Preparation method of desulfurization catalyst, desulfurization catalyst and application of desulfurization catalyst

Abstract

The embodiment of the invention relates to a preparation method of a desulfurization catalyst, the desulfurization catalyst and application of the desulfurization catalyst. The catalyst comprises at least one VIII group metal, at least two VIB group metals and one IVA group nonmetal. The invention also discloses a preparation method and application of the catalyst. The catalyst is used for hydrodesulfurization of a diesel fraction containing 4, 6-dimethyl dibenzothiophene, has extremely high hydrodesulfurization activity, realizes ultra-deep desulfurization, and reduces the cost of the catalyst by introducing IVA family nonmetal.

Description

Technical Field

[0001] The present disclosure relates to the technical field of energy processing, and particularly to a preparation method of a desulfurization catalyst, the desulfurization catalyst, and its application. Background Art

[0002] Due to the decline in oil reserves, the problems of heavy and inferior oil quality are becoming increasingly prominent. The amount of high-sulfur crude oil is increasing year by year worldwide, and the environmental legislation of various countries regarding the requirement to limit the sulfur content in fuel is becoming increasingly strict. Therefore, the development of a super-deep hydrodesulfurization catalyst with excellent performance has not only become the core in the field of hydrodesulfurization but also made the hydrotreating technology increasingly valued in the petroleum processing industry. Sulfides in oil products are the main source of air pollution. The SOx generated after the combustion of organic sulfur compounds in fuel can not only cause acid rain but also cause irreversible poisoning of the three-way catalyst in the vehicle engine exhaust purification system. It will also participate in the formation of particulate matter PM2.5, leading to an increasing number of hazy days, seriously harming the environment and human health, and thus attracting wide attention. For this reason, various countries have promulgated strict fuel sulfur content standards. Europe achieved a diesel sulfur content of less than 10 ppmw in 2005. In China, the Beijing V clean diesel standard with a sulfur content lower than 10 ppmw was first implemented in Beijing on June 1, 2012, and the diesel sulfur index equivalent to Euro IV (<50 ppmw) emission standards was comprehensively implemented nationwide in 2015. On July 1, 2017, China comprehensively implemented the clean diesel sulfur index equivalent to Euro V (<10 ppmw) emission standards, and the fuel sulfur content standard equivalent to Euro V (<10 ppmw) was promoted and used nationwide in 2023.

[0003] As the standards for sulfur content limitation are getting higher and higher, adjusting process operating conditions and using new reactors both require huge investment costs. In contrast, developing a new catalyst that can perform super-deep hydrodesulfurization on existing production units under current operating conditions is a more economical and feasible method.

[0004] U.S. Patents US09 / 518741, US08 / 900389, US09 / 869988, etc. all reported a NiMoW bulk catalyst. The synthesis methods of this catalyst all use ammonia water as a complexing agent to complex with the reaction raw material Ni 2+ complex, and through a slow heating process, the nickel ammonia complex slowly decomposes to release Ni 2+React with molybdenum and tungsten in the solution to form a NiMoW catalyst precursor, and then form a NiMoWS sulfide catalyst through calcination and sulfidation. Chinese Patent CN1339985A also discloses a method for synthesizing a NiMoW catalyst. This patent mainly involves reacting molybdenum and tungsten salts with nickel basic carbonate in an aqueous solution, ensuring that at least part of the metal components exist in a solid state during the reaction, and finally obtaining the catalyst through sulfidation.

[0005] It is not difficult to find from the existing reported work that the existing synthesis methods of bulk catalysts have the following deficiencies:

[0006] (1) The raw materials used are not environmentally friendly;

[0007] (2) The preparation cost of the catalyst is relatively high. SUMMARY OF THE INVENTION

[0008] The object of the present disclosure is to provide a preparation method of a desulfurization catalyst, a desulfurization catalyst and its application.

[0009] To achieve the above object, in one aspect of the present disclosure, there is provided a preparation method of a desulfurization catalyst, including:

[0010] Providing solution A containing a soluble salt of at least one Group VIII metal; providing solution B including a soluble salt of at least one Group IVA non-metal; mixing and reacting solution A containing a soluble salt of at least one Group VIII metal with solution B containing a soluble salt of at least one Group IVA non-metal and an alkaline precipitating agent, and obtaining a catalyst precursor through filtration and washing; mixing the obtained catalyst precursor with a polar solvent in a wet state and stirring to prepare a catalyst precursor slurry; providing solution C containing a soluble salt of at least two Group VIB metals, and mixing solution C containing a soluble salt of at least two Group VIB metals with the catalyst precursor slurry and heating to dryness to obtain the catalyst.

[0011] Further, the concentration of Group VIII metal ions in solution A is 0.01 - 0.3 mol / L, the concentration of Group IVA non-metal ions in solution B is 0.01 - 0.3 mol / L, the concentration of the alkaline precipitating agent is 0.7 - 2.1 mol / L, the concentration of the catalyst precursor slurry is 0.01 - 0.9 mol / L, and the concentration of Group VIB metal ions in solution C is 0.01 - 0.2 mol / L.

[0012] Further, solution A and solution B react at 20°C - 220°C for 4 - 50 hours, and solution C and the catalyst precursor slurry are heated to dryness at 50°C - 350°C.

[0013] Further, the soluble salts of Group IVA non-metals include one or more of sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate pentahydrate, and sodium metasilicate nonahydrate; the soluble salts of Group VIII metals include one or more of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, or cobalt acetate; the basic precipitants include one or more of sodium hydroxide and potassium hydroxide; the soluble salts of Group VIB metal anions include one of ammonium molybdate, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid, and sodium molybdate, and one of ammonium tungstate, phosphotungstic acid, ammonium metatungstate, tungstic acid, or sodium tungstate; and the polar solvents include one or more of water and ethylene glycol.

[0014] One aspect of the present disclosure also provides a desulfurization catalyst, which includes a mixed metal oxide composed of at least one Group VIII metal, at least two Group VIB metals, and one Group IVA non-metal; wherein, calculated as oxides, the desulfurization catalyst contains 1-50 wt% of Group VIII metal, 1-50 wt% of Group VIB metal, and 1-50 wt% of Group IVA non-metal.

[0015] Further, the desulfurization catalyst includes at least one Group VIII metal, two Group VIB metals, and one Group IVA non-metal, and the molar ratio of the Group VIII metal to the Group VIB metal is 20:1 - 1:20; the molar ratio of the Group VIII metal to the Group IVA non-metal is 20:1 - 1:1; and the molar ratio of the two Group VIB metals is 5:1 - 1:5.

[0016] Further, the Group VIII metal includes Ni or Co; the Group VIB metals include Mo and W; and the Group IVA non-metal includes Si.

[0017] Further, the desulfurization catalyst has a multi-walled nanotube structure or a layered nanosheet structure. The specific surface area of the desulfurization catalyst with a multi-walled nanotube structure is 30 - 300 m 2 / g, and the pore volume is 0.1 - 0.5 mL / g. The specific surface area of the desulfurization catalyst with a layered nanosheet structure is 30 - 300 m 2 / g, and the pore volume is 0.1 - 0.5 mL / g.

[0018] The embodiments of the present disclosure also provide an application of the desulfurization catalyst in the hydrodesulfurization reaction of sulfur-containing organic compound fuels.

[0019] Further, the conditions of the hydrodesulfurization reaction are: temperature 250 - 450 °C, hydrogen pressure 1 - 20 MPa, the volume ratio of hydrogen to the sulfur-containing organic compound fuel is 50 - 1500 Nm 3 / m 3 ; the volume space velocity of the sulfur-containing organic compound fuel is 0.1 - 10 h -1 .

[0020] Compared with the prior art, the present disclosure has at least the following advantages:

[0021] 1) In the present disclosure, a compound with a multi-walled nanotube structure or a layered nanosheet structure is used as a precursor for synthesizing a catalyst, and a multi-metal bulk catalyst with a multi-walled nanotube structure or a layered nanosheet structure is designed and synthesized. The synthesis process is easy to operate, environmentally friendly, and the catalyst can be industrially produced.

[0022] 2) A Group VIB active metal is successfully introduced into the precursor, so that the distribution and dispersion of the active metal are more uniform, forming more active centers, which determines that this catalyst has ultra-high hydrodesulfurization activity. Under mild operating conditions, the sulfur content in 4,6-dimethyldibenzothiophene in the diesel fraction can be reduced from 517 ppm to below 10 ppm, achieving ultra-deep desulfurization.

[0023] 3) By introducing a Group IVA non-metal, the cost of the catalyst is reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the XRD pattern of the desulfurization catalyst and its catalyst precursor prepared in Example 1 of the present disclosure.

[0025] Figure 2 is the TEM image of the catalyst precursor prepared in the examples of the present disclosure.

[0026] Figure 3 is the SEM image of the desulfurization catalyst prepared in the examples of the present disclosure.

[0027] Figure 4 is the curve graph of the change in hydrodesulfurization activity of the desulfurization catalyst prepared in the examples of the present disclosure. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0028] The preparation method of the catalyst provided by the present disclosure, the catalyst and its application will be described in detail below with reference to the drawings.

[0029] In other embodiments of the present disclosure, a preparation method of a catalyst is provided, and the method includes:

[0030] S01: Add a soluble salt of at least one Group VIII metal to a solvent to prepare a solution A, add a soluble salt of at least one Group IVA non-metal to water to prepare a solution B, mix and react the solution A and the solution B, and then add particles of a basic precipitant or a solution of a basic precipitant and mix and react for a period of time. After filtration and washing, a catalyst precursor is obtained. The obtained catalyst precursor is mixed with a polar solvent in a wet state and stirred to prepare a catalyst precursor slurry;

[0031] S02: Prepare a solution C by mixing soluble salts of at least two Group VIB metals, and mix the solution C with the catalyst precursor slurry and then heat to evaporate the solvent to obtain the catalyst.

[0032] In one embodiment of the present disclosure, S01 specifically includes: adding soluble salts of at least one Group VIII metal into a mixed solution of water, an organic solvent and a surfactant to prepare a solution A of the soluble salts, then dissolving soluble salts of a Group IVA non-metal in water to form a solution B, and finally adding the solution B into the solution A containing soluble salts of at least one Group VIII metal for coprecipitation reaction, and then adding particles of a basic precipitant or a solution of a basic precipitant to react for a period of time, and obtaining a catalyst precursor with a multi-walled nanotube or layered nanosheet structure through filtration and washing. Mix the obtained catalyst precursor with a polar solvent in a wet state and stir to prepare a catalyst precursor slurry;

[0033] S02 specifically includes: mixing the catalyst precursor slurry with a multi-walled nanotube or layered nanosheet structure and a polar solvent containing soluble salts of at least two Group VIB metal anions, heating to evaporate the solvent, and after the reaction is completed, calcining at 400 - 500 °C for 2 - 10 hours to obtain a desulfurization catalyst with a layered structure containing at least one Group VIII metal, one Group IVA non-metal and two Group VIB metals.

[0034] In one embodiment of the present disclosure, the surfactant in S01 is one or more of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, octadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, PEG, PEG - 400, PEG - 600, PEG - 800, PEG - 4000, PVA, SA20, Triton - 100.

[0035] In one embodiment of the present disclosure, the concentration of Group VIII metal ions in the solution A is 0.01 - 0.3 mol / L, the concentration of Group IVA non-metal ions in the solution B is 0.01 - 0.3 mol / L, the concentration of the catalyst precursor solution is 0.01 - 0.9 mol / L, and the concentration of Group VIB metal ions in the solution C is 0.01 - 0.2 mol / L.

[0036] In one embodiment of the present disclosure, the solution A and the solution B react at 20 °C - 220 °C for 4 - 50 hours, and the solution C and the catalyst precursor slurry are mixed and heated to evaporate the solvent at 50 °C - 350 °C.

[0037] In one embodiment of the present disclosure, the soluble salts of Group IVA non-metals include one or more of sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate pentahydrate, and sodium metasilicate nonahydrate. The soluble salts of Group VIII metals include one or more of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, or cobalt acetate. The soluble salts of Group VIB metal anions include one of ammonium molybdate, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid, and sodium molybdate, and one of ammonium tungstate, phosphotungstic acid, ammonium metatungstate, tungstic acid, or sodium tungstate. The polar solvents include one or more of water and ethylene glycol.

[0038] To further illustrate the preparation method of the catalyst of the present disclosure, the following multiple examples are listed for illustration. Among them, Examples 1 and 2 and Examples 4 - 12 are for the preparation of NiSiMoW catalysts with multi-walled nanotube structures, and Examples 3 and Examples 13 - 24 are for the preparation of NiSiMoW catalysts with layered nanosheet structures.

[0039] Example 1

[0040] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0041] a) Weigh nickel nitrate (29.08 g, where Ni 2+ 0.1 mol) and sodium silicate (56.84 g, where SiO3 2- 0.2 mol) separately, dissolve them in a 1500 ml mixed solution containing water, ethylene glycol, and Triton-100, add 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a light green mixed reaction solution. Reflux this solution at 80 °C for 25 hours to obtain a light green product. Filter and wash the obtained light green product to obtain a catalyst precursor, which is NiSiO3 with a multi-walled nanotube structure. Add this catalyst precursor to 200 ml of water in a wet state and stir to prepare a catalyst precursor slurry.

[0042] b) Weigh ammonium molybdate (5.4 g, where Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, where W 6+0.03 mol), dissolve them in a mixed solution composed of 300 ml of water and ethylene glycol, heat this solution to the reaction temperature, and continuously stir to form a colorless transparent solution; then heat the catalyst precursor slurry prepared in step a) to the reaction temperature; slowly add the catalyst precursor slurry to the colorless transparent solution to form a light green reaction solution, heat it to dryness at 100 °C to obtain a light green paste; dry the light green paste at 120 °C to obtain the NiSiMoW catalyst (8.1 g). The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 40.2 m 2 / g, and the pore volume is 0.10 mL / g.

[0043] This catalyst is a light green powder, and its molecular formula is determined by XRF to be 6NiO·4SiO2·MoO3·WO3. The catalyst synthesized in this example is denoted as NT-NSMW-1. The XRD characterization results of its precursor NiSiO3 and the catalyst are as Figure 1 shown in Figure a in it. It can be found that in the spectrum of NiSiO3, characteristic peaks of the multi-walled NiSiO3 nanotube structure exist at 12.5°, 20°, 25°, 35°, 37.5°, and 62°. After further mixing with Mo and W salts, the characteristic peaks of the nanotube structure of the catalyst still exist, and some peaks shift from 20° to 17°. These all well illustrate that NiSiO3 with a nanotube structure has been successfully synthesized, and Mo and W active metals have been successfully introduced into the catalyst precursor to form a bulk catalyst with highly dispersed active species. The TEM characterization results of the precursor NiSiO3 are listed in Figure 2 Figure a in it. It can be seen that the NiSiO3 nanotube structure is more obvious, with a length of about 100 nm, an inner diameter of about 10 nm, and an outer diameter of about 22 nm. The SEM characterization of NT-NSMW-1 is as Figure 3 shown in Figure a in it. It can be seen that the catalyst still well maintains the multi-walled nanotube structure after introducing Mo and W.

[0044] Example 2

[0045] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0046] a) Weigh nickel nitrate (29.08 g, where Ni 2+ 0.1 mol) and sodium silicate (56.84 g, where SiO3 2-(0.2 mol), dissolve them in 1500 ml of a mixed solution containing water, ethylene glycol and Triton-100, add 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a light green mixed reaction solution. Reflux the reaction solution at 80 °C for 25 hours to obtain a light green product; filter and wash the light green product obtained from the reaction to obtain a catalyst precursor, which is NiSiO₃ with a multi-walled nanotube structure; add this catalyst precursor to 200 ml of water in a wet state and stir to prepare a catalyst precursor slurry.

[0047] b) Weigh ammonium molybdate (10.8 g, where Mo 6+ 0.06 mol) and ammonium metatungstate (14.4 g, where W 6+ 0.06 mol) to replace the ammonium molybdate (5.4 g, where Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, where W 6+ 0.03 mol) used in Example 1, heat to dryness at 150 °C instead of 100 °C in Example 1, and prepare a multi-metal bulk catalyst (14.4 g) in the same manner as in Example 1. The synthesized multi-metal bulk catalyst is denoted as NT-NSMW-2, and the morphology of this catalyst is similar to that of the NT-NSMW-1 catalyst. Its ultra-high hydrodesulfurization activity is as Figure 4 shown in Figure a of. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 39.8 m 2 / g, and the pore volume is 0.11 mL / g.

[0048] Example 3

[0049] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0050] a) Weigh nickel nitrate (29.08 g, where Ni 2+ 0.1 mol), sodium silicate (56.84 g, where SiO₃ 2- 0.2 mol), dissolve them in 1500 ml of a mixed solution containing water, ethylene glycol and Triton-100, add 1500 ml of a solution containing 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a light green mixed reaction solution. Reflux the reaction solution at 80 °C for 25 hours to obtain a light green product; filter and wash the light green product obtained from the reaction to obtain a catalyst precursor, which is NiSiO₃ with a layered nanosheet structure; add this catalyst precursor to 200 ml of water in a wet state and stir to prepare a catalyst precursor slurry.

[0051] b) Weigh out ammonium molybdate (5.4 g, Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, of which W 6+ 0.03mol), dissolve them in a polar solvent (300ml) to form a solution, and heat the solution to the reaction temperature, stirring continuously to form a colorless transparent solution; then heat the catalyst precursor slurry prepared in step a) to the reaction temperature; slowly add the slurry to the colorless transparent solution to form a light green reaction liquid, heat it at 100°C and evaporate it to dryness to obtain a light green paste; dry the light green paste at 120°C to obtain a NiSiMoW catalyst (7.4g). The specific surface area of ​​the catalyst measured by low-temperature nitrogen adsorption is 33.7m 2 / g, and the pore volume is 0.12mL / g.

[0052] The catalyst is a light green powder, and its molecular formula is 7NiO·0.5SiO2·MoO3·WO3 as determined by XRF. The catalyst synthesized in this example is represented by NS-NSMW. The XRD characterization results of its precursor NiSiO3 and catalyst are shown in Figure 1 As shown in Figure b, it can be found that in the spectrum of NiSiO3, characteristic peaks of layered NiSiO3 nanosheet structure exist at 19°, 33°, 39°, 52°, 59° and 62°. After further reaction with Mo and W salts, the characteristic peaks of the catalyst's nanosheet structure still exist. These all well illustrate that we have successfully synthesized NiSiO3 with a nanosheet structure and successfully introduced Mo and W active metals into the catalyst precursor to form a bulk catalyst with highly dispersed active species. The TEM characterization results of the precursor NiSiO3 are listed in Figure 2 In Figure b, we can see that the NiSiO3 nanosheet structure is more obvious, with a size of about 50nm and mostly hexagonal. Figure 3 As shown in Figure b, it can be seen that after the introduction of Mo and W, the catalyst still maintains a layered nanosheet structure. The ultra-high hydrodesulfurization activity of NS-NSMW catalyst is shown in Figure 2. Figure 4 As shown in Figure b.

[0053] Example 4

[0054] This example illustrates the preparation method of NiSiMoW catalyst with multi-walled nanotube structure:

[0055] Except that in step a, the reaction was carried out at 100 °C for 10 hours instead of 80 °C for 25 hours used in Example 1, and in step b, heating and evaporation to dryness was carried out at 150 °C instead of 100 °C used in Example 1, a multi-metal bulk catalyst (7.9 g) was prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-A, and this Cat-A catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 42.1 m 2 / g, and the pore volume is 0.12 mL / g.

[0056] Example 5

[0057] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0058] Except that in step a, the reaction was carried out at 100 °C for 25 hours instead of 80 °C for 25 hours used in Example 1, and in step b, heating and evaporation to dryness was carried out at 180 °C instead of 100 °C used in Example 1, a multi-metal bulk catalyst (7.8 g) was prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-B, and this Cat-B catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 42.2 m 2 / g, and the pore volume is 0.13 mL / g.

[0059] Example 6

[0060] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0061] Except that in step a, the reaction was carried out at 100 °C for 45 hours instead of 80 °C for 25 hours used in Example 1, and in step b, heating and evaporation to dryness was carried out at 210 °C instead of 100 °C used in Example 1, a multi-metal bulk catalyst (7.5 g) was prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-C, and this Cat-C catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 39.9 m 2 / g, and the pore volume is 0.12 mL / g.

[0062] Example 7

[0063] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0064] Except that in step a, the reaction was carried out at 150 °C for 15 hours instead of 80 °C for 25 hours used in Example 1, and in step b, heating and evaporation to dryness were carried out at 150 °C instead of 100 °C used in Example 1, a multi-metal bulk catalyst (8.1 g) was prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-D, and this Cat-D catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 43.9 m 2 / g, and the pore volume is 0.12 mL / g.

[0065] Example 8

[0066] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0067] Except that in step a, the reaction was carried out at 150 °C for 25 hours instead of 80 °C for 25 hours used in Example 1, and in step b, heating and evaporation to dryness were carried out at 180 °C instead of 100 °C used in Example 1, a multi-metal bulk catalyst (7.9 g) was prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-E, and this Cat-E catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 43.1 m 2 / g, and the pore volume is 0.12 mL / g.

[0068] Example 9

[0069] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0070] Except that in step a, a mixed solution of water and Triton-100 was used instead of the mixed solution of water, ethylene glycol and Triton-100 used in Example 1, and in step b, heating and evaporation to dryness were carried out at 150 °C instead of 100 °C used in Example 1, a multi-metal bulk catalyst (8.1 g) was prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-F, and this Cat-F catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 44.3 m 2 / g, and the pore volume is 0.13 mL / g.

[0071] Example 10

[0072] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0073] Except that in step a, a mixed solution of water and Triton-100 is used instead of the mixed solution of water, ethylene glycol and Triton-100 used in Example 1, and in step b, heating and evaporation to dryness is carried out at 180 °C instead of 100 °C in Example 1, a multi-metal bulk catalyst (8.0 g) is prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-G, and this Cat-G catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 43.6 m 2 / g, and the pore volume is 0.12 mL / g.

[0074] Example 11

[0075] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0076] Except that in step b, an aqueous solution is used instead of the mixed solution of water and ethylene glycol used in Example 1, and heating and evaporation to dryness is carried out at 150 °C instead of 100 °C in Example 1, a multi-metal bulk catalyst (8.1 g) is prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-H, and this Cat-H catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 43.2 m 2 / g, and the pore volume is 0.12 mL / g.

[0077] Example 12

[0078] This example illustrates the preparation method of the NiSiMoW catalyst with a multi-walled nanotube structure:

[0079] Except that in step b, a mixed solution of water and Triton-100 is used instead of the mixed solution of water and ethylene glycol used in Example 1, and heating and evaporation to dryness is carried out at 180 °C instead of 100 °C in Example 1, a multi-metal bulk catalyst (8.2 g) is prepared in the same manner as described in Example 1. The synthesized multi-metal bulk catalyst is denoted as Cat-I, and this Cat-I catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 43.1 m 2 / g, and the pore volume is 0.12 mL / g.

[0080] Example 11

[0081] This example illustrates the preparation method of the NiCoSiMoW catalyst with a multi-walled nanotube structure:

[0082] a) Weigh nickel nitrate (23.264 g, where Ni 2+0.08 mol), cobalt chloride (4.758 g, in which Co 2+ 0.02 mol), sodium silicate (56.84 g, in which SiO3 2- 0.2 mol), dissolve them in 1500 ml of a mixed solution containing water, ethylene glycol and Triton-100, add 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a grayish-green mixed reaction solution. Reflux the reaction solution at 80 °C for 25 hours to obtain a grayish-green product; filter and wash the obtained grayish-green product to obtain a catalyst precursor, which is NiCoSiO3 with a multi-walled nanotube structure; add this catalyst precursor to 200 ml of water in a wet state and stir to prepare a catalyst precursor slurry.

[0083] b) Weigh ammonium molybdate (5.4 g, in which Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, in which W 6+ 0.03 mol) respectively, dissolve them in water and ethylene glycol (300 ml) to form a solution, and heat this solution to the reaction temperature, stirring continuously to form a colorless transparent solution; then heat the catalyst precursor slurry prepared in step a) to the reaction temperature; slowly add this slurry to the colorless transparent solution to form a grayish-green reaction solution, heat it to dryness at 150 °C to obtain a grayish-green paste; dry the grayish-green paste at 120 °C to obtain a NiCoSiMoW catalyst (7.8 g). The NiCoSiMoW catalyst synthesized in this example is denoted as Cat-J. The specific surface area of this catalyst measured by low-temperature nitrogen adsorption is 43.0 m 2 / g, and the pore volume is 0.12 mL / g.

[0084] Example 12

[0085] This example illustrates the preparation method of a NiCoSiMoW catalyst with a multi-walled nanotube structure:

[0086] a) Weigh nickel nitrate (17.448 g, in which Ni 2+ 0.06 mol), cobalt chloride (9.516 g, in which Co 2+ 0.04 mol), sodium silicate (56.84 g, in which SiO3 2-0.2 mol), dissolve them in a mixed solution of 1500 ml containing water, ethylene glycol and Triton-100, add 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a grayish-green mixed reaction solution. Reflux and react this solution at a reaction temperature of 80 °C for 25 hours to obtain a grayish-green product; filter and wash the grayish-green product obtained from the reaction to obtain a catalyst precursor, which is NiCoSiO3 with a multi-walled nanotube structure; add this catalyst precursor to 200 ml of water in a wet state and stir to prepare a catalyst precursor slurry.

[0087] b) Weigh ammonium molybdate (5.4 g, where Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, where W 6+ 0.03 mol) respectively, dissolve them in water and ethylene glycol (300 ml) to form a solution, and heat this solution to the reaction temperature, stirring continuously to form a colorless transparent solution; then heat the catalyst precursor slurry prepared in step a) to the reaction temperature; slowly add this slurry to the colorless transparent solution to form a grayish-green reaction solution, heat it to dryness at 180 °C to obtain a grayish-green paste; dry the grayish-green paste at 120 °C to obtain a NiCoSiMoW catalyst (7.7 g). The NiCoSiMoW catalyst synthesized in this example is denoted as Cat-K. The specific surface area of this catalyst measured by low-temperature nitrogen adsorption is 41.3 m 2 / g, and the pore volume is 0.13 mL / g.

[0088] Example 13

[0089] This example illustrates the preparation method of a NiSiMoW catalyst with a layered nanosheet structure:

[0090] a) Weigh nickel nitrate (29.08 g, where Ni 2+ 0.1 mol) and sodium silicate (56.84 g, where SiO3 2- 0.2 mol) respectively, dissolve them in a mixed solution of 1500 ml containing water, ethylene glycol and Triton-100, add a solution of 1500 ml containing 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a light green mixed reaction solution. Reflux and react this solution at a reaction temperature of 80 °C for 25 hours to obtain a light green product; filter and wash the light green product obtained from the reaction to obtain a catalyst precursor, which is NiSiO3 with a layered nanosheet structure; add this catalyst precursor to 200 ml of water to prepare a catalyst precursor slurry;

[0091] b) Weigh ammonium molybdate (10.8 g, where Mo 6+0.06 mol) and ammonium metatungstate (14.4 g, where W 6+ 0.06 mol) was used to replace ammonium molybdate (5.4 g, where Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, where W 6+ 0.03 mol). A polymetallic bulk catalyst (13.6 g) was prepared in the same manner as in Example 3. The synthesized polymetallic bulk catalyst is denoted as Cat-L. This Cat-L catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 34.8 m 2 / g, and the pore volume is 0.13 mL / g.

[0092] Example 14

[0093] This example illustrates the preparation method of a NiSiMoW catalyst with a layered nanosheet structure:

[0094] Except that in step a, the reaction was carried out at 100 °C for 10 hours instead of at 80 °C for 25 hours used in Example 3, and in step b, heating to dryness was carried out at 150 °C instead of at 100 °C used in Example 3, a polymetallic bulk catalyst (7.0 g) was prepared in the same manner as described in Example 3. The synthesized polymetallic bulk catalyst is denoted as Cat-M. This Cat-M catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 32.9 m 2 / g, and the pore volume is 0.14 mL / g.

[0095] Example 15

[0096] This example illustrates the preparation method of a NiSiMoW catalyst with a layered nanosheet structure:

[0097] Except that in step a, the reaction was carried out at 100 °C for 25 hours instead of at 80 °C for 25 hours used in Example 3, and in step b, heating to dryness was carried out at 180 °C instead of at 100 °C used in Example 3, a polymetallic bulk catalyst (6.9 g) was prepared in the same manner as described in Example 3. The synthesized polymetallic bulk catalyst is denoted as Cat-N. This Cat-N catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 33.2 m 2 / g, and the pore volume is 0.15 mL / g.

[0098] Example 16

[0099] This example illustrates the preparation method of a NiSiMoW catalyst with a layered nanosheet structure:

[0100] Except that in step a, the reaction was carried out at 100 °C for 45 hours instead of 80 °C for 25 hours used in Example 3, and in step b, heating and evaporation to dryness was carried out at 210 °C instead of 100 °C used in Example 3, a multi-metal bulk catalyst (7.1 g) was prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-O, and this Cat-O catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 35.4 m 2 / g, and the pore volume is 0.15 mL / g.

[0101] Example 17

[0102] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0103] Except that in step a, the reaction was carried out at 150 °C for 15 hours instead of 80 °C for 25 hours used in Example 3, and in step b, heating and evaporation to dryness was carried out at 150 °C instead of 100 °C used in Example 3, a multi-metal bulk catalyst (7.2 g) was prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-P, and this Cat-P catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 34.9 m 2 / g, and the pore volume is 0.14 mL / g.

[0104] Example 18

[0105] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0106] Except that in step a, the reaction was carried out at 150 °C for 25 hours instead of 80 °C for 25 hours used in Example 3, and in step b, heating and evaporation to dryness was carried out at 180 °C instead of 100 °C used in Example 3, a multi-metal bulk catalyst (7.3 g) was prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-Q, and this Cat-Q catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 33.1 m 2 / g, and the pore volume is 0.14 mL / g.

[0107] Example 19

[0108] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0109] Except that in step a, a mixed solution of water and Triton-100 is used instead of the mixed solution of water, ethylene glycol and Triton-100 used in Example 3, and in step b, heating to dryness is carried out at 150 °C instead of 100 °C in Example 3, a multi-metal bulk catalyst (8.1 g) is prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-R, and this Cat-R catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 34.3 m 2 / g, and the pore volume is 0.13 mL / g.

[0110] Example 20

[0111] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0112] Except that in step a, a mixed solution of water and Triton-100 is used instead of the mixed solution of water, ethylene glycol and Triton-100 used in Example 3, and in step b, heating to dryness is carried out at 180 °C instead of 100 °C in Example 3, a multi-metal bulk catalyst (7.0 g) is prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-S, and this Cat-S catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 34.6 m 2 / g, and the pore volume is 0.12 mL / g.

[0113] Example 21

[0114] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0115] Except that in step b, an aqueous solution is used instead of the mixed solution of water and ethylene glycol used in Example 3, and heating to dryness is carried out at 150 °C instead of 100 °C in Example 3, a multi-metal bulk catalyst (7.1 g) is prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-T, and this Cat-T catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 33.0 m 2 / g, and the pore volume is 0.13 mL / g.

[0116] Example 22

[0117] This example illustrates the preparation method of the NiSiMoW catalyst with a layered nanosheet structure:

[0118] Except that in step b, a mixed solution of water and Triton-100 is used instead of the mixed solution of water and ethylene glycol used in Example 3, and heating to dryness is carried out at 180 °C instead of 100 °C in Example 3, a multi-metal bulk catalyst (7.2 g) is prepared in the same manner as described in Example 3. The synthesized multi-metal bulk catalyst is denoted as Cat-U, and this Cat-U catalyst is a light green powder. The specific surface area of the catalyst measured by low-temperature nitrogen adsorption is 33.5 m 2 / g, and the pore volume is 0.13 mL / g.

[0119] Example 23

[0120] This example illustrates the preparation method of a NiCoSiMoW bulk catalyst with a layered nanosheet structure:

[0121] a) Weigh nickel nitrate (23.264 g, where Ni 2+ 0.08 mol), cobalt chloride (4.758 g, where Co 2+ 0.02 mol), and sodium silicate (56.84 g, where SiO3 2- 0.2 mol) respectively, dissolve them in a mixed solution of 1500 ml containing water, ethylene glycol, and Triton-100, add a solution of 1500 ml containing 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a gray-green mixed reaction solution. Reflux and react this solution at 80 °C for 25 hours to obtain a gray-green product; filter and wash the obtained gray-green product to obtain a catalyst precursor, which is NiCoSiO3 with a layered nanosheet structure; add this catalyst precursor to 200 ml of water in a wet state and stir to prepare a catalyst precursor slurry.

[0122] b) Weigh ammonium molybdate (5.4 g, where Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, where W 6+ 0.03 mol) respectively, dissolve them in water and ethylene glycol (300 ml) to form a solution, and heat this solution to the reaction temperature while stirring continuously to form a colorless transparent solution; then heat the catalyst precursor slurry prepared in step a) to the reaction temperature; slowly add this slurry to the colorless transparent solution to form a gray-green reaction solution, heat it to dryness at 100 °C to obtain a gray-green paste; dry the gray-green paste at 120 °C to obtain a NiCoSiMoW catalyst (6.8 g). The NiCoSiMoW catalyst synthesized in this example is denoted as Cat-V. The specific surface area of this catalyst measured by low-temperature nitrogen adsorption is 34.7 m 2 / g, and the pore volume is 0.15 mL / g.

[0123] Example 24

[0124] This example illustrates the preparation method of a NiCoSiMoW catalyst with a layered nanosheet structure:

[0125] a) Weigh out nickel nitrate (17.448 g, where Ni 2+ 0.06 mol), cobalt chloride (9.516 g, where Co 2+ 0.04 mol), and sodium silicate (56.84 g, where SiO3 2- 0.2 mol) respectively. Dissolve them in a mixed solution of 1500 ml containing water, ethylene glycol, and Triton-100. Add a solution of 1500 ml containing 290 g of the basic precipitant NaOH particles, and heat to the reaction temperature to form a grayish-green mixed reaction solution. Reflux the reaction solution at 80 °C for 25 hours to obtain a grayish-green product; filter and wash the obtained grayish-green product to obtain a catalyst precursor, which is NiCoSiO3 with a layered nanosheet structure; add the catalyst precursor in a wet state to 200 ml of water and stir to prepare a catalyst precursor slurry.

[0126] b) Weigh out ammonium molybdate (5.4 g, where Mo 6+ 0.03 mol) and ammonium metatungstate (7.2 g, where W 6+ 0.03 mol) respectively. Dissolve them in water and ethylene glycol (300 ml) to form a solution, and heat this solution to the reaction temperature with continuous stirring to form a colorless and transparent solution; then heat the catalyst precursor slurry prepared in step a) to the reaction temperature; slowly add this slurry to the colorless and transparent solution to form a grayish-green reaction solution, heat it to dryness at 100 °C to obtain a grayish-green paste; dry the grayish-green paste at 120 °C to obtain a NiCoSiMoW catalyst (6.9 g). The NiCoSiMoW catalyst synthesized in this example is denoted as Cat-W. The specific surface area of this catalyst measured by low-temperature nitrogen adsorption is 34.3 m 2 / g, and the pore volume is 0.15 mL / g.

[0127] Some embodiments of the present disclosure also provide a desulfurization catalyst, which includes a mixed metal oxide composed of at least one Group VIII metal, at least two Group VIB metals, and one Group IVA non-metal; wherein, calculated as oxides, the catalyst contains 1-50 wt% of Group VIII metal, 1-50 wt% of Group VIB metal, and 1-50 wt% of Group IVA non-metal.

[0128] In other embodiments of the present disclosure, the content of Group VIII metal, calculated as the oxide, can be 5 wt%, 10 wt%, 15 wt% or 25 wt%, 30 wt%; the content of Group VIB metal can be 10 wt%, 15 wt%, 20 wt% or 30 wt%, 45 wt%; the content of Group IVA non-metal can be 15 wt%, 20 wt%, 30 wt% or 35 wt%, 45 wt%.

[0129] In one embodiment of the disclosure, the catalyst comprises at least one Group VIII metal, two Group VIB metals and one Group IVA non-metal, wherein the molar ratio of the Group VIII metal to the Group VIB metal is 20:1 - 1:20; the molar ratio of the Group VIII metal to the Group IVA non-metal is 20:1 - 1:1; the molar ratio of the two Group VIB metals is 5:1 - 1:5.

[0130] In other embodiments of the present disclosure, the molar ratio of the Group VIII metal to the Group VIB metal can be 10:5, 10:15, 15:5 or 18:15; the molar ratio of the Group VIII metal to the Group IVA non-metal can be 5:10, 10:12, 15:5, 15:10 or 20:5; the molar ratio of the two Group VIB metals can be 1:2, 2:5 or 5:2.

[0131] In one embodiment of the present disclosure, the catalyst is NiSiMoW, that is, the Group VIII metal in the catalyst comprises Ni, the Group VIB metals comprise Mo and W, and the Group IVA non-metal comprises Si.

[0132] In one embodiment of the present disclosure, the Group VIII metal comprises Co, the Group VIB metals comprise Mo and W, and the Group IVA non-metal comprises Si.

[0133] In one embodiment of the present disclosure, the catalyst has a multi-walled nanotube or layered nanosheet structure. The specific surface area of the catalyst with the multi-walled nanotube structure is 30 - 300 m 2 / g, and the pore volume is 0.1 - 0.5 mL / g. The specific surface area of the catalyst with the layered nanosheet structure is 30 - 300 m 2 / g, and the pore volume is 0.1 - 0.5 mL / g. In other embodiments of the present disclosure, the specific surface area of the catalyst with the multi-walled nanotube or layered nanosheet structure can be 30 - 150 m 2 / g, 40 - 180 m 2 / g, 300 - 200 m 2 / g or 30 - 250 m 2 / g, and the pore volume can be 0.1 - 0.3 mL / g, 0.25 - 0.3 mL / g or 0.3 - 0.35 mL / g.

[0134] In another embodiment of the present disclosure, there is provided an application of the catalyst as described above in the hydrodesulfurization reaction of sulfur-containing organic compound fuel.

[0135] In one embodiment of the present disclosure, the conditions for the hydrodesulfurization reaction of the catalyst prepared in the above embodiment are as follows: temperature 250 - 450 °C, hydrogen pressure 1 - 20 MPa, volume ratio of hydrogen to the sulfur-containing organic compound fuel is 50 - 1500 Nm 3 / m 3 , and the volume space velocity of the sulfur-containing organic compound fuel is 0.1 - 10 h -1 .

[0136] Before carrying out the hydrodesulfurization reaction on the above catalyst, the following pretreatment is carried out: a) grinding, kneading, and forming; and b) in a hydrodesulfurization fixed-bed reactor, in-situ presulfurization is carried out with a mixed gas of sulfur compound and hydrogen at 250 - 450 °C; the presulfurization time is 2 - 10 hours.

[0137] In one embodiment of the present disclosure, the sulfur compound can be hydrogen sulfide, carbon disulfide, or dimethyl disulfide. Performance evaluation of the catalyst in the hydrodesulfurization reaction.

[0138] Using a diesel fraction with a sulfur content of 517 ppm (dissolving 4,6-DMDBT in a decalin solvent) to investigate the performance of the catalyst in the hydrodesulfurization reaction, and the reaction is carried out in a fixed-bed reactor. The reaction conditions are as follows: catalyst mass 0.5 g, reaction temperature at 300 °C, hydrogen pressure 3.0 Mpa, ratio of hydrogen to diesel fraction is 800 Nm 3 hydrogen / m 3 diesel fraction, volume space velocity 9 h -1 . The sulfur content in the sample is measured using an ANTEK sulfur analyzer.

[0139] The hydrodesulfurization activity of the catalyst prepared in Example 1 is as Figure 4 shown. It can be seen that among these catalysts, the highest desulfurization rate can reach over 98%, and the sulfur in the diesel fraction, that is, 4,6-dimethyldibenzothiophene, can be reduced from 517 ppm to below 10 ppm, achieving ultra-deep desulfurization.

[0140] The sulfur content of the diesel fraction after hydrodesulfurization with the catalysts prepared in Examples 2 - 9 is listed in Table 1.

[0141] Table 1 Performance comparison of the catalyst in the hydrodesulfurization reaction

[0142]

[0143] In the above hydrodesulfurization reaction of diesel fractions, experiments were carried out using the catalysts prepared in the examples of the present disclosure. The desulfurization results showed that the desulfurization effects of all catalysts reached the best, and the sulfur content in the raw materials could be reduced from 517 ppm to below 10 ppm.

[0144] The commercial reference agent in Table 1 was provided by the China National Petroleum and Chemical Corporation, and its composition was Co3O4·2.2NiO·5.9MoO3·2WO3.

[0145] The activity of the catalysts prepared in the examples of the present disclosure is expressed by relative activity, that is, taking the activity of the reference agent operating for 200 hours as 100, and the activity obtained by comparing the present disclosure catalyst with it represents the relative activity of the inventive catalyst. The relative desulfurization activity is calculated according to the following formula:

[0146] Relative desulfurization activity = 100×[(1 / S p ) 0.65 -(1 / S f ) 0.65 / [(1 / S pr ) 0.65 -(1 / S fr ) 0.65

[0147] In the formula, S fr and S pr respectively represent the sulfur concentration of the diesel fraction used by the reference agent and the product after hydrotreating with the reference agent, and S f and S p respectively represent the sulfur concentration of the diesel fraction used by the inventive catalyst and the product after hydrotreating with the inventive catalyst.

[0148] In summary, the examples of the present disclosure synthesized a multi-metal bulk catalyst with a layered structure, a relatively high specific surface area, a high pore volume and ultra-high hydrodesulfurization activity compared with patents and literatures. This catalyst has a multi-walled nanotube layered structure or a layered nanosheet structure, and the active metal is exchanged into the interlayer. Its dispersion degree is relatively high, showing more active centers. Under mild operating conditions, through the hydrodesulfurization reaction, this catalyst can reduce the sulfur in the diesel fraction containing 4,6-DMDBT from 517 ppmw to below 10 ppmw, thus realizing ultra-deep desulfurization and showing great industrial application potential.​

Claims

1. A preparation method of a desulfurization catalyst, characterized in that, The method includes: providing solution A containing a soluble salt of at least one Group VIII metal; providing solution B including a soluble salt of at least one Group IVA non-metal; mixing and reacting solution A containing the soluble salt of at least one Group VIII metal, solution B containing the soluble salt of at least one Group IVA non-metal, and an alkaline precipitant, and obtaining a catalyst precursor after filtration and washing; mixing the obtained catalyst precursor with a polar solvent in a wet state and stirring to prepare a catalyst precursor slurry; providing solution C containing soluble salts of at least two Group VIB metals, mixing solution C containing the soluble salts of at least two Group VIB metals with the catalyst precursor slurry, and heating to dryness to obtain the catalyst.

2. The method according to claim 1, wherein The concentration of the Group VIII metal ions in solution A is 0.01 - 0.3 mol / L, the concentration of the Group IVA non-metal ions in solution B is 0.01 - 0.3 mol / L, the concentration of the alkaline precipitant is 0.7 - 2.1 mol / L, the concentration of the catalyst precursor slurry is 0.01 - 0.9 mol / L, and the concentration of the Group VIB metal ions in solution C is 0.01 - 0.2 mol / L.

3. The method according to claim 1, characterized in that Solution A and solution B react at 20°C - 220°C for 4 - 50 hours, and solution C and the catalyst precursor slurry are heated to dryness at 50°C - 350°C.

4. The method according to claim 1, characterized in that The soluble salt of the Group IVA non-metal includes one or more of sodium silicate, potassium silicate, lithium silicate, ammonium silicate, sodium metasilicate pentahydrate, and sodium metasilicate nonahydrate. The soluble salt of the Group VIII metal includes one or more of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate, or cobalt acetate. The alkaline precipitant includes one or more of sodium hydroxide and potassium hydroxide. The soluble salt of the Group VIB metal anion includes one of ammonium molybdate, molybdic acid, ammonium phosphomolybdate, phosphomolybdic acid, and sodium molybdate, and one of ammonium tungstate, phosphotungstic acid, ammonium metatungstate, tungstic acid, or sodium tungstate. The polar solvent includes one or more of water and ethylene glycol.

5. A desulfurization catalyst formed by the preparation method according to any one of claims 1-4, characterized in that: a mixed metal oxide composed of at least one Group VIII metal, at least two Group VIB metals, and one Group IVA non-metal; wherein, calculated as oxides, the catalyst contains 1 - 50 wt% of Group VIII metal, 1 - 50 wt% of Group VIB metal, and 1 - 50 wt% of Group IVA non-metal.

6. The desulfurization catalyst according to claim 5, characterized in that, The desulfurization catalyst includes at least one Group VIII metal, two Group VIB metals, and one Group IVA non-metal. The molar ratio of the Group VIII metal to the Group VIB metal is 20:1 - 1:20; the molar ratio of the Group VIII metal to the Group IVA non-metal is 20:1 - 1:1; the molar ratio of the two Group VIB metals is 5:1 - 1:

5.

7. The desulfurization catalyst according to claim 5, characterized in that, The Group VIII metal includes Ni or Co; the Group VIB metals include Mo and W; the Group IVA non-metal includes Si.

8. The desulfurization catalyst according to claim 5, wherein, The desulfurization catalyst has a multi-walled nanotube structure or a layered nanosheet structure. The specific surface area of the desulfurization catalyst with a multi-walled nanotube structure is 30 - 300 m 2 / g, and the pore volume is 0.1 - 0.5 mL / g. The specific surface area of the desulfurization catalyst with a layered nanosheet structure is 30 - 300 m 2 / g, and the pore volume is 0.1 - 0.5 mL / g.

9. Use of the desulfurization catalyst according to any one of claims 5 to 8 in the hydrodesulfurization reaction of sulfur-containing organic compound fuel oil.

10. The application according to claim 9, characterized in that, The conditions for the hydrodesulfurization reaction are as follows: temperature 250 - 450 °C, hydrogen pressure 1 - 20 MPa, volume ratio of hydrogen to the sulfur-containing organic compound fuel is 50 - 1500 Nm 3 / m 3 ; the volume space velocity of the sulfur-containing organic compound fuel is 0.1 - 10 h -1 .

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