Enhancing bio-oil quality and energy recovery by atmospheric hydrodeoxygenation of wheat straw pyrolysis vapors using Pt and Mo-based catalysts

Atmospheric hydrodeoxygenation (HDO) of wheat straw fast pyrolysis vapors was studied as a promising route for the production of renewable liquid transportation fuels. The performance of TiO2-supported Pt (0.5 wt.%) and MoO₃ (10 wt.%) catalysts was compared to an industrial Mo-based catalyst using a bench scale reactor operated at atmospheric pressure and up to high biomass-to-catalyst ratios (B:C). Mass and energy balances were complemented by detailed bio-oil characterization including advanced methods such as GC×GC-ToF/MS or−FID and 13C NMR. At 50 vol.% H2, all three HDO catalysts effectively reduced the oxygen content of the bio-oils to ~7-12 wt.% (dry basis) compared to a non-catalytic reference (23 wt.% O). MoO₃/TiO₂ was least efficient in conversion of acids (TAN = 28 mg/KOH), while Pt/TiO₂ and MoO₃/Al₂O₃ obtained oils with TAN ~13 mg KOH/g (non-catalytic = 66 mg KOH/g). Compared to the TiO₂-supported catalysts, the industrial Mo/Al2O3 catalyst produced higher yields of coke at the expense of condensed bio-oil. MoO₃/TiO₂ performed similar to Pt/TiO₂ in terms of deoxygenation and energy recovery of condensed bio-oil, and by increasing the H₂ concentration to 90 vol.% the energy recovery of bio-oil increased to 39 and 42% at 8 and 10 wt.% O (d.b.), respectively. Pt/TiO₂ showed the highest selectivity to aliphatics and the lowest coke yields, e.g. the coke yield at B:C ~8 was only 0.6 wt.% of fed biomass. This study demonstrates that by using low-pressures of hydrogen and appropriate HDO catalysts, the quality of bio-oil can be improved without severely compromising its quantity (carbon yield) as observed under catalytic fast pyrolysis conditions using acidic catalysts in the absence of hydrogen.