Vapor phase hydrodeoxygenation of furfural to 2-methylfuran on molybdenum carbide catalysts

Vapor phase hydrodeoxygenation (HDO) of furfural over Mo2C catalysts at low temperatures (423 K) and ambient pressure showed high/low selectivity to C=O bond/C-C bond cleavage, resulting in selectivity to 2-methylfuran (2MF) and furan of similar to 50-60% and <1%, respectively. Efficient usage of H-2 for deoxygenation, instead of unwanted sequential hydrogenation, was evidenced by the low selectivity to 2-methyltetrahydrofuran. The apparent activation energy and H-2 order for 2MF production rates were both found to be invariant with furfural conversion caused by catalyst deactivation, suggesting that (1) the measured reaction kinetics are not influenced by the products of furfural HDO and (2) the loss of active sites, presumably by formation of carbonaceous species observed by TEM analysis, is the reason for the observed catalyst deactivation. The observed half order dependence of 2MF production rates on H-2 pressure at different furfural pressures (similar to 0.12-0.96 kPa) and the 0-0.3 order dependence in furfural pressure support the idea of two distinct sites required for vapor phase furfural HDO reactions on Mo2C catalysts. The invariance of 2MF production rates normalized by the number of catalytic centers assessed via ex situ CO chemisorption suggests that metal-like sites on Mo2C catalysts are involved in selective HDO reactions.