Methanol dehydrogenation to methyl formate catalyzed by SiO2-, hydroxyapatite-, and MgO-supported copper catalysts and reaction kinetics

• Methanol dehydrogenation over Cu/SiO2, Cu/HAP, and Cu/MgO catalysts was studied.
• Cu/SiO2 with low basicity favored the methanol dehydrogenation to methyl formate.
• Cu/HAP and Cu/MgO with high basicities caused the methyl formate degradation to CO.
• Kinetics for methanol dehydrogenation and methyl formate degradation were studied.

Catalytic dehydrogenation of methanol to methyl formate over SiO2-, hydroxyapatite (HAP)-, and MgO-supported copper catalysts was investigated. Metallic copper (Cu0) was the active site for the methanol dehydrogenation to methyl formate. Cu/SiO2 catalyst with low basicity and weak-strength basic site effectively catalyzed the methanol dehydrogenation to methyl formate. Cu/HAP and Cu/MgO catalysts with high basicities and strong-strength basic sites caused the degradation of the resultant methyl formate to CO and H2. Over Cu(5)/SiO2 catalyst, the reaction activation energies for methanol dehydrogenation to methyl formate and methyl formate degradation to CO and H2 were 58.3 and 91.1 kJ mol−1, respectively.

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