Mutual inhibition effect of sulfur compounds in the hydrodesulfurization of thiophene, 2-ethylthiophene and benzothiophene ternary mixture

Abstract

The hydrodesulphurization of a model component and equimolar ternary mixture of thiophene, 2-ethylthiophene and benzothiophene over sulphided CoMo/γ-Al₂O₃ and CoMo/γ-Al₂O₃-Nb₂O₅ catalysts were investigated in a fixed bed flow reactor. The catalysts were prepared by incipient wetness impregnation method and characterized by textural characteristics, total acidity and chemical species present on the catalysts surface. The characterization results showed that both CoMo/γ-Al₂O₃-Nb₂O₅ and sulphided CoMo/γ-Al₂O₃ catalysts exhibit a mesoporous structure with cylindrical pores open at both ends, evidenced by the IV type adsorption–desorption isotherm with a H1 hysteresis loop and have an average pore diameter between 3 and 4 nm. The chemical species present on the catalysts surface evaluated by XPS indicated that Co²⁺ and Mo⁴⁺ species are present in the sulfide form on both catalysts surfaces. In addition, there are also found oxidic species arising from incomplete reduction and sulphidation. The presence of niobium oxide in the catalytic support had a positive effect in leading to higher specific surface area (170 m²/g) and total acidity (0.421 meq/g) compared with CoMo/γ-Al₂O₃ catalyst (140 m²/g and 0.283 meq/g) respectively. The evaluation results from the hydrodesulfurization showed that CoMo/γ-Al₂O₃-Nb₂O₅ catalyst had a higher activity in hydrodesulphurization process of thiophene, 2-ethylthiophene and benzothiophene. The CoMo/γ-Al₂O₃-Nb₂O₅ catalyst eliminated sulfur from the single component feed (corresponding to 2380 ppm S) and reduced below 10 ppm, for the feed consisting in the equimolar ternary mixture of thiophene, 2-ethylthiophene and benzothiophene (2380 ppm S). The reactivity of thiophen compounds was reduced due to competitive adsorption. It was observed that benzothiophene inhibits the transformation of thiophene and 2-ethylthiophene. A mutual inhibition effect between sulfur compounds was also observed when thiophene, 2-ethylthiophene and benzothiophene were combined and tested over the CoMo/γ-Al₂O₃ catalyst. The inhibition effect had a lower intensity by introducing Nb₂O₅ in the catalyst support.