Promoted catalysts for hydrogenation of bicyclic aromatic hydrocarbons obtained in situ from molybdenum and tungsten carbonyls

Аннотация

Promoted Мo and W catalysts have been prepared in situ via thermal decomposition of precursors, oil-soluble salts Mo(CO)₆, W(CO)₆, С°C₁₆H₃₀O₄, and NiC₁₆H₃₀O₄. TiO₂, Al₂O₃, and ZrO(NO₃)₂ · 6H₂O have been used as the acidic additives. Also, Mo and W unsupported sulfide catalysts have been prepared in the presence of elemental sulfur as the sulfiding agent. The catalysts have been characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The activity of the catalysts prepared in situ has been evaluated in the hydrogenation reaction of bicyclic aromatic hydrocarbons by the example of model mixtures of 10% solutions of naphthalenes (unsubstituted naphthalene, 1- and 2-methylnaphthalenes, and 1,5- and 2,3-dimethylnaphthalenes) in n-hexadecane. The effect of the precursor/acidic oxide ratio on the activity of the formed catalyst has been found. Hydrogenation of bicyclic aromatic hydrocarbons has been conducted at a hydrogen pressure of 2 and 5 MPa and a temperature of 380 and 400°C for 2 h. Hydrogenation of the unsubstituted aromatic ring has been preferable due to the absence of steric hindrances. The degree of conversion of n-hexadecane under the reaction conditions has been 1.5–7.5% depending on the reaction temperature. It has been found that the activity of the sulfided catalyst in the conversion of 1- and 2-methylnaphthalenes is inferior to the activity of the unsulfided analogue, while partial replacement of TiO₂ by Al₂O₃ results in a decrease in the conversion of the substrates as opposed to the unsulfided catalysts, in which the use of nanocrystalline Al₂O₃ promotes an increase in the conversion.