Conversion of heavy gasoil into ultra-low sulfur and aromatic diesel over NiWRu/TiO2–γAl2O3 catalysts: Role of titanium and ruthenium on improving catalytic activity

This contribution deals with about selective conversion of heavy gas oils into middle distillates fuels that meet ultra-low sulfur and aromatic compound quality standards by using a novel NiWRu/TiO2–γAl2O3 catalyst under typical hydrotreatment conditions. A diesel fuel fraction having sulfur, nitrogen and aromatics compound content of about 50 ppm, 10 ppm and 15 v%, respectively, was obtained when the reactor was operated at T = 370 °C, P = 12.4 MPa, LHSV = 0.5 h−1 and H2/hydrocarbon ratio = 800 Nm3/m3. Titanium and ruthenium additives used in the preparation of the NiWRu/TiO2–γAl2O3 catalyst, remarkably improved the catalytic activities for the hydrogenolysis, hydrogenation and hydrocracking reactions compared to the reference NiW/γAl2O3 catalyst. The coprecipitation of titanium and aluminum hydroxides produced a catalyst support having greater surface area, pore volume and surface acidity. An improvement in mechanical properties of the support extrudates was also observed. Characterization analysis by XPS, AUGER and XRD techniques of the TiO2–γAl2O3 support suggested the formation of an aluminum-titanate mixed phase (AlxTiyOz) having a non-well-defined stoichiometry. The NiW/TiO2–γAl2O3 and NiWRu/TiO2–γAl2O3 exhibited a greater surface dispersion of the supported nickel and tungsten species compared to the NiW/γAl2O3 catalyst. The promoter effect of ruthenium on the NiW bimetallic system caused a strong increase in both hydrogenolysis and hydrogenation reactions. Hydrodenitrogenation and hydrocracking reactions were also favored by the increase in the hydrogenation capacity and in the surface acidity of the catalyst. The highest conversion levels for all investigated reactions were obtained when the NiWRu/TiO2–γAl2O3 catalyst was prepared by co-impregnation of Ni and Ru in a second step. This catalyst showed sulfur tolerance properties when the reaction was conducted in the presence of different H2S partial pressures. The catalytic behavior of the NiWRu/TiO2–γAl2O3 catalyst was explained by the existence of a promoting effect between separated Ni and Ru sulfides species and the NiWS phase (dual mechanism).