CHEMICAL-EQUILIBRIA AND CATALYTIC REACTION OF GAS-PHASE METHANOL SYNTHESIS FROM METHYL FORMATE

Gas-phase methanol synthesis from methyl formate was studied by thermodynamic evaluations of the hydrogenolysis reaction (HCOOCH3+2H2=2CH3OH) and the decarbonylation reaction (HCOOCH3=CH3OH+CO) concurrently. Based upon the chemical equilibria being calculated from these thermodynamic results, the gas-phase methanol synthesis reaction over copper chromites was carried out and the catalytic data were collected. Copper chromite catalysts prepared by the decomposition of an homogeneous citrate complex were characterized to investigate the active site for the gas-phase reaction. Copper metallic (Cu0) and cuprous chromite spinel (CuCrO2) Phases were proved to play important roles in methanol production. The catalyst prepared from the citrate complex, especially, showed higher activity and selectivity to methanol in the hydrogenolysis reaction than the commercial catalysts. The maximum activity and selectivity for methanol formation were obtained when the catalysts with 50-70% copper content were calcined at 623 K.