Selective Transformation of 5-Hydroxymethylfurfural into the Liquid Fuel 2,5-Dimethylfuran over Carbon-Supported Ruthenium

Abstract

A simple and efficient process was presented for the selective hydrogenation of 5-hydroxymethylfurfural (HMF) into the high-quality liquid fuel 2,5-dimethylfuran (DMF) in the presence of tetrahydrofuran (THF). Among the employed metal catalysts, the relatively inexpensive carbon-supported ruthenium (Ru/C) displayed the highest catalytic performance, which led to 94.7% DMF yield with 100% HMF conversion at a relatively mild reaction temperature of 200 °C for only 2 h. Although Ru/ C had a little loss in the catalytic activity when it was used for five successive reaction runs, the partially deactivated Ru/C could be easily regenerated by heating at a mixed flow of H 2 and N 2 . Moreover, the plausible mechanism involving an aldehyde group, a hydroxyl group, and a furan ring for the selective hydrogenation of HMF into DMF was also proposed. Subsequently, DMF was separated from the crude hydrogenation mixture according to their various boiling points by the combination of atmospheric distillation and vacuum distillation, and then, the chemical structures and physical properties of the separated DMF were confirmed to be consistent with the authentic DMF. More gratifyingly, Ru/C and THF were also found to be a good combination for the direct hydrogenation of carbohydrate-derived HMF into DMF, which is very important for the practical production of DMF from a variety of biomass-derived carbohydrates such as fructose, glucose, sucrose, maltose, cellobiose, starch, and cellulose.

Selective Hydrodeoxygenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Heterogeneous Iron Catalysts

“…[15] Vlachos and co-workers reported the catalytic transfer hydrogenation (CTH) of HMFt oD MF by using secondary alcohols as the H-donors over aR u/C catalyst with aD MF yield of up to 80 %, [16] and then the role of Ru and RuO 2 phases was studied in detail. [20] Kawanami and co-workersr eportedt he use of supercritical CO 2 -watero nt he HDO of HMF over aP d/C catalyst, and av ery high yield (100 %) of DMF was observed at 80 8Ca fter 2h. [18] Wang and co-workersr eported the HDO of HMF over Ru/ Co 3 O 4 at 130 8Ca nd 0.7 MPa H 2 in THF with aD MF yield of 93.4 %.…”

Effects of Water on the Copper‐Catalyzed Conversion of Hydroxymethylfurfural in Tetrahydrofuran

“…For example, HMF is derived from glucoseand can be converted into various fuel molecules and valuable industrialchemicals. [5][6][7][8][9][10][11][12][13][14][15] For example, 81 %D MF yield was achieved at full HMF conversion using Ru/C in isopropanol solutions. [4] The production of DMF from HMF hydrogenolysis in organic solvents was studied by means of catalytic transfer hydrogenation and also using molecular hydrogen, achieving high selectivity and yield.…”

Recent Trends in the Production, Combustion and Modeling of Furan-Based Fuels

“…These studies demonstrated different yields and conversion rates. The highest 2,5-DMF yield was reported by Hu et al [70], which reached 94.7% with total HMF conversion at a reaction temperature of 473 K for 2 h. The results showed that further temperature increase up to 533 K did not affect 2,5-DMF yields [45].…”

“…The use of Ru/C catalysts for the hydrogenation of HMF to 2,5-DMF was extensively investigated in a number of studies [36,45,[67][68][69][70] under various temperature ranges and using difference hydrogen sources. These studies demonstrated different yields and conversion rates.…”