Coupling Hydrogenation of Guaiacol with In Situ Hydrogen Production by Glycerol Aqueous Reforming over Ni/AlO and Ni-X/AlO (X = Cu, Mo, P) Catalysts.

Biomass-derived liquids, such as bio-oil obtained by fast pyrolysis, can be a valuable source of fuels and chemicals. However, these liquids have high oxygen and water content, needing further upgrading typically involving hydrotreating using H at high pressure and temperature. The harsh reaction conditions and use of expensive H have hindered the progress of this technology and led to the search for alternative processes. In this work, hydrogenation in aqueous phase is investigated using in-situ produced hydrogen from reforming of glycerol, a low-value by-product from biodiesel production, over Ni-based catalysts. Guaiacol was selected as a bio-oil model compound and high conversion (95%) to phenol and aromatic ring hydrogenation products was obtained over Ni/γ-AlO at 250 °C and 2-h reaction time. Seventy percent selectivity to cyclohexanol and cyclohexanone was achieved at this condition. Hydrogenation capacity of P and Mo modified Ni/γ-AlO was inhibited because more hydrogen undergoes methanation, while Cu showed a good performance in suppressing methane formation. These results demonstrate the feasibility of coupling aqueous phase reforming of glycerol with bio-oil hydrogenation, enabling the reaction to be carried out at lower temperatures and pressures and without the need for molecular H.