Combination of supported bimetallic rhodium–molybdenum catalyst and cerium oxide for hydrogenation of amide

摘要

Hydrogenation of cyclohexanecarboxamide to aminomethylcyclohexane was conducted with silica-supported bimetallic catalysts composed of noble metal and group 6–7 elements. The combination of rhodium and molybdenum with molar ratio of 1:1 showed the highest activity. The effect of addition of various metal oxides was investigated on the catalysis of Rh–MoO_x/SiO₂, and the addition of CeO₂ much increased the activity and selectivity. Higher hydrogen pressure and higher reaction temperature in the tested range of 2–8 MPa and 393–433 K, respectively, were favorable in view of both activity and selectivity. The highest yield of aminomethylcyclohexane obtained over Rh–MoO_x/SiO₂?+?CeO₂ was 63%. The effect of CeO₂ addition was highest when CeO₂ was not calcined, and CeO₂ calcined at >773 K showed a smaller effect. The use of CeO₂ as a support rather decreased the activity in comparison with Rh–MoO_x/SiO₂. The weakly-basic nature of CeO₂ additive can affect the surface structure of Rh–MoO_x/SiO₂, i.e. reducing the ratio of Mo–OH/Mo–O^? sites.