Catalytic reduction of carbon monoxide: Selective synthesis of C1 and higher oxygenates.

摘要

A-step synthesis of methyl formate, a C2 oxygenate, has been developed at BNL. The following features of the LLTMeOH technology and related studies are of interest: The BNL approach exemplifies a synergistic effect of two combined catalysts. The chosen reaction conditions favor methyl formate synthesis. The only identified by-product is methanol. The effect of stirring speed, temperature, solvent, catalyst loading, and syngas composition is noted.Of particular interest is a run with H(sub 2)CO = 37%/63% in which methyl formate selectivity approached 100%. Bases (K(sub 2)CO(sub 3)KHCO(sub 2), KOCO(sub 2)Me) other than alkoxide have been used for methyl formate synthesis. A gas phase infrared mechanistic study of methanol carbonylation reaction, carried out with methoxide catalyst at 130(degree)C under 1/1 (H(sub 2)CO) syngas, showed that the fast alkyl formate anion formations was followed by an extremely slow protonation step. It appears that under these conditions, protonation step is rate determining (RDS). This approach results in enhancing carbon conversion of syngas derived from coal or other sources that produce CO-rich gas.