2387. NATTA, G. [Synthesis of Methanol and Higher Alcohols From Water Gas.] Österr. Chem.-Ztg., vol. 1937, p. 162-170; British Chem. Abs., 1937, B, p. 756; Chem. Abs., vol. 31, 1937, p. 5978. Curves showing the equilibrium constant and velocity constant for the synthesis and the decomposition of MeOH are given. The synthesis is a trimolecular reaction. The best catalyst is ZnO obtained by heating natural smithsonite at 350°. The calcined catalyst has a porosity of 47%, high mechanical strength, and will absorb 10,000 vol. of CO2 at low pressures. With calcined smithsonite impregnated with K acetate as a catalyst and a gas containing an excess of H2, CH3OH, and higher alcohols are obtained. If the gas contains an excess of CO, the alcohols contain a high % of ketones, aldehydes, and acids. Reactions are given and experimentally verified in which the alkali in the contact mass acts directly in the formation of the higher alcohols. The higher alcohols contain high % of isobutanol and n-PrOH and low % of EtOH iso-PrOH and n-BuOH. MeOH with 1/3 of its volume of higher alcohols is miscible in all proportions with benzine. MeOH requires 6.33 kg. air per kg., while benzine required 14.8 kg. air per kg. 10% of MeOH instead of 26% EtOH or 60% benzene is required to raise the octane value of a benzine from 66 to 80. |