Hydrogenation of 5-hydroxymethylfurfural in supercritical carbon dioxide–water: a tunable approach to dimethylfuran selectivity

Abstract

The use of supercritical carbon dioxide–water on the hydrogenation of 5-hydroxymethylfurfural (HMF) was investigated over a Pd/C catalyst. It was possible to achieve a very high yield (100%) of DMF within the reaction time of 2 hours at 80 °C. A significant effect of CO2 pressure was observed on the product distribution. Simply by tuning the CO2 pressure it was possible to achieve various key compound, such as tetrahydro-5-methyl-2-furanmethanol (MTHFM) (<10 MPa), 2,5-dimethylfuran (DMF) (10 MPa) and 2,5-dimethyltetrahydrofuran (DMTHF) (>10 MPa) with very high selectivity. Optimization of other reaction parameters revealed that H2 pressure, temperature, as well as the CO2–water mole ratio, played an important role in the selectivity to the targeted DMF. It is interesting to note that a very high yield of DMF was achieved when a combination of CO2 and water was used. For instance, in the absence of water or CO2, the selectivity of DMF was low; similarly, an excess of water against the fixed pressure of CO2 reduced the selectivity to DMF. Hence, an optimized amount of water was mandatory in the presence of CO2 for the formation of DMF with high selectivity. This method was successfully extended to the hydrogenation of furfural, which could afford 100% selectivity to 2-methylfuran with complete conversion within a very short reaction time of 10 min. The studied catalyst could be recycled successfully without significant loss of catalytic activity.