Heterogeneous Catalytic Conversion of Dry Syngas to Ethanol and Higher Alcohols on Cu-Based Catalysts

Ethanol and higher alcohols have been identified as potential fuel additives or hydrogen carriers for use in fuel cells. One method of ethanol production is catalytic conversion of syngas (a mixture of CO, H2, CO2, and H2O), derived from biomass, coal, or natural gas. Thermodynamics of CO hydrogenation shows that ethanol is favored as the sole product at conditions of practical interest, but if methane is allowed as product in this analysis, essentially no ethanol is formed at equilibrium. The kinetics of ethanol formation must therefore be maximized. Although rhodium-based catalysts give C2+ oxygenates with high selectivity, their prohibitive cost has spurred research on less expensive copper-based alternatives. Copper-based catalysts require an optimum amount of promoter to suppress undesired reactions and maximize the yields of ethanol and higher alcohols. Common promoters include alkali, transition metals and their oxides, and rare earth oxides. Careful selection of operating variables is also necessary to achieve the desired activity and selectivity. This review describes the effects of promoters, supports, and operating conditions on the performance of copper-based catalysts for conversion of dry syngas to ethanol and higher alcohols. Proposed mechanisms from the literature for ethanol and higher-alcohol synthesis are outlined.