Gasoline selective hydrodesulfurization bulk phase catalyst, and preparation method and application thereof

Abstract

The invention relates to a gasoline selective hydrodesulfurization bulk phase catalyst, and a preparation method and an application thereof. The catalyst is mixed metal oxide comprising a group VIII metal, a +3 valence metal, a group IIA metal, a group IA metal and a group VIB metal, and the catalyst comprises 20-95 wt% of group VIII metal oxide, 0-25 wt% of +3 valence metal oxide, 0-50 wt% of group IIA metal oxide, 0-2 wt% of group IA metal oxide and 5-30 wt% of group VIB metal oxide. The specific surface area of the catalyst is 80-210 m<2> / g, and the pore volume of the catalyst is 0.3-0.8 ml / g. Compared with present catalysts, the catalyst provided by the invention has the advantages of low olefin hydrogenation saturation exponent and low sulfur-containing compound hydrodesulfurization rate when being applied to gasoline selective hydrodesulfurization reactions.

Description

technical field [0001] The invention belongs to the field of petrochemical industry and relates to a hydrorefining bulk catalyst and its preparation and application, in particular to a selective hydrodesulfurization bulk catalyst and its preparation method and its use in gasoline selective hydrodesulfurization reaction application. Background technique [0002] The problem of urban air pollution caused by automobile exhaust is becoming more and more serious. Among them, the sulfur oxides (SOx) produced by the combustion of sulfur compounds in gasoline can not only irreversibly poison the three-way catalyst of the engine exhaust purification system, but also emit into the atmosphere. It will cause acid rain, and lead to particle floating in the atmosphere, causing a series of problems such as the increase of PM 2.5 value. With the improvement of people's awareness of environmental protection, countries have formulated strict environmental regulations to limit the sulfur cont...

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Problems solved by technology

The hydrodesulfurization selectivity of the catalyst is relatively improved, but the disadvantage is that its complicated and harsh carbon deposition process increases the difficulty of industrial operation and limits its industrial application

Chinese patents CN1339985A, CN101544904A, CN101153228A, CN101733120A and CN103657672A also disclose a preparation method of a NiMoW tri-metal bulk catalyst and its application in ultra-deep desulfurization of diesel oil, although the prepared catalyst is used in the ultra-deep hydrodesulfurization reaction of diesel oil It shows high activity, but when it is used in gasoline hydrodesulfurization, because the hydrogenation activity of this type of catalyst is too high, it will cause the saturation of a large amount of olefins, which limits its application in gasoline selective hydrodesulfurization

[0009] (1) While the traditional hydrodesulfurization catalyst removes sulfur compounds in gasoline, it causes hydrogenation saturation of a large number of olefins in gasoline, resulting in a sharp drop in gasoline octane number and a large amount of unnecessary hydrogen consumption;

[0010] (2) The existing technology adopts the mode of pre-distillation to separate light and heavy components, which causes a large amount of energy waste;

[0011] (3) The dispersion of active components and the improvement of catalyst selectivity of traditional supported catalysts are affected by the carrier;

[0012] (4) Most of the existing bulk catalysts are aimed at diesel components, have high hydrogenation activity, and can cause a large amount of saturation of olefins, so they cannot be directly applied to the selective hydrodesulfurization reaction of gasoline

Previously, our group reported the preparation method of NiMoW bulk catalyst in patents CN101733120A and CN103657672A. This type of catalyst can realize ultra-deep hydrodesulfurization of diesel under relatively mild conditions. However, due to the extremely high hydrogenation activity of this type of catalyst, it cannot For the selective hydrodesulfurization reaction of gasoline

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