Hydrodeoyxgenation (HDO) is one of the effective methods for bio-oil upgrading. However, the HDO catalysts applied have all been deactivated after a maximum 100 h on line. Because oxygenated compounds, particularly aldehydes, in the bio-oil have produced coke that eventually plugs the active pore sites of the catalysts. In this study, raw bio-oil was pretreated by oxidation prior to performing HDO. The oxidized bio-oil plus raw bio oil control were hydrotreated with sulfided CoMo/γ-Al2O3 catalysts in a fixed-bed continuous reactor. Bio-oil types catalyzed included raw bio-oil, PTBO A, PTBO B, and raw bio oil previously hydrotrearted (HB). PTBO-A was produced by adding raw bio-oil mixed with 10 wt% hydrogen peroxide and 5 wt% oxone for 90 minutes under ambient temperature and pressure. PTBO-B was produced by mixing PTBO-A with 20 wt% butyric anhydride in a batch reactor, and the reaction was processed at 90 oC under ambient pressure for 1 h. HB was obtained by hydtrotreating raw bio-oil with Ni/Silica-alumina for 2 h in a 1.8 L batch reactor at a temperature of 340 oC and initial H2 pressure of 1000 psi. The sulfided CoMo/γ-Al2O3 catalysts catalyzed the four types of bio-oil. The application of HB showed the best hydrocarbon properties with total oil yield of 32.8 %. For this treated bio-oil type there was stable hydrocarbon selectivity during the first 600 min of the reaction, the hydrocarbon product contained 90 % of hydrocarbons, water content lower than 5 % and HHV of around 43 MJ/Kg.

Treated bio-oils upgraded in a fixed-bed continuous reactor with sulfided CoMo/ γ -Al2O3 catalysts

249th National Meeting (2015)

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