Reactivities of Various Alkyl Dibenzothiophenes in Oxidative Desulfurization of Middle Distillate with Cumene Hydroperoxide
2017
Safa, Muhieddine A. | Al-Shamary, Tahani | Al-Majren, Rawan | Bouresli, Rashed | Ma, Xiaoliang
The oxidation reactivities of various alkyl dibenzothiophenes (DBTs) were evaluated and compared by measuring the rate constant of each alkyl DBT in oxidative desulfurization of a hydrotreated middle distillate (HMD) with cumene hydroperoxide at 75 °C over a MoO₃/Al₂O₃ catalyst. It was found that the major sulfur compounds with higher abundance in HMD are the DBTs with alkyl substituents at the 4- and/or 6-positions, and the oxidative reaction of each alkyl DBT follows a pseudo-first-order reaction. The measured rate constants indicate that the oxidation reactivity of these alkyl DBTs decreases in the order of 4-MDBT > 2,4,6-TMDBT ≈ 3,4,6-TMDBT > 1,4,6-TMDBT ≈ 4,6-DMDBT > 4-E,6-MDBT. Comparison of the molecular structures of these sulfur species with their reactivities implies that the oxidation activity of alkyl DBTs with oil-soluble oxidant over a solid catalyst is mainly dependent on the steric hindrance around the central sulfur atom caused by the alkyl substituents at the 4- and/or 6-positions.
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