A hydrogenation catalyst and its preparation method and application

Abstract

The present invention discloses a hydrogenation catalyst, its preparation method, and application. The catalyst preparation method of the present invention comprises: preparing a pseudo-boehmite wet filter cake, drying it to obtain pseudo-boehmite; mixing the obtained pseudo-boehmite with a porous carbon-nitrogen / SiO2 composite support, shaping it, drying it, and then washing it with hydrofluoric acid to obtain a catalyst precursor; and then impregnating the catalyst with an active metal solution, drying it, and calcining it to obtain a hydrogenation catalyst. The hydrogenation catalyst provided by the present invention is used in residual oil hydrotreating and has excellent desulfurization, denitrification, and demetallization properties, and its residual carbon removal performance is particularly outstanding.

Description

Technical Field

[0001] The present invention relates to a hydrogenation catalyst and a preparation method and application thereof. Background Art

[0002] Residue oil hydrogenation catalysts are primarily metal-supported catalysts, often using alumina and / or silica as supports and nickel, molybdenum, cobalt, and other active metal components. Existing methods, when the active metal loading is high, can easily lead to metal particle agglomeration or uneven distribution. Furthermore, during the calcination process, the strong interaction between the metal and the support can lead to the formation of metal-oxygen-aluminum bonds, which can affect the catalyst's catalytic efficiency and ultimately reduce its hydrogenation activity. Introducing an appropriate amount of silica into the alumina support can help increase the alumina's acidity and specific surface area, facilitating polymerization and hydrogenation reactions.

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

[0004] CN105582945A discloses a method for preparing a hydroprocessing catalyst. The method involves first impregnating an alumina support with an aqueous urea solution, then spraying a polyol or monosaccharide aqueous solution onto the alumina support in descending concentration order, so that the polyol and / or monosaccharide concentration forms a gradient distribution from low to high on the support from the outside to the inside, and then loading the active metal component. This method requires multiple spray impregnation steps to form a polymer carbonized shell, and has high solution concentration requirements, making the actual operation process relatively complex.

[0005] CN1257754A discloses a method for preparing a silica-alumina catalyst support. The method involves introducing water glass and aluminum sulfate to produce a silica-alumina precursor. The prepared support has a pore volume of 0.45 to 0.75 mL / g and an average pore diameter of 5 to 10 nm. However, the resulting silica-alumina support has a small pore size, making it unsuitable for use as a catalyst for the hydrotreating of heavy oils or residual oils with relatively high molecular weights.

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

[0007] To address the shortcomings of the prior art, the present invention provides a hydrogenation catalyst, its preparation method, and its application. The catalyst provided by the present invention has a high metal loading, is uniformly dispersed, has high mechanical strength, has a suitable pore distribution and specific surface area, has suitable surface acidity, and has a large pore size, making it suitable for residual oil hydroprocessing.

[0008] A first aspect of the present invention provides a method for preparing a hydrogenation catalyst, comprising the following steps:

[0009] (1) preparing a pseudo-boehmite wet filter cake, and drying the cake to obtain the pseudo-boehmite;

[0010] (2) mixing the pseudo-boehmite obtained in step (1) with a porous carbon nitrogen / SiO2 composite support, shaping, drying, and then washing with hydrofluoric acid to obtain a catalyst precursor;

[0011] (3) The catalyst precursor obtained in step (2) is impregnated with an active metal solution, dried, and calcined to obtain the catalyst.

[0012] In the method of the present invention, in step (1), the method for preparing a pseudo-boehmite wet filter cake comprises:

[0013] (A) adding a first alkaline solution to a first reaction kettle, introducing a mixed gas containing carbon dioxide to react, and adjusting the pH value of the system to 2 to 4;

[0014] (B) adding bottom water to the second reaction kettle, heating to the reaction temperature, and then adding the second alkaline solution and the material obtained in step (A) into the second reaction kettle in parallel to react;

[0015] (C) aging the slurry obtained after the reaction in step (B), filtering and washing after the aging to obtain a pseudo-boehmite filter cake.

[0016] In the method of the present invention, in step (A), the first alkaline solution is one or both of a sodium metaaluminate solution and a potassium metaaluminate solution, preferably a sodium metaaluminate solution; the concentration of the sodium metaaluminate solution and / or potassium metaaluminate is 10 to 30 g Al2O3 / L in terms of Al2O3, and the caustic ratio of the first alkaline solution is 1.35 to 1.65.

[0017] In the method of the present invention, in step (A), the volume of the first alkaline solution added to the first reactor is 2 / 3 to 3 / 4 of the volume of the first reactor; the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 30% to 70%; and the carbon dioxide-containing mixed gas can be a mixture of carbon dioxide and air.

[0018] In the method of the present invention, in step (A), the initial reaction temperature for the reaction of the mixed gas containing carbon dioxide is 15 to 65°C. 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 at the end of the reaction is 40 to 75°C.

[0019] In the method of the present invention, in step (B), the second alkaline solution is one or both of a sodium metaaluminate solution and a potassium metaaluminate solution, preferably a sodium metaaluminate solution; the concentration of sodium metaaluminate and / or potassium metaaluminate in the second alkaline solution is 130 to 350 g Al2O3 / L, preferably 150 to 250 g Al2O3 / L, calculated as Al2O3, and the caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.10 to 1.40, preferably 1.15 to 1.35.

[0020] 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.

[0021] In the method of the present invention, in step (B), the material obtained in step (A) is added to the second reactor, and the material addition time is controlled to be 60 to 150 minutes. Furthermore, in step (B), the second alkaline solution and the material obtained in step (A) are added to the second reactor in parallel to react, and the pH value is controlled to be 7.5 to 9.0.

[0022] In the method of the present invention, in step (B), the reaction is carried out under stirring at a reaction temperature of 40°C to 70°C, preferably 45°C to 65°C.

[0023] In the method of the present invention, in step (C), the aging conditions are: temperature of 50° C. to 95° C., and time of 30 min to 20 min.

[0024] In the method of the present invention, in step (C), the washing can be carried out by conventional washing methods in the art, preferably by washing with deionized water at 50° C. to 80° C. until the mixture is neutral.

[0025] In the method of the present invention, in step (C), the solid content of the obtained pseudo-boehmite wet filter cake is 30wt% to 45wt%.

[0026] In the method of the present invention, in step (1), the drying temperature is 60 to 150° C., and the drying time is 4 to 10 hours.

[0027] In the method of the present invention, in step (2), the porous carbon nitrogen / SiO2 composite support comprises:

[0028] (a) dissolving cyanamide in silica sol, stirring, and then adding an organic solvent to form a gel;

[0029] (b) The above gel is heated and calcined under an inert atmosphere to obtain a porous carbon nitrogen / SiO2 composite carrier, which is then ground into powder.

[0030] In the method of the present invention, in step (a), the concentration of the silica sol is 30% to 55%, preferably 40% to 50%, calculated as SiO2.

[0031] In the method of the present invention, in step (a), the mass ratio of the added amount of cyanamide to the silica sol is 0.5 to 1.5, preferably 0.6 to 1.2.

[0032] In the method of the present invention, in step (a), the organic solvent is selected from ethanol or ethylene glycol, preferably ethanol, and the added amount is in a mass ratio of 0.5 to 1.5 to the silica sol.

[0033] In the method of the present invention, in step (b), the calcination temperature is 250-650°C, preferably 300-450°C, the time is 2-15h, and the inert atmosphere is selected from at least one of Ar, He, and N2.

[0034] In the method of the present invention, in step (2), the mass ratio of the porous carbon-nitrogen / SiO2 composite support to the pseudo-boehmite is 0.05 to 0.3. The molding can be performed by extrusion molding. An extrusion aid can be added during the molding process, and the extrusion aid can be sesbania powder. The amount of the extrusion aid added is 1% to 6% of the mass of the pseudo-boehmite.

[0035] In the method of the present invention, in step (2), the drying temperature is 80-120° C. and the drying time is 4-6 hours.

[0036] In the method of the present invention, in step (2), the concentration of hydrofluoric acid is 5% to 20%, and the pickling time is 20 to 60 minutes.

[0037] In the method of the present invention, in step (3), the impregnation is performed by saturated impregnation. The active metal in the active metal solution is selected from 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; wherein the concentration of the Group VIB metal in the active metal solution as oxide is 0.2 to 0.4 g / mL, and the concentration of the Group VIII metal as oxide is 0.01 to 0.09 g / mL.

[0038] In the method of the present invention, in step (3), the drying temperature is 80-120° C., the drying time is 2-5 hours, the roasting temperature is 600-900° C., and the roasting time is controlled within 3-5 hours.

[0039] The second aspect of the present invention provides a hydrogenation catalyst obtained by the preparation method described in the first aspect.

[0040] In the present invention, in the catalyst, the active metal is at least one of the Group VIB metals and at least one of the 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.

[0041] In the present invention, the content of the Group VIB metal oxide in the catalyst is 15% to 25%, and the content of the Group VIII metal oxide is 1% to 6%, based on the mass of the catalyst.

[0042] In the present invention, the catalyst further contains N, and the content of N as a single substance is 0.5% to 1.0% based on the mass of the catalyst.

[0043] In the present invention, the active metal dispersion in the catalyst is: VIB / I Al (×100) is 3 to 8, I VIII / I Al (×100) is 2 to 8.

[0044] In the present invention, in the catalyst, the pore volume of pores with a pore diameter of 15 to 30 nm accounts for 15 to 30% of the total pore volume, and the pore volume of pores with a pore diameter of 8 nm or less accounts for less than 7% of the total pore volume, preferably 3% to 5%.

[0045] In the present invention, the specific surface area of the catalyst is 150 to 260 m 2 / g, preferably 170 to 220 m 2 / g, pore volume is 0.9~1.4cm 3 / g, preferably 0.95 to 1.20 cm3 / g, and preferably has a mechanical strength of 14 to 26 N / mm, preferably 17 to 23 N / mm.

[0046] The third aspect of the present invention provides the use of the above hydrogenation catalyst in a residue oil hydrogenation process.

[0047] In the present invention, residual oil and hydrogen-containing gas are contacted and reacted under hydrogenation reaction conditions in the presence of the above-mentioned hydrogenation catalyst or the hydrogenation catalyst obtained according to the above-mentioned preparation method.

[0048] In the above-mentioned residue oil hydrogenation reaction, the residue oil material is selected from one of atmospheric residue oil, vacuum residue oil and high-temperature coal tar.

[0049] In the above-mentioned residue oil hydrogenation reaction, 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 more preferably not less than 95%.

[0050] In the above-mentioned residue oil hydrogenation process, the operating conditions of the residue oil hydrogenation are as follows: reaction pressure of 5-20 MPaG, reaction temperature of 280-400°C, liquid hourly volume space velocity of 0.1-3.0 h -1 , the volume ratio of hydrogen to oil is 100~1000.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] The hydrogenation catalyst provided by the present invention has a high metal loading, is evenly dispersed, has high mechanical strength, suitable pore distribution and specific surface area, a large pore size, and suitable surface acidity. When applied to residual oil hydroprocessing, it has good desulfurization and denitrification performance, and also exhibits excellent catalytic performance in demetallization, with particularly outstanding carbon residue removal performance.

[0053] In the preparation method of the residue oil hydrogenation catalyst of the present invention, on the one hand, monocyanamide undergoes a thermal polymerization reaction in a silica sol to form a nitrogen-carbon composite support containing silicon dioxide. Since the nitrogen-carbon support has a certain band gap, and the band gap size can be adjusted by adjusting the calcination temperature, it is first mixed with pseudo-boehmite strips and then impregnated with a metal. Since it can form a metal-semiconductor heterojunction with the metal, the interaction between the metal and the nitrogen-carbon support is strengthened. Therefore, the metal is more likely to be loaded on the surface of the nitrogen-carbon support, which not only improves the metal dispersion and increases the metal loading, but also significantly reduces the electron transfer efficiency between the active metal and the alumina support, weakening the adsorption and bonding between the two. The synthesized catalyst has higher activity in the residue oil hydrogenation process. On the other hand, the nitrogen-carbon support contains a large number of silicon dioxide spheres. After dissolving with hydrofluoric acid and removing the silicon dioxide, a large number of vacancies will exist in the nitrogen-carbon support. In the subsequent composite process with pseudo-boehmite, it can act as a pore expander, making the catalyst pore size larger and more conducive to the diffusion of residue oil hydrogenation reactants. In addition, the pseudo-boehmite wet filter cake prepared by the present invention has low gibbsite content and high crystallinity, and the alumina obtained after calcination has a large pore volume and pore diameter; at the same time, the pseudo-boehmite wet filter cake prepared by the present invention has a high peptization index, which provides a guarantee for the preparation of a carrier with high lateral compressive strength. DETAILED DESCRIPTION

[0054] In the present invention, the ASAP2020 fully automatic physical adsorption instrument produced by Micromeritics Corporation of the United States was used to test the nitrogen adsorption-desorption curve of the sample at -196°C to determine the specific surface area, pore volume and pore size distribution.

[0055] In the present invention, the mechanical strength is tested using a ZQJ-III intelligent particle strength testing machine manufactured by Dalian Zhiqu Testing Machine Factory to measure the average mechanical strength of a group of samples with a length of 4-6 mm.

[0056] In the present invention, the metal dispersion is measured by XRS (the instrument is a Kratos Axis Ultra DLD model) to measure the XPS peak intensity ratio of the active metal and the aluminum element.

[0057] The technical solutions and effects of the present invention are further described below with reference to the following embodiments, but are not limited to the following embodiments.

[0058] Example 1

[0059] (1) A sodium metaaluminate mixed solution with a caustic ratio of 1.45 and a concentration of 25 g Al2O3 / L was added to a 5000 mL first reactor. A mixture of carbon dioxide and air containing 55% carbon dioxide by volume was then introduced to reduce the pH value of the system to 3.4. The temperature of the material at the end of the reaction was 55°C.

[0060] 1500 mL of bottom water was added to a 10,000 mL second reactor, and the stirring and heating devices were started. When the temperature rose to 65° C., the above materials were added to the second reactor at a flow rate of 35 mL / min for 90 minutes. A sodium aluminate solution with a concentration of 180 g Al2O3 / L and a caustic ratio of 1.25 was added concurrently. The pH value of the slurry in the second reactor was controlled to 8.0 by adjusting the flow rate of the sodium aluminate solution, while maintaining the temperature of the slurry in the second reactor constant. The reaction was terminated after the above materials were used up, and the slurry was aged at 90° C. for 80 minutes. After aging, the slurry was washed with deionized water at 70° C. until neutral, filtered, and a pseudo-boehmite wet cake with a solid content of 37% was obtained. The cake was then dried at 120° C. for 6 hours to obtain the pseudo-boehmite required by the present invention.

[0061] (2) Dissolve 10 g of cyanamide in 12.5 g of 40% silica sol. Then, add 12 mL of anhydrous ethanol with vigorous stirring to form a gel. Transfer the gel to a crucible and heat to 400°C in a tube furnace for 6 h under nitrogen protection. Grind the resulting sample into a powder, i.e., the porous carbonitride / SiO2 composite support.

[0062] (3) Weigh 100 g of the porous carbon-nitrogen / SiO2 composite support after the above treatment, mix it with 500 g of pseudo-boehmite and 15 g of sesbania powder, and extrude it into strips. Dry it at 120° C. for 4 hours, and then wash it with 8% hydrofluoric acid solution for 30 minutes to obtain a catalyst precursor.

[0063] (4) An impregnation solution containing 0.290 g / mL of MoO3 and 0.087 g / mL of NiO was prepared and the catalyst precursor was saturated with the solution. After complete impregnation, the solution was dried at 120°C for 5 hours and calcined at 650°C for 3 hours to obtain the final hydrogenation catalyst A. The physicochemical properties of the catalyst are shown in Table 1.

[0064] Example 2

[0065] The rest of the synthesis process was the same as in Example 1, except that the amount of 40% silica sol added was changed to 14.3 g, to obtain the final hydrogenation catalyst B, whose physicochemical properties are shown in Table 1.

[0066] Example 3

[0067] The rest of the synthesis process was the same as in Example 1, except that the concentration of Al2O3 in the first reactor in step (1) was changed to 15 g / L, the volume fraction of carbon dioxide in the mixture of carbon dioxide and air was 45%, and the aging temperature was changed to 95°C to obtain the pseudo-boehmite required by the present invention, and the final hydrogenation catalyst C. The physicochemical properties are shown in Table 1.

[0068] Example 4

[0069] The rest of the synthesis process was the same as in Example 1, except that in step (3), a 20% hydrofluoric acid solution was used for washing for 15 minutes. The physicochemical properties of the final hydrogenation catalyst D are shown in Table 1.

[0070] Comparative Example 1

[0071] The rest of the synthesis process was the same as in Example 1, except that an equal amount of activated carbon powder was used instead of the porous carbon nitrogen / SiO2 composite support. The final hydrogenation catalyst E was obtained, and its physicochemical properties are shown in Table 1.

[0072] Comparative Example 2

[0073] The other synthetic processes were the same as in Example 1, except that the preparation process of pseudo-boehmite was modified: 3000 mL of a sodium aluminate solution having a concentration of 65 gAl O / L and a caustic ratio of 1.35 was added to a 5.0 L reactor. A mixture of carbon dioxide and air having a carbon dioxide content of 80% (volume fraction) was then introduced. The initial reaction temperature was 25° C. The slurry was cooled to maintain a constant temperature, and the reaction time was controlled to be 45 min, so that the pH value of the sodium aluminate solution was reduced to 8.8. The slurry was filtered, washed with 75° C. deionized water, and dried at 120° C. for 6 hours to obtain pseudo-boehmite. Final hydrogenation catalyst F was obtained, and its physicochemical properties are shown in Table 1.

[0074] Example 5

[0075] The catalysts obtained in Examples 1-4 and Comparative Examples 1-2 were respectively used in residue oil hydrogenation reactions. The properties of the raw materials are shown in Table 2, and the evaluation conditions and results are shown in Table 3.

[0076] Table 1 Physicochemical properties of various hydrogenation catalysts

[0077]

[0078]

[0079] Table 2 Properties of crude oil

[0080] <![CDATA[Density (20 °C), kg / m 3 > 986.3 S,wt% 4.25 N,ppm 2439 CCR,wt% 12.8 Ni,ppm 22.3 V,ppm 70.9

[0081] Table 3 Evaluation conditions and evaluation results of the hydrogenation catalysts obtained in each case

[0082]

Claims

1. A method for preparing a hydrogenation catalyst, comprising the following steps: (1) preparing a pseudo-boehmite wet filter cake, and drying it to obtain pseudo-boehmite; (2) mixing the pseudo-boehmite obtained in step (1) with a porous carbon nitrogen / SiO2 composite support, shaping, drying, and then washing with hydrofluoric acid to obtain a catalyst precursor; (3) impregnating the catalyst precursor obtained in step (2) with an active metal solution, drying, and calcining to obtain the catalyst; In step (1), the method for preparing pseudo-boehmite wet filter cake comprises: (A) adding a first alkaline solution to a first reaction kettle, introducing a mixed gas containing carbon dioxide to react, and adjusting the pH value of the system to 2-4; (B) adding bottom water to the second reaction kettle, heating to the reaction temperature, and then adding the second alkaline solution and the material obtained in step (A) into the second reaction kettle in parallel to react; (C) aging the slurry obtained after the reaction in step (B), filtering and washing after the aging to obtain a pseudo-boehmite filter cake; In step (A), the volume fraction of carbon dioxide in the carbon dioxide-containing mixed gas is 30% to 70%; In step (A), the first alkaline solution is one or both of a sodium metaaluminate solution and a potassium metaaluminate solution; the concentration of the sodium metaaluminate solution and / or the potassium metaaluminate is 10-30 g Al2O3 / L in terms of Al2O3, and the caustic ratio of the first alkaline solution is 1.35-1.65; In step (B), the second alkaline solution is one or both of a sodium metaaluminate solution and a potassium metaaluminate solution; the concentration of sodium metaaluminate and / or potassium metaaluminate in the second alkaline solution is 130-350 g Al2O3 / L in terms of Al2O3, and the caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.10-1.40; In step (3), the active metal in the active metal solution is selected from at least one of Group VIB metals and at least one of Group VIII metals; In the catalyst, based on the mass of the catalyst, the content of the Group VIB metal oxide is 15% to 25%, and the content of the Group VIII metal oxide is 1% to 6%; In the catalyst, the pore volume of pores with a pore diameter of 15 to 30 nm accounts for 15% to 30% of the total pore volume, and the pore volume of pores with a pore diameter of less than 8 nm accounts for less than 7% of the total pore volume.

2. The preparation method according to claim 1, characterized in that In step (2), the porous carbon nitrogen / SiO2 composite support comprises: (a) dissolving cyanamide in silica sol, stirring, and then adding an organic solvent to form a gel; (b) The above gel is heated and calcined under an inert atmosphere to obtain a porous carbon nitrogen / SiO2 composite carrier, which is then ground into powder.

3. The preparation method according to claim 1, characterized in that In step (2), the mass ratio of the porous carbon-nitrogen / SiO2 composite support to pseudo-boehmite is 0.05-0.

3.

4. The preparation method according to claim 1, characterized in that In step (2), the concentration of hydrofluoric acid is 5% to 20%, and the pickling time is 20 to 60 minutes.

5. The preparation method according to claim 1, characterized in that In step (3), the active metal in the active metal solution is at least one of Mo and W as the Group VIB metal, and at least one of Co and Ni as the Group VIII metal; wherein the concentration of the Group VIB metal in the active metal solution as oxide is 0.2-0.4 g / mL, and the concentration of the Group VIII metal as oxide is 0.01-0.09 g / mL.

6. The preparation method according to claim 1, characterized in that In step (3), the active metal in the active metal solution is Mo as the Group VIB metal and Ni as the Group VIII metal.

7. The preparation method according to claim 1, characterized in that In step (3), the calcination temperature is 600-900° C., and the calcination time is controlled within 3-5 hours.

8. A hydrogenation catalyst prepared by the preparation method according to any one of claims 1 to 7.

9. The catalyst according to claim 8, characterized in that In the catalyst, the active metal is at least one of Group VIB metals and at least one of Group VIII metals, 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.

10. The catalyst according to claim 8, characterized in that In the catalyst, the Group VIB metal is Mo and the Group VIII metal is Ni.

11. The catalyst according to claim 8, characterized in that The catalyst further contains nitrogen, and the content of nitrogen as a single substance is 0.5% to 1.0% based on the mass of the catalyst.

12. The catalyst according to claim 8, characterized in that In the catalyst, the active metal dispersion is: VIB / I Al (×100) is 3~8, I VIII / I Al (×100) is 2~8.

13. The catalyst according to claim 8, characterized in that In the catalyst, the pore volume of pores with a pore diameter of less than 8 nm accounts for 3% to 5% of the total pore volume.

14. The catalyst according to claim 8, characterized in that The specific surface area of the catalyst is 150~260m 2 / g, pore volume is 0.9~1.4cm 3 / g, and the mechanical strength is 14~26N / mm.

15. The catalyst according to claim 8, characterized in that The specific surface area of the catalyst is 170~220m 2 / g, pore volume is 0.95~1.20cm 3 / g, and the mechanical strength is 17~23N / mm.

16. Use of the catalyst according to any one of claims 8 to 15 in a residue oil hydrogenation process.

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