Recycling the CoMo/Al2O3 catalyst for effectively hydro-upgrading shale oil with high sulfur content and viscosity

Abstract

Hydrotreatment is an effective upgrading technology for removing contaminants and saturating double bonds. Still, few studies have reported the hydro-upgrading of shale oil, with unusually high sulfur (13200 ppm) content, using the CoMo/Al₂O₃ catalyst. Here we report an extensive study on the upgrading of shale oil by hydrotreatment in a stirred batch autoclave reactor (500 ml) for sulfur removal and viscosity reduction. From a preliminary optimization of the reaction factors, the best-operating conditions were 400 °C, an initial H₂-pressure of 5 MPa, and an agitation rate of 800 rpm, a catalyst-to-oil ratio of 0.1, and a reaction time of 1 h. We could achieve a sulfur removal efficiency of 87.1% and 88.2% viscosity reduction under the optimal conditions. After that, the spent CoMo/Al₂O₃ was repeatedly used for subsequent upgrading tests without any form of pre-treatment. The results showed an increase in the sulfur removal efficiency with an increase in the number of catalyst runs. Ultimately, 99.5–99.9% sulfur removal from the shale oil was achieved by recycling the spent material. Both the fresh and the spent CoMo/Al₂O₃ were characterized and analyzed to ascertain their transformation levels by XRD, TEM, TG, XPS, TPD and N₂ adsorption analysis. The increasing HDS efficiency is attributed to the continuing rise in the sulfidation degree of the catalyst in the sulfur-rich shale oil. The light fraction component in the liquid products (IBP–180 °C) was 30–37 vol% higher than in the fresh shale oil. The product oil can meet the sulfur content requirement of the national standard marine fuel (GB17411-2015/XG1-2018) of China.