Aqueous-phase hydrogenation and hydrodeoxygenation of biomass-derived oxygenates with bimetallic catalysts

Abstract

The reaction rate on a per site basis for aqueous-phase hydrogenation (APH) of propanal, xylose, and furfural was measured over various alumina-supported bimetallic catalysts (Pd–Ni, Pd–Co, Pd–Fe, Ru–Ni, Ru–Co, Ru–Fe, Pt–Ni, Pt–Co, and Pt–Fe) using a high-throughput reactor (HTR). The results in this paper demonstrate that the activity of bimetallic catalysts for hydrogenation of a carbonyl group can be 110 times higher than monometallic catalysts. The addition of Fe to a Pd catalyst increased the activity for hydrogenation of propanal, xylose, and furfural. The Pd₁Fe₃ catalyst had the highest reaction rate for APH of propanal among all catalysts tested in the HTR. The addition of Fe to the Pd catalyst increased the reaction rate for xylose hydrogenation by a factor of 51, compared to the monometallic Pd catalyst. However, no bimetallic catalyst tested in this study was more active than the monometallic Ru catalyst for hydrogenation of xylose. The Pd₁Fe₃ catalyst had the highest reaction rate for APH of furfural, which was 9 times higher than the rate of the Pd catalyst. The Pd₁Fe₃/Zr–P, a bimetallic bifunctional catalyst, was 14 times more active on a per site basis than a Pd/Zr–P catalyst for aqueous-phase hydrodeoxygenation (HDO) of sorbitol in a continuous flow reactor. The addition of Fe to the Pd catalyst increased the rate of C–C cleavage reactions and promoted the conversion of sorbitan and isosorbide in HDO of sorbitol. Pd₁Fe₃/Zr–P also had a higher yield of gasoline-range products than the Pd/Zr–P catalyst.