Nickel- and Cobalt-Molybdenum Sulfide Catalysts for Hydrogenation and Hydrodesulfurization Prepared in Situ from Bimetal Precursors

Non-supported niockel-molybdenum and cobalt-molybdenum sulfide catalysts were prepared through in situ decomposition of water-soluble bimetal precursors in hydrocarbon feedstock. The precursors were nickel- and cobalt-molybdenum complexes with citric, oxalic, amber, glutaric and tartaric acids. The prepared sulfide catalysts were characterized using transmission electron microscopy and X-ray photoelectron spectroscopy. The catalyst activities to hydrogenation of bicyclic aromatic hydrocarbons and to hydrodesulfurization of dibenzothiophene were studied. The composition of the ‘precursor solution in hydrocarbon feedstock’ emulsion was established to influence the catalyst activity. The high activity was reached as soon as in an hour after the reaction started. The reactions under consideration were hydrogenation of mono-, di- and trimethylnaphthalenes, as well as hydrogenation of ethylnaphthalene. The optimal promoter:molybdenum ratio equal to 0.25 : 1 was determined. The catalyst activity was demonstrated not to decrease upon recirculation because of the absence of the negative effect of water (constituent of the emulsion) that oxidizes the catalyst surface. After the second cycle of the reaction, the catalyst particles are longer and bear more MoS₂ layers than the particles after the first cycle. XPS studies revealed that recirculation results in a decrease in the total oxygen content on the catalyst surface, in an increase in the metal proportion in the sulfide surrounding and sulfur in the sulfide state.

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