Residue hydroprocessing catalyst, method for making and use thereof

Abstract

This invention discloses a residue hydrotreating catalyst, its preparation method, and its application. The catalyst preparation method includes the following steps: impregnating a first active metal solution onto a porous carbon-nitrogen / SiO2 composite support, drying, and calcining to obtain a metal / composite support material; preparing a pseudoboehmite wet filter cake, drying it, and obtaining pseudoboehmite; mixing the metal / composite support with the pseudoboehmite, molding, and drying to obtain a catalyst precursor; and then impregnating it with a second active metal solution, drying, and calcining to obtain the catalyst. The catalyst provided by this invention is suitable for residue hydrotreating, especially exhibiting excellent catalytic performance in desulfurization and denitrification.

Description

Technical Field

[0001] This invention relates to a hydrogenation catalyst, its preparation method, and its application; more specifically, it relates to a residue oil hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Residue hydrotreating catalysts are mainly metal-supported catalysts, often using alumina and / or silica as supports, with Ni, Mo, Co, etc., as active metal components. In existing methods, when the active metal loading is high, metal particle agglomeration or uneven distribution is prone to occur. Furthermore, during roasting, the strong interaction between the metal and the support leads to the formation of metal-oxygen-aluminum bonds, affecting the catalyst's catalytic efficiency and ultimately reducing its hydrotreating activity. Introducing an appropriate amount of silica into the alumina support is beneficial for improving the acidity and specific surface area of ​​the alumina, which is conducive to polymerization and hydrogenation reactions.

[0003] CN103055908A discloses a method for preparing a hydrotreating catalyst. The method first involves slurrying aluminum hydroxide or alumina into a slurry, then adding concentrated phosphoric acid to react and obtain a sol. This sol is then used as a binder, mixed with macroporous and microporous alumina, kneaded, shaped, dried, and calcined to obtain an alumina support. Finally, the alumina support is impregnated with an active metal component impregnation solution, followed by drying and calcination to obtain the hydrotreating catalyst. This method is complex, the introduction of acidic sites promotes bonding between the active metal and the support, the application of large amounts of concentrated acid causes environmental pollution, and industrial production is relatively dangerous.

[0004] CN105582945A discloses a method for preparing a hydrogenation catalyst. This method involves first impregnating an alumina support with a urea aqueous solution, then spraying a polyol or monosaccharide aqueous solution onto the alumina support in descending order of concentration. This creates a gradient distribution of polyol and / or monosaccharide concentrations on the support, from low to high, from the outside in. An active metal component is then loaded. This method requires multiple spray impregnation steps to form a polymer carbonized shell and has high requirements for solution concentration, making the actual operation quite complex.

[0005] CN1257754A discloses a method for preparing a silicon-aluminum catalyst support, which involves introducing water glass and aluminum sulfate to prepare a silicon-aluminum precursor. The prepared support has a pore volume of 0.45~0.75 mL / g and an average pore size of 5-10 nm. However, the final synthesized silicon-aluminum support has a small pore size, making it unsuitable for use as a catalyst for the hydrotreating of heavy oil or residue oil with a large molecular weight.

[0006] CN1169614C discloses a method for preparing silicon-containing aluminum hydroxide. By introducing a certain amount of sodium silicate during the gelation process of aluminum hydroxide preparation by carbonization, and continuing to add a certain amount of sodium silicate during the subsequent aging process, silicon-containing aluminum oxide can be prepared. Its average pore size is relatively small. Although it is suitable for heavy oil or residue oil hydrodesulfurization or hydrodenitrification catalysts, its pore size is relatively small for residue oil hydrodemetallization catalysts, and further improvement is needed. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a residue oil hydrotreating catalyst, its preparation method, and its application. The catalyst provided by this invention exhibits high metal loading, uniform dispersion, high mechanical strength, suitable pore distribution and specific surface area, and appropriate surface acidity, making it suitable for residue oil hydrotreating.

[0008] The first aspect of this invention provides a method for preparing a residue oil hydrogenation catalyst, comprising the following steps:

[0009] (1) The first active metal solution is impregnated onto a porous carbon-nitrogen / SiO2 composite support, dried and calcined to obtain a metal / composite support material;

[0010] (2) Prepare a wet filter cake of boehmite and dry it to obtain boehmite;

[0011] (3) Mix the metal / composite support obtained in step (1) with the pseudoboehmite obtained in step (2), shape and dry to obtain the catalyst precursor;

[0012] (4) The catalyst precursor obtained in step (3) is impregnated with a second active metal solution, dried, and calcined to obtain the catalyst.

[0013] In this invention, in step (1), the porous carbon-nitrogen / SiO2 composite support comprises:

[0014] (a) Dissolve cyanamide in silica sol, stir, and then add an organic solvent to form a gel;

[0015] (b) The above gel was heated and calcined under an inert atmosphere to obtain a porous carbon-nitrogen / SiO2 composite carrier, which was then ground into powder.

[0016] In the method of the present invention, in step (a), the concentration of the silica sol is 30% to 55% based on SiO2, preferably 40% to 50%.

[0017] In the method of the present invention, in step (a), the mass ratio of the amount of cyanamide added to the silica sol is 0.5 to 1.5, preferably 0.6 to 1.2.

[0018] In the method of the present invention, in step (a), the organic solvent is selected from ethanol or ethylene glycol, preferably ethanol, and the amount added is 0.5~1.5 times the mass ratio of silica sol.

[0019] In the method of the present invention, in step (b), the calcination temperature is 250~650℃, preferably 300~450℃, and the time is 2~15h. The inert atmosphere is selected from at least one of Ar, He, and N2.

[0020] In the method of the present invention, in step (1), the active metal in the first active metal solution is selected from at least one of Group VIII metals, cobalt and nickel, preferably nickel; the loading amount is 30% to 50% of the total mass of Group VIII active metal oxides in the catalyst, calculated as oxides; wherein, the concentration of the first active metal solution, calculated as active metal oxides, is 0.02 to 0.40 g / mL.

[0021] In the method of the present invention, in step (1), the drying temperature is 100~120℃ and the time is 2~5h; the calcination temperature is 400~450℃, protected by an inert atmosphere, and the time is 2~3h, wherein the inert atmosphere is selected from at least one of Ar, He and N2.

[0022] In the method of the present invention, step (2), the method for preparing pseudoboehmite wet filter cake, includes:

[0023] (A) Add a first alkaline solution to the first reaction vessel and pass a mixed gas containing carbon dioxide through it to make the pH of the system 2~4;

[0024] (B) Add bottom water to the second reactor and heat it to the reaction temperature. Then, add the second alkaline solution and the material obtained in step (A) into the second reactor in parallel to carry out the reaction.

[0025] (C) The slurry obtained after the reaction in step (B) is aged, filtered and washed after aging to obtain a pseudo-boehmite filter cake.

[0026] In the method of the present invention, in step (A), the first alkaline solution is one or both of sodium aluminate solution and potassium aluminate solution, preferably sodium aluminate solution; the concentration of the sodium aluminate solution and / or potassium aluminate is 10~30g Al2O3 / L, and the caustic ratio of the first alkaline solution is 1.35~1.65.

[0027] In the method of the present invention, in step (A), the volume of the first alkaline solution added to the first reaction vessel is 2 / 3 to 3 / 4 of the volume of the first reaction vessel; the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 30% to 70%; the carbon dioxide-containing mixed gas can be a mixture of carbon dioxide and air.

[0028] In the method of the present invention, in step (A), the initial reaction temperature of the mixed gas containing carbon dioxide is 15~65℃. The reaction is an exothermic reaction, and the system temperature gradually increases. The entire reaction process does not require cooling to maintain a low temperature. Generally, the temperature of the slurry is 40~75℃ at the end of the reaction.

[0029] In the method of the present invention, in step (B), the second alkaline solution is one or both of sodium aluminate solution and potassium aluminate solution, preferably sodium aluminate solution; the concentration of sodium aluminate and / or potassium aluminate in the second alkaline solution is 130~350g Al2O3 / L, preferably 150~250g Al2O3 / L, and the caustic ratio of the sodium aluminate solution or potassium aluminate solution is 1.10~1.40, preferably 1.15~1.35.

[0030] In the method of the present invention, in step (B), the bottom water added to the second reactor is 1 / 10 to 1 / 5 of the volume of the second reactor.

[0031] In the method of the present invention, in step (B), the material obtained in step (A) is added to the second reaction vessel, and the material addition time is controlled to be 60-150 min. Further, in step (B), the second alkaline solution and the material obtained in step (A) are added to the second reaction vessel in parallel flow to react, and the pH value is controlled to be 7.5-9.0.

[0032] In the method of the present invention, in step (B), the reaction is carried out under stirring. The reaction temperature is 40℃~70℃, preferably 45℃~65℃.

[0033] In the method of the present invention, in step (C), the aging conditions are: temperature of 50℃~95℃ and time of 30min~20min.

[0034] In the method of the present invention, in step (C), the washing can be carried out using conventional washing methods in the art, preferably using deionized water at 50°C to 80°C until neutral.

[0035] In the method of the present invention, in step (C), the solid content in the obtained pseudoboehmite wet filter cake is 30wt%~45wt%.

[0036] In the method of the present invention, in step (2), the drying temperature is 60~150℃ and the drying time is 4~10h.

[0037] In the method of the present invention, in step (3), the mass ratio of the metal / composite carrier material obtained in step (1) to the pseudoboehmite is 0.05~0.3. The molding can be carried out by extrusion molding. An extrusion aid can be added during the molding process. The extrusion aid can be guar gum powder, and the amount of extrusion aid added is 1%~6% of the mass of the pseudoboehmite.

[0038] In the method of the present invention, in step (3), the drying temperature is 80~120℃ and the time is 4~6h.

[0039] In the method of the present invention, in step (4), the impregnation is saturated impregnation. The active metal in the second active metal solution is selected from at least one group VIB metal and at least one group VIII metal, wherein the group VIB metal is preferably at least one of Mo and W, more preferably Mo, and the group VIII metal is preferably at least one of Co and Ni, more preferably Ni; wherein the concentration of the group VIB metal in the second active metal solution, calculated as oxide, is 0.05~0.5 g / mL, and the concentration of the group VIII metal, calculated as oxide, is 0.01~0.2 g / mL.

[0040] In the method of the present invention, the amount of Group VIII metal introduced into the catalyst by step (4) accounts for 50% to 70% of the total mass of Group VIII metal oxides in the catalyst, based on oxides.

[0041] In the method of the present invention, in step (4), the catalyst contains 10% to 30% of group VIB metal oxides and 2% to 15% of group VIII metal oxides, based on the mass of the catalyst.

[0042] In the method of the present invention, in step (4), the drying temperature is 80~120℃, the drying time is 2~5 hours, and after drying, it is roasted at a temperature of 600~900℃ for a time of 3~5 hours.

[0043] The second aspect of the present invention provides a residue oil hydrogenation catalyst obtained by the preparation method described in the first aspect.

[0044] In this invention, the active metal in the catalyst is at least one of Group VIB metals and at least one of Group VIII metals, wherein the Group VIB metal is preferably at least one of Mo and W, more preferably Mo, and the Group VIII metal is preferably at least one of Co and Ni, more preferably Ni.

[0045] In this invention, the catalyst contains 10% to 30% group VIB metal oxides and 2% to 15% group VIII metal oxides, based on the mass of the catalyst.

[0046] In this invention, the content of silicon dioxide in the catalyst is 8% to 20% based on the mass of the catalyst.

[0047] In this invention, the catalyst also contains N, and the content of N as an element is 0.5% to 1.0% based on the mass of the catalyst.

[0048] In this invention, the dispersion of the active metal in the catalyst is: I VIB / I Al (×100) is 3~10, I VIII / I Al (×100) is 3~9.

[0049] In this invention, the catalyst has a specific surface area of ​​140~230 m². 2 / g, preferably 170~200m 2 / g, pore volume 0.5~1.2cm 3 / g, preferably 0.7~0.9cm 3 / g, with a mechanical strength of 16~27 N / mm, preferably 18~24 N / mm, and the pore volume of pores with a diameter of 15~80nm accounts for 6%~23% of the total pore volume, preferably 10%~14%, and the pore volume of pores with a diameter of less than 8nm accounts for less than 8% of the total pore volume, preferably 4%~7%.

[0050] In this invention, the acid content of the catalyst is 0.4~0.9 mmol / g, preferably 0.6~0.8 mmol / g. The ratio of Brønsted acid to Lewis acid is C. B / C L The value is 0.02~0.09, preferably 0.04~0.07.

[0051] The third aspect of this invention provides the application of the above-mentioned residue hydrotreating catalyst in the residue hydrotreating process.

[0052] In this invention, residual oil and hydrogen-containing gas are reacted in contact under hydrogenation reaction conditions in the presence of the above-mentioned residual oil hydrogenation catalyst or the residual oil hydrogenation catalyst obtained according to the above preparation method.

[0053] In the above-mentioned hydrogenation reaction of residual oil, the residual oil material is selected from one of atmospheric residue oil, vacuum residue oil, and high-temperature coal tar.

[0054] In the above-mentioned hydrogenation reaction of residual oil, the hydrogen-containing gas is hydrogen or a mixture of hydrogen and other gases. The volume content of hydrogen in the mixture is generally not less than 80%, preferably not less than 85%, and even more preferably not less than 95%.

[0055] In the above-mentioned residue hydrotreating process, the operating conditions for residue hydrotreating are as follows: reaction pressure of 5~20 MPaG, reaction temperature of 280~400℃, and liquid hourly space velocity of 0.1~3.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-1000.

[0056] Compared with the prior art, the present invention has the following beneficial effects:

[0057] The residue hydrotreating catalyst provided by this invention has a high metal loading, uniform dispersion, high mechanical strength, suitable pore distribution and specific surface area, and suitable surface acidity. When applied to residue hydrotreating, it exhibits excellent catalytic performance, especially in desulfurization and denitrification, and also has good activity in removing residual carbon and metals.

[0058] In the preparation method of the residue oil hydrogenation catalyst of this invention, on the one hand, cyanamide undergoes a thermal polymerization reaction in silica sol to form a nitrogen-carbon composite support containing silica. Since the nitrogen-carbon support has a certain band gap, and the band gap can be adjusted by changing the calcination temperature, a metal-semiconductor heterojunction can be formed during its loading with Group VIII metals. This strengthens the interaction between the metal and the nitrogen-carbon support, improving metal dispersion and increasing the metal loading. Furthermore, it significantly weakens the electron migration efficiency between the active metal and alumina, reducing adsorption and bonding between them. The synthesized catalyst exhibits higher activity during residue oil hydrogenation. On the other hand, the nitrogen-carbon support contains a large number of silica spheres. After secondary impregnation and calcination in air, the carbon support can be removed, and the silica spheres enter the alumina support. The silicon element not only expands the pores but also adjusts the surface acidity of the alumina support, forming a silicon-containing hydrogenation catalyst. This synthesis method is highly efficient and controllable, providing higher activity for the hydrogenation catalyst. In addition, the boehmite wet filter cake prepared by this invention has low gibbsite content and high crystallinity, and the alumina obtained after calcination has a large pore volume and pore size; at the same time, the boehmite wet filter cake prepared by this invention has a high colloidal index, which provides a guarantee for the preparation of a high lateral pressure strength carrier. Detailed Implementation

[0059] In this invention, the nitrogen adsorption-desorption curves of the samples were tested at -196℃ using a Micromeritics ASAP2020 fully automated physical adsorption instrument to determine the specific surface area, pore volume, and pore size distribution.

[0060] In this invention, the mechanical strength is tested using a ZQJ-Ⅲ intelligent particle strength tester manufactured by Dalian Zhiqu Testing Machine Factory, and the average mechanical strength of a group of samples with a length of 4-6 mm is determined.

[0061] In this invention, the metal dispersion is measured using XPS (the instrument is a Kratos Axis Ultra DLD model) to measure the XPS peak intensity ratio of the active metal and aluminum.

[0062] In this invention, the infrared acid content was measured using a Nicolet 870 Fourier transform infrared spectrometer from Nicolet Corporation, USA.

[0063] The technical solutions and effects of the present invention will be further illustrated below with reference to the embodiments, but the invention is not limited to the following embodiments. Example 1

[0064] (1) Add a sodium aluminate mixed solution with a caustic ratio of 1.45 and a concentration of 25g Al2O3 / L to a 5000mL first reaction vessel, and then pass in a mixed gas of carbon dioxide and air with a volume fraction of 55% carbon dioxide to reduce the pH value of the system to 3.4. The temperature of the material at the end of the reaction is 55℃.

[0065] Add 1500 mL of bottom water to a 10000 mL second reaction vessel, start the stirring and heating device, and when the temperature rises to 65°C, add the above material to the second reaction vessel at a flow rate of 35 mL / min for 90 min. Simultaneously add a sodium aluminate solution with a concentration of 180 g Al2O3 / L and a caustic ratio of 1.25. Control the pH value of the slurry in the second reaction vessel to 8.0 by adjusting the flow rate of the sodium aluminate solution, while maintaining a constant temperature of the slurry in the second reaction vessel. After the above material is used up, the reaction ends. The slurry is aged at 90°C for 80 min. After aging, it is washed with deionized water at 70°C until neutral. After filtration, a pseudoboehmite wet filter cake with a solid content of 37% is obtained. Then, it is dried at 120°C for 6 hours to obtain the pseudoboehmite required by this invention.

[0066] (2) Dissolve 10g of cyanamide in 12.5g of 40% silica sol, and then add 12mL of anhydrous ethanol under vigorous stirring to form a gel. Transfer the gel to a crucible and heat it to 400℃ in a tube furnace for 6h under nitrogen protection. Grind the sample into powder to obtain a porous carbon-nitrogen / SiO2 composite support.

[0067] (3) 80 mL of active metal solution with NiO content of 0.135 g / mL was impregnated onto 100 g of porous carbon-nitrogen / SiO2 composite support and dried at 110 °C for 4 h. Then, it was calcined at 430 °C for 3 h under nitrogen atmosphere protection to obtain metal / composite support material. In this case, the amount of Ni introduced into the catalyst in step (3) accounts for 31.3% of the total Ni in the catalyst, based on the mass of oxide.

[0068] (4) Weigh 100g of the above-treated sample, mix it with 500g of boehmite and 15g of guar gum powder, extrude it into strips, and dry it at 120℃ for 4 hours to obtain an intermediate.

[0069] (5) Prepare an impregnation solution containing 0.309 g / mL MoO3 and 0.058 g / mL NiO to saturate the above catalyst intermediate. After the impregnation is complete, dry at 120°C for 5 hours and calcine at 650°C for 3 hours to obtain the final hydrogenation catalyst A. Its physicochemical properties are shown in Table 1. Example 2

[0070] The other synthesis process is the same as in Example 1, except that the amount of 40% silica sol added is changed to 14.3g to obtain the final hydrogenation catalyst B, whose physicochemical properties are shown in Table 1. Example 3

[0071] The other synthesis process is the same as in Example 1, except that the NiO concentration in the first impregnation solution is changed to 0.206 g / mL, the second impregnation solution is a MoO3 and NiO solution, wherein the MoO3 concentration is changed to 0.312 g / mL, the NiO concentration is 0.045 g / mL, and the calcination temperature after impregnation is changed to 450 °C, and the final hydrogenation catalyst C is obtained (physicochemical properties are shown in Table 1). In this case, based on the mass of oxides, the amount of Ni introduced into the catalyst in step (3) accounts for 46.9% of the total Ni in the catalyst. Example 4

[0072] The other synthesis process is the same as in Example 1, except that the amount of metal / composite support material added in step (4) is changed to 50g to obtain the final hydrogenation catalyst D, whose physicochemical properties are shown in Table 1. Comparative Example 1

[0073] The rest of the synthesis process was the same as in Example 1, except that the support was replaced with an equal amount of activated carbon powder. The final hydrogenation catalyst E was obtained, and its physicochemical properties are shown in Table 1. Comparative Example 2

[0074] The other synthesis processes are the same as in Example 1, except that:

[0075] (3) 80 mL of active metal solution with NiO content of 0.284 g / mL is impregnated onto 100 g of porous carbon-nitrogen / SiO2 composite support. Based on the mass of oxides, the amount of Ni introduced into the catalyst in step (3) accounts for 64.5% of the total Ni in the catalyst.

[0076] (5) Prepare an impregnation solution containing 0.312 g / mL MoO3 and 0.030 g / mL NiO to saturate the catalyst intermediate and obtain the final hydrogenation catalyst F. Its physicochemical properties are shown in Table 1. Comparative Example 3

[0077] The other synthesis processes are the same as in Example 1, except that the preparation process of pseudoboehmite in step (1) is as follows: 3000 mL of sodium aluminate solution with a concentration of 65 g Al2O3 / L and a caustic ratio of 1.35 is added to a 5.0 L reactor. Then, a mixture of carbon dioxide and air with a carbon dioxide content of 80% (volume fraction) is introduced. The initial reaction temperature is 25 °C. The slurry temperature is kept constant during cooling, and the reaction time is controlled at 45 min to reduce the pH value of the sodium aluminate solution to 8.8. The slurry is filtered and washed with deionized water at 75 °C. After washing, it is dried at 120 °C for 6 hours to obtain pseudoboehmite. The final hydrogenation catalyst G is obtained, and its physicochemical properties are shown in Table 1. Example 5

[0078] The catalysts obtained in Examples 1-4 and Comparative Examples 1-3 were used in the hydrogenation reaction of residue oil, respectively. The properties of the feedstock are shown in Table 2, and the evaluation conditions and results are shown in Table 3.

[0079] Table 1 Physicochemical properties of hydrogenation catalysts

[0080]

[0081] Table 2 Properties of Crude Oil

[0082]

[0083] Table 3 Evaluation conditions and results of hydrogenation catalysts obtained in each example

[0084]

Claims

1. A method for preparing a residue oil hydrotreating catalyst, comprising the following steps: (1) The first active metal solution is impregnated onto a porous carbon-nitrogen / SiO2 composite support, dried and calcined to obtain a metal / composite support material; (2) Prepare a wet filter cake of boehmite and dry it to obtain boehmite; (3) Mix the metal / composite support obtained in step (1) with the pseudoboehmite obtained in step (2), shape and dry to obtain the catalyst precursor; (4) The catalyst precursor obtained in step (3) is impregnated with a second active metal solution, dried, and calcined to obtain the catalyst; In step (1), the porous carbon-nitrogen / SiO2 composite support comprises: (a) Dissolve cyanamide in silica sol, stir, and then add an organic solvent to form a gel; (b) The above gel was heated and calcined under an inert atmosphere to obtain a porous carbon-nitrogen / SiO2 composite carrier, which was then ground into powder; In step (2), the method for preparing pseudoboehmite wet filter cake includes: (A) Add a first alkaline solution to the first reaction vessel and pass a mixed gas containing carbon dioxide through it to make the pH of the system 2~4; (B) Add bottom water to the second reactor and heat it to the reaction temperature. Then, add the second alkaline solution and the material obtained in step (A) into the second reactor in parallel to carry out the reaction. (C) The slurry obtained after the reaction in step (B) is aged, filtered and washed after aging to obtain a pseudo-boehmite filter cake. In step (1), the active metal in the first active metal solution is selected from at least one of Group VIII metals, cobalt and nickel; In step (4), the active metal in the second active metal solution is selected from at least one of Group VIB metals molybdenum and tungsten and at least one of Group VIII metals cobalt and nickel; In the catalyst, based on the mass of the catalyst, the content of group VIB metal oxide is 10%~30%, the content of group VIII metal oxide is 2%~15%, and the content of silicon oxide is 8%~20%.

2. The preparation method according to claim 1, characterized in that, In step (1), the active metal in the first active metal solution is selected from group VIII metal nickel; the concentration of the active metal oxide in the first active metal solution is 0.02~0.40 g / mL.

3. The preparation method according to claim 1, characterized in that, In step (1), the drying temperature is 100~120℃ and the time is 2~5h; the calcination temperature is 400~450℃, protected by an inert atmosphere, and the time is 2~3 hours. The inert atmosphere is selected from at least one of Ar, He, and N2.

4. The preparation method according to claim 1, characterized in that, In step (3), the mass ratio of the metal / composite carrier material to the pseudoboehmite is 0.05~0.

3.

5. The preparation method according to claim 1, characterized in that, In step (4), the impregnation is saturated impregnation; the concentration of Group VIB metals in the second active metal solution, calculated as oxides, is 0.05~0.5 g / mL, and the concentration of Group VIII metals, calculated as oxides, is 0.01~0.2 g / mL.

6. The preparation method according to claim 5, characterized in that, In step (4), the active metal in the second active metal solution is Mo, a group VIB metal, and Ni, a group VIII metal.

7. The preparation method according to claim 1, characterized in that, The amount of Group VIII metal introduced into the catalyst in step (1) is 30% to 50% of the total mass of Group VIII active metal oxides in the catalyst, calculated as oxides; the amount of Group VIII metal introduced into the catalyst in step (4) is 50% to 70% of the total mass of Group VIII metal oxides in the catalyst, calculated as oxides.

8. The preparation method according to claim 1, characterized in that, In step (4), the roasting temperature is 600~900℃ and the roasting time is controlled at 3~5 hours.

9. The residue oil hydrogenation catalyst prepared by any one of the preparation methods described in claims 1-8.

10. The catalyst according to claim 9, characterized in that, In the catalyst, the active metal is at least one of a Group VIB metal and at least one of a Group VIII metal, wherein the Group VIB metal is at least one of Mo and W, and the Group VIII metal is at least one of Co and Ni.

11. The catalyst according to claim 10, characterized in that, Group VIB metals are Mo and Group VIII metals are Ni.

12. The catalyst according to claim 9, characterized in that, In the catalyst, based on the mass of the catalyst, the content of group VIB metal oxide is 10%~30%, the content of group VIII metal oxide is 2%~15%, and the content of silicon oxide is 8%~20%.

13. The catalyst according to claim 9, characterized in that, The catalyst also contains nitrogen (N), with the N content (based on catalyst mass) being 0.5% to 1.0% by element.

14. The catalyst according to claim 9, characterized in that, In the catalyst, the dispersion of the active metal is: I VIB / I Al (×100) is 3~10, I VIII / I Al (×100) is 3~9, where the metal dispersion is the ratio of the XPS peak intensity of the active metal to that of aluminum.

15. The catalyst according to claim 9, characterized in that, The catalyst has a specific surface area of ​​140~230 m². 2 / g, pore volume 0.5~1.2cm 3 / g, with a mechanical strength of 16~27N / mm, and pores with a diameter of 15~80nm accounting for 6%~23% of the total pore volume, and pores with a diameter of less than 8nm accounting for less than 8% of the total pore volume.

16. The catalyst according to claim 15, characterized in that, The catalyst has a specific surface area of ​​170~200m². 2 / g, pore volume 0.7~0.9cm 3 / g, with a mechanical strength of 18~24N / mm, the pore volume of pores with a diameter of 15~80nm accounts for 10%~14% of the total pore volume, and the pore volume of pores with a diameter of less than 8nm accounts for 4%~7% of the total pore volume.

17. The catalyst according to claim 9, characterized in that, The catalyst has an acid content of 0.4~0.9 mmol / g; the ratio of Brønsted acid to Lewis acid is C. B / C L The value is 0.02~0.

09.

18. The catalyst according to claim 17, characterized in that, The catalyst has an acid content of 0.6~0.8 mmol / g; the ratio of Brønsted acid to Lewis acid is C. B / C L The value is 0.04~0.

07.

19. The use of the catalyst according to any one of claims 9-18 in the residue hydrotreating process.

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