/MgO/CeO{sub 2} and MgO/CeO{sub 2} catalysts indicate that Cu enhances the rates of alcohol dehydrogenation. The cross-coupling reactions of acetaldehyde and {sup 13}C-labeled methanol produce singly-labeled propionaldehyde, suggesting that it forms by the condensation of acetaldehyde and a reactive intermediate derived from methanol. Isobutyraldehyde, a precursor to isobutanol, forms via the condensation of propionaldehyde and a reactive C{sub 1} intermediate resulting from methanol. CO{sub 2}, one of the reaction products, poisons both basic and metal sites on Ce-containing CuMgO{sub x} catalysts, resulting in decreases in the rates of both alcohol dehydrogenation (Cu sites) and chain-growth condensation reactions (basic sites). CO{sub 2} inhibits ethanol dehydrogenation on both low-Cu and high-Cu CuMgCeO{sub x} catalysts; however, CO{sub 2} has no effect on the activity of low-Cu Ce-free Cu-MgO{sub x} catalysts, suggesting that the Cu on CuMgCeO{sub x} catalysts is more likely to be oxidized by CO{sub 2} to Cu{sup +} species that can be subsequently stabilized by CeO{sub 2}. CO{sub 2} effects on high-pressure isobutanol synthesis from CO/H{sub 2} have been studied on low- and high-Cu CuMgCeO{sub x} catalysts at 320{degrees}C and 4.5 MPa. CO{sub 2} addition and removal on low- and high-Cu catalysts show similar directional effects on CO conversion. CO conversion is lower at all space velocities in the presence of CO{sub 2}, and removal Of CO{sub 2} from the feed partially recovers CO conversion. CO{sub 2} decreases methanol and isobutanol productivities on both catalysts. Addition of 1-propanol to CO/H{sub 2} feed increases isobutanol production, suggesting that 1-propanol is a precursor to isobutanol