Enhancing Hydrodeoxygenation of Bio-oil via Bimetallic Ni-V Catalysts Modified by Cross-Surface Migrated-Carbon from Biochar.

Abstract

Aromatics from selective hydrodeoxygenation (HDO) of biomass-derived bio-oil are an ideal feedstock for replacing industrial fossil products. In this study, biochar-modified Hβ/Ni-V catalysts were prepared and tested in the atmospheric HDO of guaiacol and bio-oil to produce aromatics. Compared with unmodified Hβ/Ni-V, higher HDO activity was achieved in catalysts with all kinds of biochar modifications. Especially, the pine nut shell biochar (PB)-modified PB-Hβ-8/Ni-V showed the highest selectivity to aromatics (69.17%), mainly including benzene and toluene. Besides, under the conditions of 380 °C and weight hourly space velocity (WHSV) of 0.5 h-1, the cleavage of CAr-OH (CAr means the carbon in the benzene ring) was promoted to form more aromatics. Moreover, great recyclability (58.77% aromatics for the reactivated run-3 test) and efficient HDO of bio-oil (44.9% aromatic yield) were also achieved. Based on the characterization results, the enhanced aromatic selectivity of PB-Hβ-8/Ni-V was attributed to the synergetic effect between PB and Hβ/Ni-V. In detail, a stable surface migrated-carbon layer was formed on Hβ/Ni-V via the metal catalytic chemical vapor deposition (CVD) process of the pyrolysis PB volatiles. Simultaneously, a carbothermal reduction driven by the migrated-carbon took place to decorate the surface metals, obtaining more Ni0 and V3+ active sites. With this synergism, increased Ni0 sites promoted H2 adsorption and dissociation, which improved the hydrogenation activity. Furthermore, the higher affinity of the reactant and increased oxygen vacancies both contributed to enhancing the selective surface adsorption of oxygenous groups and the cleavage of the CAr-OH bond, thus improving the deoxygenation activity. Therefore, the HDO activity was improved to form more target aromatics over biochar-modified catalysts. This work highlighted a potential avenue to develop economic and environmental catalysts for the upgrading of bio-oil.