Deep oxidative desulfurization of gas oil by iron(III)-substituted polyoxometalate immobilized on nickel(II) oxide, ((n-C4H9)4N)4H[PW11FeO39]@NiO, as an efficient nanocatalyst

Mohammad Ali Rezvani; Kolsom Ghasemi; Hadi Hassani Ardeshiri; Masomeh Aghmasheh

doi:10.1038/s41598-023-42545-9

Deep oxidative desulfurization of gas oil by iron(III)-substituted polyoxometalate immobilized on nickel(II) oxide, ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO, as an efficient nanocatalyst

Sci Rep. 2023 Sep 14;13(1):15233. doi: 10.1038/s41598-023-42545-9.

Authors

Mohammad Ali Rezvani¹, Kolsom Ghasemi², Hadi Hassani Ardeshiri^{2

3}, Masomeh Aghmasheh²

Affiliations

¹ Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan, 451561319, Iran. marezvani@znu.ac.ir.
² Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan, 451561319, Iran.
³ Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran, 16846-13114, Iran.

Abstract

Sulfur compounds are among the most unfavorable constituents of petroleum derivatives, so stringent regulations have been established to curb their atmospheric emissions. In this regard, a new nanocomposite ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO) was synthesized composed of quaternary ammonium bromide salt of iron^III-substituted Keggin-type polyoxometalate immobilized on nickel(II) oxide nanoceramics via sol-gel method. The assembled (n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO nanocomposite was identified by FT-IR, UV-Vis, XRD, SEM, EDX, and TGA-DTG methods. The characterization results exhibited that ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉] dispersed uniformly over the surface of the NiO nanoceramics. The ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO nanocomposite was employed as a heterogeneous nanocatalyst in the extractive coupled oxidation desulfurization (ECOD) of real gas oil and dibenzothiophene (DBT) as a model compound. Under relatively moderate conditions, the catalytic performance of the ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO in the ECOD procedure was studied by incorporating acetic acid/hydrogen peroxide as an oxidant system at a volume ratio of 1:2. According to the ECOD results, the ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO demonstrated the effectiveness of up to 95% with 0.1 g at 60 °C under optimal operating conditions. Moreover, the ((n-C₄H₉)₄N)₄H[PW₁₁FeO₃₉]@NiO nanocatalyst could be separated and reused for five runs without a noticeable decrease in the ECOD process. This study provides a promising way to meet the target of ultra-low sulfur as an essential process in oil refineries.