Oxidative desulfurization of model and real oil samples using Mo supported on hierarchical alumina-silica: Process optimization by Box-Behnken experimental design

The catalytic performance of Mo supported on hierarchical alumina-silica (Si/Al=15) with Mo loadings of 3, 6 and 15 wt% was investigated for the oxidative desulfurization (ODS) of model and real oil samples. Hierarchical alumina-silica (hAl-Si) was synthesized by economical and ecofriendly silicate-1 seed-induced route using cetyltrimethylammonium bromide (CTAB) as mesoporogen. The effect of CTAB on the structure of catalyst was studied by characterization techniques. The results revealed that 6%Mo/hAl-Si had the highest sulfur removal compared to the other catalyst loadings. The effect of operating parameters was evaluated using Box-Behnken experimental design. The optimal desulfurization conditions with the 6%Mo/hAl-Si catalyst were determined at oxidation temperature of 67℃, oxidation time of 42 min, H₂O₂/S molar ratio of 8 and catalyst dosage of 0.008 g·ml^-1 for achieving a conversion of 95%. Under optimal conditions, different sulfur-containing compounds with initial concentration of 1000 ppm, Dibenzothiophene (DBT), Benzothiophene (BT) and Thiophen (Th), showed the catalytic oxidation reactivity in the order of DBT > BT > Th. According to the regeneration experiments, the 6%Mo/hAl-Si catalyst was reused 4 times with a little reduction in the performance. Also, the total sulfur content of gasoline and diesel after ODS process reached 156.6 and 4592.2 ppm, respectively.