Stabilization of acid-rich bio-oil by catalytic mild hydrotreating

Although liquid products derived from the pyrolysis of biomass are promising for the production of petroleum-like hydrocarbon fuels, the catalytic burden of hydrodeoxygenation must be reduced to achieve feasible upgrading processes. Herein, mild hydrotreating of an acid-rich biomass pyrolysis oil (bio-oil) with an unusually high total acid number (588 mg KOH/g bio-oil) was performed to stabilize the low-quality bio-oil. Ru-added TiO₂-supported transition metal catalysts stabilized the bio-oil by reducing its acidity more compared to what could be achieved by Ru-free catalysts; this process also leads to lower loss of organic compounds compared to when using a Ru/TiO₂ catalyst. Based on the performance of transition metal catalysts, including Ni, Co, and Cu, supported on TiO₂, tungstate-zirconia, or SiO₂, supported bimetallic catalysts were prepared by adding Ru to the TiO₂-supported metal catalysts. The bimetallic catalysts Ru/Ni/TiO₂ and Ru/Co/TiO₂ exhibited good decarboxylation activity for the removal of carboxylic acids and a higher yield of organic compounds compared to that provided by Ru, which can be deemed appropriate for feedstocks when hydrodeoxygenation needs to suppress the loss of organic reactants. Using these catalysts, the carboxylic acid concentration was reduced to 319-323 mg KOH/g bio-oil with organic yields of 62-63 wt% at reaction temperatures 150-170 °C lower than the temperature required for direct conversion of carboxylic acids to alcohols or deoxygenates. The improved catalytic hydrotreating activity of Ru-added transition metals can be attributed to the high acid site densities of these catalysts along with their improved hydrogenation activities.