Zinc-Assisted Hydrodeoxygenation of Biomass-Derived 5-Hydroxymethylfurfural to 2,5-Dimethylfuran

• Published in: ChemSusChem Vol. 7; no. 11; pp. 3095 - 3101
• Main Authors: Saha, Basudeb, Bohn, Christine M., Abu-Omar, Mahdi M.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-11-2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Biomass; biomass conversion; Carbon - chemistry; Catalysis; Furaldehyde - analogs & derivatives; Furaldehyde - chemistry; Furans - chemistry; heterogeneous catalysis; hydrodeoxygenation; Lewis acids; Palladium - chemistry; Recycling; ruthenium; Zinc; Zinc - chemistry; Lewis acids; biomass conversion; hydrodeoxygenation; ruthenium; heterogeneous catalysis
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.201402530

2,5‐Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis‐acidic ZnII and Pd/C components is effective for 5‐hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99 %) and selectivity (85 % DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60 % less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one‐pot conversion of fructose to DMF.
Are you thinking what I′m zincing? The addition of zinc salt enhances the catalytic effectiveness of a palladium–carbon (Pd/C) catalyst in the hydrodeoxygenation (HDO) of 5‐hydroxymethylfurfural (HMF) into 2,5‐dimethylfuran (DMF) by a factor of more than 3. The finding allows to use catalysts with less palladium. The synergistic effect of the zinc salt with different hydrodeoxygenation catalysts is compared to elucidate the role of the zinc component.