Hydrogenolysis of 5-Hydroxymethyl-Furfural (HMF)

5-Hydroxymethyl-furfural (HMF) can be obtained in a biphasic reactor from the acid-cata­lyzed dehydration of hexoses[33]. HMF by itself cannot be used as motor fuel due to its high boiling point (283°C). However, it can be transformed to 2,5-dimethylfuran (DMF) through a two consecutive hydrogenolysis reactions (see Figure 7). DMF not only decreases the boiling point to a value suitable for liquid fuels, but also attains the lowest water solubility and the highest octane number (RON) of the mono-oxygenated C6 compounds, while preserving a high energy density 30 kJ cm-3, which is 40% higher that the energy density of bio-ethanol and comparable to the one of gasoline (35 KJ cm-3) [34]. Roman-Leshkov et al. [34] used CuRu/C catalysts (prepared by incipient wetness impregnation) in a flow reactor using 5 wt % HMF in a 1-butanol solution at 220 °C and 6.8 bar H2 pressure. Yields to DMF of 71% were measured. An important aspect in their process is that the catalyst should be chloride-resist­ant, because, NaCl was used in the dehydration step of hexoses to HMF to increase their sol­ubility in water. Very recently, Luijkx et al. [35] reported the production of 2,5-DMF by the hydrogenolysis of 5-HMF over a Pd/C catalyst in 1-propanol. Due to simultaneous alcoholy­sis, significant amount of ethers products were formed.