Nickel-Catalysed Vapour-Phase Hydrogenation of Furfural, Insights into Reactivity and Deactivation
Kathryn MacIntosh, Simon K. Beaumont
Abstract
Abstract Furfural is a key bioderived platform molecule, and its hydrogenation affords access to a number of important chemical intermediates that can act as “drop-in” replacements to those derived from crude oil or novel alternatives with desirable properties. Here, the vapour phase hydrogenation of furfural to furfuryl alcohol at 180 °C over standard impregnated nickel catalysts is reported and contrasted with the same reaction over copper chromite. Whilst the selectivity to furfuryl alcohol of the unmodified nickel catalysts is much lower than for copper chromite as expected, the activity of the nickel catalysts in the vapour phase is significantly higher, and the deactivation profile remarkably similar. In the case of the supported nickel catalysts, possible contribution to the deactivation by acidic sites on the catalyst support is discounted based on the similarity of deactivation kinetics on Ni/SiO 2 with those seen for less acidic Ni/TiO 2 and Ni/CeO 2 . Powder X-ray diffraction is used to exclude sintering as a primary deactivation pathway. Significant coking of the catalyst (~ 30 wt% over 16 h) is observed using temperature programmed oxidation. This, in combination with the solvent extraction analysis and infrared spectroscopy of the coked catalysts points to deactivation by polymeric condensation products of (reactant or) products and hydrocarbon like coke. These findings pave the way for targeted modification of nickel catalysts to use for this important biofeedstock-to-chemicals transformation.