Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation

Because of the global necessity to decrease CO₂ emissions, biomass-based fuels have become an interesting option to explore; although, bio-oils need to be upgraded, for example, by catalytic hydrodeoxygenation (HDO), to reduce oxygen content. This reaction generally requires bifunctional catalysts with both metal and acid sites. For that purpose, Pt-Al₂O₃ and Ni-Al₂O₃ catalysts containing heteropolyacids (HPA) were prepared. HPAs were added by two different methods: the impregnation of a H₃PW₁₂O₄₀ solution onto the support and a physical mixture of the support with Cs_2.5H_0.5PW₁₂O₄₀. The catalysts were characterized by powder X-ray diffraction, Infrared, UV-Vis, Raman, X-ray photoelectron spectroscopy and NH₃-TPD experiments. The presence of H₃PW₁₂O₄₀ was confirmed by Raman, UV-Vis and X-ray photoelectron spectroscopy, while the presence of Cs_2.5H_0.5PW₁₂O₄₀ was confirmed by all of the techniques. However, HPW was shown to strongly interact with the supports, especially in the case of Pt-Al₂O₃. These catalysts were tested in the HDO of guaiacol, at 300 °C, under H₂ and at atmospheric pressure. Ni-based catalysts led to higher conversion and selectivity to deoxygenated compound values, such as benzene. This is attributed to both a higher metal and acidic contents of these catalysts. Among all tested catalysts, HPW/Ni-Al₂O₃ was shown to be the most promising, although it suffered a more severe deactivation with time-on-stream.