Gasoline selective hydrodesulfurization catalyst and preparation and application thereof

A hydrodesulfurization and catalyst technology, applied in the direction of catalyst activation/preparation, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of increased carbon deposition process, decreased gasoline octane number, high hydrogenation activity, etc., to achieve The effect of low production cost and high yield

Active Publication Date: 2017-01-04
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

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 shows However, when it is used in the hydrodesulfurization of gasoline, 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 the selective hydrodesulfurization of gasoline.
[0012] (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;
[0013] (2) The improvement of the selectivity of traditional supported catalysts is limited by the carrier;
[0014] (3) Most of the existing bulk catalysts are aimed at diesel components, have high hydrogenation activity, and easily cause a large amount of saturation of olefins, so they cannot be directly applied to the selective hydrodesulfurization reaction of gasoline;
[0015] (4) Most of the existing methods for preparing molybdenum disulfide by hydrothermal or solvothermal use reducing agent, surfactant or inorganic salt, which increases the complexity of preparation;
[0016] (5) The existing selective hydrodesulfurization process uses pre-distillation to separate light and heavy components, resulting in a lot of energy waste
[0017] At present, there are not many catalysts with high selectivity and high desulfurization rate for selective hydrodesulfurization of gasoline

Method used

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  • Gasoline selective hydrodesulfurization catalyst and preparation and application thereof
  • Gasoline selective hydrodesulfurization catalyst and preparation and application thereof
  • Gasoline selective hydrodesulfurization catalyst and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Mix 4.94g of ammonium heptamolybdate and 9.13g of thiourea and add 140ml of deionized water to dissolve it, transfer to a 200ml hydrothermal kettle, put it in an oven, conduct hydrothermal at 220°C for 18h, and then cool naturally. Suction filtration, ultrasonic washing with a mixed solvent of 1 volume ratio of water and absolute ethanol for 2-4 times, vacuum drying to obtain the precursor of molybdenum disulfide nanosheets; 0.428g cobalt acetate was dissolved in 6ml water, and 2.5g molybdenum disulfide nanosheets The tablet precursor was added to the previously prepared cobalt-containing solution, sonicated and stirred until it became viscous, and then transferred to a vacuum drying oven at 50°C for 24 hours to obtain a catalyst. The catalyst synthesized in this example is represented by Cat-A. The ICP element analysis of the molybdenum disulfide nanosheet precursor in this example showed that the molar ratio of sulfur to molybdenum was 2.03, and the specific surface ar...

Embodiment 2

[0051] A catalyst was prepared in the same manner as described in Example 1, except that 6.39 g of thiourea was used instead of the thiourea used in Example 1. The catalyst synthesized in this example is represented by Cat-B. The ICP element analysis of the molybdenum disulfide nanosheet precursor in this example showed that the molar ratio of sulfur to molybdenum was 1.98, and the specific surface area determined by nitrogen adsorption was 60m. 2 / g, its XRD characterization is as figure 1 As shown, the Raman spectrum is as figure 2 Shown.

Embodiment 3

[0053] A catalyst was prepared in the same manner as described in Example 1, except that 4.26 g of thiourea was used instead of the thiourea used in Example 1. The catalyst synthesized in this example is represented by Cat-C. The ICP element analysis of the molybdenum disulfide nanosheet precursor in this example showed that the molar ratio of sulfur to molybdenum was 1.94, and the specific surface area determined by nitrogen adsorption was 41 m. 2 / g.

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Abstract

The invention relates to a gasoline selective hydrodesulfurization catalyst and preparation and application thereof. According to the total mass of the catalyst being 100%, the catalyst is prepared from 3-15 wt% of VIII group metal, 45-58 wt% of Mo and 35-40 wt% of S. A preparation method of the catalyst comprises the following steps that 1, a defect-rich molybdenum disulfide nanosheet precursor with a non-stoichiometric ratio is prepared; 2, one kind of VIII group metal is added into the molybdenum disulfide nanosheet precursor through an ultrasonic assisting dipping method, the molar ratio of the VIII group metal to Mo is (0.1-0.5):1, the specific surface area of the molybdenum disulfide nanosheet precursor ranges from 40 m<2>/g to 90 m<2>/g, the pore volume ranges from 0.1 ml/g to 0.25 ml/g, and the molar ratio of sulfur to molybdenum is (1.92-2.10):1. Defect-rich molybdenum disulfide is prepared by controlling the stoichiometric ratio of molybdenum disulfide, and meanwhile more active loci are exposed. Compared with an existing catalyst, the catalyst is applied to a gasoline selective hydrodesulfurization reaction, the hydrogenation saturation factor of olefin is low, and the hydrodesulfurization rate of a sulfur-containing compound is high.

Description

Technical field [0001] The invention belongs to the field of petrochemical industry, and relates to a gasoline selective hydrodesulfurization catalyst and its preparation and application, in particular to a selective hydrodesulfurization bulk catalyst and a preparation method thereof and a selective hydrodesulfurization reaction in gasoline In the application. Background technique [0002] The problem of urban air pollution caused by motor vehicle exhaust is becoming more and more serious. Among them, sulfur oxides (SOx) produced by the combustion of sulfur compounds in gasoline can not only cause irreversible poisoning of the three-way catalyst of the engine exhaust purification system, and discharge it into the atmosphere. It can also cause acid rain and cause floating particles in the atmosphere, causing a series of problems such as increased PM 2.5 values. With the improvement of people's environmental awareness, countries have formulated strict environmental regulations to ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J37/34B01J37/10B01J27/051C10G45/08
Inventor 李灿蒋宗轩李萍刘铁峰
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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