Oxidative removal of dibenzothiophene and related sulfur compounds from fuel oils under pressurized oxygen at room temperature with hydrogen peroxide and a phosphorus-free catalyst: sodium decatungstate

We investigated the removal of dibenzothiophene (DBT) and related compounds, 4-methyldibenzothiophene (4-MeDBT), 4,6-dimethyldibenzothiophene (4,6-DMeDBT), 2,8-dimethyldibenzothiophene (2,8-DMeDBT), and 1-benzothiophene (1-BT) from several oil media at room temperature under pressurized O2 (0.6 MPa) by means of a three-phase reaction system consisting of the oil phase, an aqueous phase containing the phosphorus-free polyoxotungstate catalyst Na4W10O32·8H2O, H2O2, and tetraoctylammonium bromide, and the gas phase. Under conditions in which the initial DBT concentration in octane was 10.1 mM, the desulfurization ratio reached 87% after reaction for 6.5 h. The sulfur atoms in the initial DBT were well accounted for by the sulfur atoms in the residual DBT, the dibenzothiophene sulfone and dibenzothiophene 5-oxide in the octane phase, and the dibenzothiophene sulfone that precipitated. Prolonged reaction time to 18 h resulted in 92% desulfurization. The desulfurization of octane decreased in the order 2,8-DMeDBT ~ DBT > 4-MeDBT >1-BT ~ 4,6-DMeDBT. Light oil and kerosene could also be desulfurized efficiently: after reaction for 6.5 h, the desulfurization ratios reached 77 and 78% for light oil and kerosene, respectively. •DBT in octane was efficiently removed by sodium decatungstate catalyst.•The three-phase reaction system uses aqueous decatungstate, H2O2, TOABr, and O2.•Consecutive reactions with changing octane phase were possible.•Desulfurization decreased in the order 2,8-DMeDBT ~ DBT > 4-MeDBT > 1-BT ~ 4,6-DMeDBT.•Light oil and kerosene could also be desulfurized efficiently.