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High-Durability Metal-Doped Cu/ZnO/Al2O3 Catalysts for Reforming of Model Biomethanol
Katsutoshi Nomoto1, Hiromu Akiyama2, Yasushi Sekine2
1Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, Tokyo, Japan.
Abstract:
A series of metal-doped Cu/ZnO/Al2O3 catalysts (M-CZA; M = Co, Ni, Ru, Rh, Pd, Pt) were synthesized and evaluated for the autothermal reforming (ATR) of model biomass-derived methanol (biomethanol) containing trace ethanol or 1-butanol impurities. The objective was to improve the efficient utilization of impure biomethanol for hydrogen production. The introduction of 1 mol% ethanol decreased the methanol conversion and hydrogen production rates over CZA, Co-CZA, Pd-CZA, and Pt-CZA catalysts during the initial reaction stage, with further decline over time. In contrast, Ni-CZA, Ru-CZA, and Rh-CZA maintained stable activity under identical conditions. Ethanol was converted mainly into C1-C3 byproducts such as methane, acetaldehyde, and methyl acetate on CZA, Co-CZA, Pd-CZA, and Pt-CZA, whereas Ni-CZA, Ru-CZA, and Rh-CZA predominantly formed methane and carbon monoxide with negligible formation of carbonaceous species. Temperature-programmed oxidation indicated the deposition of carbonaceous species on spent CZA, Co-CZA, Pd-CZA, and Pt-CZA, but not on Ni-, Ru-, or Rh-modified catalysts. These results suggest that Ni, Ru, and Rh enhance C-C bond cleavage in lower alcohols, thereby suppressing carbon deposition and improving catalyst durability. This study provides practical insights for designing efficient ATR catalysts for on-site hydrogen generation from biomethanol containing impurities.
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