Evaluation of hydrodeoxygenation reactivity of pyrolysis bio-oil with various Ni-based catalysts for improvement of fuel properties

摘要

Three Ni-based catalysts were prepared for hydrodeoxygenation (HDO) of bio-oil with three different support materials (active carbon, SBA-15 and Al-SBA-15) and their catalytic effects were tested with crude bio-oil at 300 °C and under 3 MPa H₂ pressure for 60 min. After the HDO reaction, gas, liquid phase (light oil and heavy oil) and char were obtained as the primary products. Heavy oil was produced at a yield of 45.8–48.1 wt%, with no significant differences among the three catalysts. Mesoporous silica-supported catalysts (Ni/SBA-15 and Ni/Al-SBA-15) produced large amounts of char (16.3–18.6%), while Ni/C yielded 8.5 wt% char. Active carbon-supported catalysts (Ni/C) yielded more gas (27.7%) than the Ni/SBA-15 and Ni/Al-SBA-15 catalysts (6.6–8.9%), due to high surface area and low char deposition on the active carbon-supported catalysts. The HDO reaction led to improvement in the fuel properties of crude bio-oil. The water content, acidity, viscosity and oxygen content decreased via de-moisturization, i.e., dehydration, as well as dehydroxylation, resulting in an increase in heating value. The heavy oil obtained from HDO with Ni/Al-SBA-15 exhibited a low water content (9.3 wt%), while that of Ni/SBA-15 revealed a high HHV (22.8 MJ kg?1), energy efficiency (62.8%), and degree of deoxygenation (54.9%). A major factor of bio/oil instability is unstable oxygen-containing compounds, such as acetic acid, furfural, vanillin and levoglucosan, which were obviously reduced in the heavy oil in this study.