Effect of sulfidation pressure on the structure and activity of Ni(CyDTA)W/γ-Al2O3 hydrodesulfurization catalysts

• Published in: Catalysis today 2021-10, Vol.377, p.92-99
• Main Authors: Santolalla-Vargas, C.E., Santes, Victor, Suarez-Toriello, V.A., de los Reyes, J.A., Pawelec, B., Fierro, J.L.G., Garcia, E. Dominguez, Oliviero, L., Maugé, F.
• Format: Article
• Language: English
• Subjects: 1, 2-cyclohexanediamine-N, N, N”, N”-tetraacetic acid; Adsorbed CO; Catalysis; Chemical Sciences; Hydrodesulfurization; Nickel; Thiophene; Tungsten
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2020.07.015

[Display omitted] •NiW/γ-Al2O3 catalysts were prepared at different pHs and in presence of a chelating agent (CyDTA).•The influence of sulfurization pressure and its effect on the active species for hydrodesulfurization.•The surface species of sulfided catalysts was studied by several characterization techniques.•Sulfided catalysts were tested in HDS of thiophene. In this paper NiW/γ-Al2O3catalysts were prepared by consecutive impregnation of a W/γ-Al2O3 catalyst with an aqueous solution of nickel salt. The structural control of the nickel ion precursor in the impregnation solution was achieved by the addition of 1, 2-cyclohexanediamine-N, N, N’, N’-tetraacetic acid (CyDTA) as a chelating agent at different pH. The influence of the sulfidation pressure (1 bar vs 40 bar) on the activity and structure of the NiW catalysts was investigated. The catalysts performances were tested in hydrodesulfurization (HDS) of thiophene after sulfidation at atmospheric or high pressure. The catalysts were characterized by X-Ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and infrared spectroscopy of adsorbed CO (IR/CO) to explain the modification in surface species composition due to the chelating agent CyDTA and sulfiding conditions. NiW catalysts prepared in presence of CydTA and sulfided under high pressure displayed the highest HDS activity. These two factors enhanced the sulfidation degree of W-based species as characterized by XPS. A linear correlation was found between the HDS activity and the sulfidation degree. In addition, chelating agent addition induced a decrease on metal-support interaction, as pointed out by TPR, and strongly favored the creation of CUS sites on the NiWS phase as seen by IR/CO. All these features favored a high catalytic activity. In addition, high pressure sulfidation not only leads to more active NiW catalysts but improved the butene-over-butane ratio.