Abstract
A series of Cu, Ni monometallic and bimetallic catalysts supported on γ-Al2O3 and activated carbon were synthesized by incipient wetness impregnation method and examined for hydrogenolysis and esterification of glycerol. Hydrogenolysis reaction was carried out in a 250 ml Teflon-coated stainless steel batch reactor at 250°C and 10 bar H2 pressure, whereas esterification of glycerol with acetic acid was carried out at 120°C at atmospheric pressure. The physiochemical properties of the catalysts were investigated by various techniques such as surface area, X-ray diffraction (XRD), NH3-temperature-programmed desorption (TPD). Characterization results dictated that the reduction behavior, acidic nature and the metal support interactions were varied with the support as well as Cu/Ni weight ratio. The XRD results confirmed the formation of mixed oxide Cu0.75Ni0.25 Al2O4 phase in Cu–Ni (3:1)/γ-Al2O3 catalyst. Among the catalysts tested, Cu–Ni bimetallic catalysts showed superior performance as compared to monometallic catalysts in both the reactions. The glycerol hydrogenolysis activity of γ-Al2O3 supported Cu–Ni catalysts was higher than the activated carbon-supported catalysts. 1,2-PDO was obtained as the main hydrogenolysis product independent of the support as well as Cu/Ni weight ratio and its selectivity was in the range of 92.8–98.5%. The acidic nature of γ-Al2O3 and the mixed oxide (Cu0.75Ni0.25Al2O4) phase played an important role for hydrogenolysis activity. Cu–Ni (3:1)/γ-Al2O3 catalyst showed the maximum 1,2-PDO selectivity to 97% with 27% glycerol conversion after a reaction time of 5 h. On the other hand, Cu–Ni(1:3)/C catalyst showed the highest glycerol conversion of 97.4% for esterification and obtained selectivity to monoacetin, diacetin and triacetin were 26.1%, 67.2% and 6.5%, respectively.
