Multi-metal non-supported hydrofining catalyst, preparation method and applications thereof

Abstract

The invention relates to a multi-metal non-supported hydrofining catalyst and a preparation method thereof. The hydrofining catalyst is composed of at least one +3 valent metal oxide, at least one VIII group metal oxide, at least one IVB group metal oxide and two VIB group metal oxides, wherein based on metal oxide, the catalyst contains 10-50 wt% of VIII group metal, 1-30 wt% of IVB group metal,1-50 wt% of + 3 valent metal and 5-80 wt% of two VIB group metals. According to the invention, the catalyst can remove sulfur and nitrogen in model diesel oil to less than 10 ppm under the conditionsthat the temperature is 280-440 DEG C, the hydrogen pressure is 1-20 MPa, the volume ratio of hydrogen to diesel oil fraction is 50-1000 V / V, and the volume space velocity of the diesel oil fraction is 0.1-10 h<-1>.

Description

technical field [0001] The invention belongs to the field of petrochemical industry, and particularly relates to a multi-metal non-supported hydrorefining catalyst, a preparation method thereof, and an application in the process of ultra-deep hydrodesulfurization and denitrification of diesel fractions. Background technique [0002] SO generated due to the combustion of sulfur-containing compounds in fuel oil x It is the main culprit of air pollution and acid rain, and it can also cause irreversible poisoning of the three-way catalyst of the exhaust gas purification system of the automobile engine. At present, all countries in the world have promulgated and implemented strict fuel sulfur content standards: the Euro V standard implemented on September 1, 2009 stipulates that the sulfur content in diesel is less than 10mg / kg, and the National V standard issued by my country also stipulates the diesel sulfur content. Below 10 mg / kg, it was first implemented in Beijing on Februa...

AI Technical Summary

Problems solved by technology

Since the catalyst in this patent is a nickel-tungsten composite oxide Ni x W y o z and MoO 3 The two insoluble particles react in the slurry state, and the degree of reaction is limited, resulting in the inability of the active metal components in the final catalyst to be completely dispersed and uniform

[0009] Chinese patents CN102451707B, CN102773108B, CN103055887B, CN106179383B, CN106179388A, and CN106179390A disclose NiAlMoW hydrogenation bulk phase catalysts. The specific surface area and pore volume of the catalyst are improved by introducing Al, but due to the interaction between Al and the active metal, its hydrogenation catalysis The activity is limited, and its catalyst is still through Al-Ni-W composite oxide and MoO 3 The two insoluble particles react in the slurry state, and the degree of reaction is limited, so that the active metal components in the final catalyst cannot be completely dispersed evenly

[0012] 1) The specific surface area and pore volume of the catalyst are small, and the activity needs to be improved;

[0013] 2) The raw materials used for synthesis are not environmentally friendly;

[0014] 3) The preparation cost of the catalyst is relatively high. If cheap metals are introduced to reduce the cost, they will interact with the active components and inhibit the catalytic activity;

[0015] 4) Most of them only pay attention to the hydrodesulfurization activity of the catalyst, and seldom pay attention to the hydrodenitrogenation activity of the catalyst

Afterwards, my research group disclosed in Chinese patent CN106268850B the introduction of Group IVB metal M IVB Prepared NiM IVB MoW non-supported hydrogenation catalyst, the dispersion degree of its active components has been greatly improved, but its preparation cost is still high

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