Improved hydrodeoxygenation of lignin-derived oxygenates and biomass pyrolysis oil into hydrocarbon fuels using titania-supported nickel phosphide catalysts

• Catalytic hydrodeoxygenation of biomass pyrolysis oil and its model compounds. • Reaction performed using titanium dioxide-supported phosphor-modified metals. • Origin of improved activity based on the catalyst characterization. • Conditions for catalyst preparation and process operation optimized. Biomass pyrolysis oil is a potentially essential renewable energy source that can serve as an alternative to petroleum-based fuels and chemicals. In this study, biomass pyrolysis oil was converted into petroleum-like deoxygenated hydrocarbons via catalytic hydrodeoxygenation using a titania-supported nickel phosphide catalyst. The phosphor precursor was added to several transition metals, including nickel, cobalt, copper, and iron, supported on titania. The formation of isolated nickel phosphide particles, which were active for complete hydrodeoxygenation, was confirmed by the characterization of prepared catalysts. As a model reactant of biomass pyrolysis oil, a mixture of alkyl-methoxyphenol compounds was hydrodeoxygenated to produce completely deoxygenated compounds, generating an 87% yield of cycloalkanes at 300 °C and 4 MPa H 2 for a reaction time of 2 h. The hydrodeoxygenation of biomass pyrolysis oil also generated a 37.4% yield of hydrocarbon fuels. The high hydrodeoxygenation activity can be attributed to the synergy between the hydrogenating metals and the acid sites, which can be improved by electron transfer from a slightly cationic nickel to a slightly anionic phosphor. Furthermore, the addition of phosphor improved the formation of highly dispersed nickel particles, increasing the quantity of hydrogen-adsorbing surface metals. The observations in this study indicate that the efficient conversion of lignocellulose-derivatives into chemicals and fuels can be achieved using modified non-precious transition metal catalysts.