Selective Hydrogenation of Diethyl Malonate to 1,3‐Propanediol Over Ga‐Promoted Cu/SiO₂ Catalysts With Enhanced Activity and Stability

Abstract

Cu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation‐gel method and studied for the selective hydrogenation of syngas or biomass‐based diethyl malonate (DEM) to valuable 1,3‐propanediol (1,3‐PDO). The Ga‐promoted 70Cu6Ga/SiO2 catalyst was found to exhibit the highest catalytic performance, achieving 100% DEM conversion and 76.6% 1,3‐PDO selectivity under reaction conditions of 160 °C and 8 MPa H2. The 70Cu6Ga/SiO2 bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO2 catalyst in a continuous flow reactor over 180 h time‐on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu2+ species, and thus increased the proportion of Cu+ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu0 and Cu+ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO2 bimetallic catalysts.