For Abstract see ChemInform Abstract in Full Text.

Utilization of carbon dioxide as a C 1 building block in chemical synthesis has been stimulated mainly by environmental considerations and its large-scale availability. Catalysis provides several opportunities for using CO 2 in chemical synthesis. The present state of these efforts in heterogeneous catalysis is briefly surveyed, placing special emphasis on more recent developments in the syntheses of methanol, methylamines and formic acid derivatives, and the production of synthesis gas.

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The kinetics of the copper-catalyzed amination of long-chain aliphatic alcohols (octanol and decanol) by monomethylamine and dimethylamine have been investigated in both the gas and liquid phases at temperatures between 440 and 540 K. The individual reactions leading to the production of stable intermediates and products are identified. The rate of dehydrogenation of the alcohol determines the overall rate of alcohol conversion to all products. The rate is first order in alcohol in both the gas and liquid phases and inhibited by alcohol, water, and the reactant amine in the gas phase only. The selectivity is determined primarily by the rate of hydrogenation of an adsorbed Intermediate and the rate of disproportionation of reactant and product amines. The selectivity of the amination reaction to the desired tertiary amine increases with increasing hydrogen pressure, and first increases and then decreases with increasing conversion of alcohol.