Hydrodesulfurization and demetallization catalyst and method for preparing the same

Abstract

The application discloses a kind of hydrodesulfurization, demetallization catalyst and preparation method thereof, the catalyst includes the alumina carrier containing spherical cavity, hydrogenation active metal molybdenum, nickel, cobalt and adjuvant phosphorus;Wherein the in-situ growth sheet-like alumina in the spherical cavity and the outer surface of carrier, the filling rate of sheet-like alumina in spherical cavity is 40%-80%, the coverage of sheet-like alumina on the outer surface of carrier is 50%-80%;The size of the spherical cavity is 1~5 μm, the sheet-like alumina grain size is 100-500nm;The active metal MoO3 content at spherical cavity is 16.5wt%-21.5wt%, the NiO content is 4.0wt%-6.0wt%, and the CoO content is 1.5wt%-3.5wt%.The catalyst controls the coverage of surface sheet-like alumina and the filling rate in cavity and metal content, so that the surface pore structure is more suitable for residue hydrodesulfurization and hydrodemetallization process.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation, specifically relating to a hydrodesulfurization and demetallization catalyst and its preparation method. Background Technology

[0002] Fixed-bed heavy oil hydrotreating technology boasts advantages such as mature processes, simple operation, and high product quality, making it the most commonly used heavy oil hydrotreating technology in industry. The main purpose of the fixed-bed heavy oil hydrotreating process is to remove a large number of impurities from the residual oil feedstock, such as sulfur, nitrogen, metals, and asphaltenes, and to provide feedstock for catalytic cracking units. The main reactions in this process include hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, aromatics saturation, and hydrocarbon hydrocracking.

[0003] For heavy distillate oils, the feedstock contains a large number of reactant molecules with complex structures, large molecular diameters, and abundant heteroatoms. Furthermore, the catalyst activity continuously decreases due to the effects of metal deposition and coking during the reaction process. Therefore, the catalyst is required to not only have good reactivity but also excellent diffusion performance and scale-holding capacity.

[0004] CN104646008A discloses a low-quality heavy oil hydrodesulfurization and demetallization catalyst and its preparation method. The catalyst uses alumina as a support and Group VIII and VIB elements, particularly Ni-Mo, as the active components. The catalyst has a pore volume of 0.61-0.70 mL / g and a specific surface area of ​​155-200 m². 2 The catalyst has an average pore diameter of 13.0-18.0 nm, which gradually increases radially from the center to the outer surface of the catalyst particles. The catalyst is prepared by treating the shaped and calcined support particles with an acid solution of continuously increasing concentration; however, the catalyst's scale-holding capacity needs further improvement.

[0005] CN111822011A discloses a support, catalyst, and preparation method thereof for hydrodesulfurization. The support is an alumina support containing additives, comprising a main alumina and rod-shaped alumina. The main alumina is alumina with micron-sized pores, with at least some rod-shaped alumina distributed on the outer surface of the main alumina and within the micron-sized pores. Additives phosphorus and / or boron are distributed within the micron-sized pores, and additive titanium is distributed on the surface of the rod-shaped alumina on the outer surface of the support. The preparation method of this support is as follows: a solution containing additives phosphorus and / or boron is adsorbed onto a physical pore-expanding agent, then mixed and kneaded with boehmite, dried, and calcined to obtain an intermediate support; this intermediate is then immersed in an ammonium bicarbonate solution, sealed, heat-treated, and dried; the outer surface of the impregnated material is sprayed with a solution containing additive titanium, dried, and calcined to obtain the alumina support. The catalyst prepared by this method has a rod-shaped surface structure, but the bonding strength between the rod-shaped alumina grown on the surface and the main alumina needs further improvement. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrodesulfurization and demetallization catalyst and its preparation method. By controlling the coverage of the surface alumina, the filling rate of the cavities, and the metal content, the catalyst enhances the impurity-accommodating capacity of the surface pore structure, making it more suitable for hydrodesulfurization and demetallization processes of residual oil.

[0007] The hydrodesulfurization and demetallization catalyst of the present invention comprises an alumina support with spherical cavities, hydrodesulfurization active metals molybdenum, nickel, and cobalt, and an auxiliary agent phosphorus; wherein lamellar alumina is grown in situ within the spherical cavities and on the outer surface of the support, the lamellar alumina filling rate in the spherical cavities is 40%-80%, and the lamellar alumina coverage rate on the outer surface of the support is 50%-80%; the size of the spherical cavities is 1-5 μm, and the size of the lamellar alumina grains is 100-500 nm; the content of the active metals MoO3 in the spherical cavities is 16.5wt%-21.5wt%, the content of NiO is 4.0wt%-6.0wt%, and the content of CoO is 1.5wt%-3.5wt%.

[0008] In the hydrodesulfurization and demetallization catalyst of the present invention, based on the total weight of the catalyst, MoO3 is 13.0wt%-18.5wt%, NiO is 3.5wt%-5.0wt%, CoO is 0.1wt%-0.5wt%, phosphorus (as elemental phosphorus) is 0.2wt%-0.8wt%, and alumina support is 75.2wt%~83.2wt%.

[0009] In the hydrodesulfurization and demetallization catalyst of the present invention, the sheet-like alumina in the micron-sized spherical cavity of the alumina support is stacked to form pores of 30-80 nm, and the filling rate of the sheet-like alumina in the micron-sized pores is 40%-80%.

[0010] In the hydrodesulfurization and demetallization catalyst of the present invention, the coverage of the plate alumina on the outer surface of the support is 50%-80%, and the plate alumina forms pores of 30-150 nm on the outer surface of the support.

[0011] The filling rate refers to the percentage of the volume of the micron-sized pores occupied by the lamellar alumina in the spherical cavity. The coverage rate refers to the percentage of the lamellar alumina occupying the outer surface area of ​​the alumina carrier.

[0012] The preparation method of hydrodesulfurization and demetallization of the present invention includes the following:

[0013] (1) Micron-sized spherical activated carbon was impregnated with a phosphorus-containing solution and a molybdenum-cobalt-nickel impregnation solution to obtain modified micron-sized spherical activated carbon;

[0014] (2) Modified micron-sized spherical activated carbon, pseudoboehmite and water are mixed into a slurry, solid and liquid are separated, the solid material is dried, kneaded, shaped, dried and calcined to obtain the first alumina carrier;

[0015] (3) The first alumina carrier is immersed in an aqueous solution of propylene oxide and sealed for heat treatment. After treatment, the material is separated into solid and liquid phases. The solid phase material is dried and calcined to obtain the second alumina carrier.

[0016] (4) The second alumina support is impregnated with molybdenum-nickel impregnation solution, dried and calcined to obtain the catalyst.

[0017] In the method of the present invention, the phosphorus-containing solution in step (1) is an aqueous phosphate solution, wherein the phosphate is one or more of ammonium phosphate, diammonium hydrogen phosphate and diammonium dihydrogen phosphate, the concentration of the aqueous phosphate solution is 1.5%-3.5% based on element P, and the immersion time is 0.5-4 hours.

[0018] In the method of the present invention, the molybdenum-cobalt-nickel impregnation solution in step (1) contains 3.5-7.5 g / 100 mL of molybdenum (calculated as molybdenum oxide), 1.0-2.5 g / 100 mL of cobalt (calculated as cobalt oxide), and 0.6-1.5 g / 100 mL of nickel (calculated as nickel oxide), and the impregnation time is 0.5-4 hours.

[0019] In the method of the present invention, there is no special requirement for the order of impregnating the micron-sized spherical activated carbon with the phosphorus-containing solution and the molybdenum-cobalt-nickel impregnation solution in step (1). It is preferred to impregnate the carbon with the phosphorus-containing solution first and then with the molybdenum-cobalt-nickel impregnation solution. After each impregnation, a drying treatment is required. The drying temperature is 120-180℃ and the drying time is 4-10 hours.

[0020] In the method of the present invention, the diameter of the micron-sized spherical activated carbon in step (1) is 1-5 microns. The micron-sized spherical activated carbon can be prepared by existing methods or purchased.

[0021] In the method of the present invention, the mass ratio of modified micron-sized spherical activated carbon to pseudoboehmite in step (2) is 1:9-1:19, and the liquid-solid mass ratio of the slurry is 5:1-10:1.

[0022] In the method of this invention, the mixing and molding in step (2) are carried out using conventional methods in the art. During molding, an extrusion aid and a solvent are added as needed. The extrusion aid is guar gum powder, added at 0.1wt%-0.5wt% of the final alumina carrier weight. The solvent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, etc., added at 0.1wt%-1.5wt% of the alumina carrier weight, depending on the final molding effect. The drying temperature is 100-160℃, and the drying time is 4-10 hours; the calcination temperature is 450-700℃, preferably 450-600℃, and the calcination time is 4-6 hours; calcination is carried out in an oxygen-containing atmosphere.

[0023] In the method of the present invention, the mass percentage concentration of the propylene oxide aqueous solution in step (3) is 2.5%-12%, preferably 4%-8%, and the mass ratio of the amount of propylene oxide aqueous solution to the mass ratio of the alumina carrier precursor is 3:1-10:1, preferably 4:1-8:1.

[0024] In the method of the present invention, the sealing heat treatment in step (3) is preferably carried out in a closed high-pressure autoclave. The sealing heat treatment process is as follows: first, it is treated at 60-100℃ for 1-4 hours, and then at 110-180℃, preferably 120-160℃, for 8-12 hours.

[0025] In the method of the present invention, the drying temperature in step (3) is 100-160℃ and the drying time is 2-8 hours. The calcination temperature is 500-750℃ and the calcination time is 4-6 hours. The calcination is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.

[0026] In the method of the present invention, the molybdenum-nickel impregnation solution in step (4) has Mo content of 10-20 g / 100 mL as metal oxide and Ni content of 2.5-5 g / 100 mL as metal oxide.

[0027] In the method of the present invention, the drying conditions in step (4) are: drying temperature 100~180℃, drying time 1~10 hours; the calcination conditions are: calcination temperature 400~500℃, calcination time 2~8 hours.

[0028] The application of the hydrodesulfurization and hydrodemetallization catalyst of the present invention in the hydrotreating process of inferior heavy oil.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] This invention controls the surface coverage of the alumina support and the filling rate of the micron-sized cavities, ensuring that 50%–80% of the surface is covered by lamellar alumina, forming open channels of 30–150 nm. The filling rate of the lamellar alumina within these micron-sized channels is 40%–80%, resulting in a catalyst with strong impurity handling and mass transfer capabilities. Simultaneously, the high content of active metals within the micron-sized cavities and the suitable acidity after phosphorus modification make each micron-sized spherical cavity a microreactor with enhanced catalytic activity and strong impurity handling capacity, thus strengthening the hydrogenation reaction and ensuring high catalyst activity stability. Attached Figure Description

[0031] Figure 1 This is a SEM image of the surface of the first alumina carrier prepared in Example 1.

[0032] Figure 2 The image shows a cross-sectional SEM image of the first alumina carrier prepared in Example 1.

[0033] Figure 3 This is a SEM image of the surface of the second alumina carrier prepared in Example 1.

[0034] Figure 4 This is a cross-sectional SEM image of the second alumina carrier prepared in Example 1.

[0035] Figure 5 The image shows the surface SEM image of the comparative alumina support prepared in Comparative Example 2.

[0036] Figure 6 The image shows a cross-sectional SEM image of the comparative alumina support prepared in Comparative Example 2. Detailed Implementation

[0037] The technical solution 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. In the present invention, wt% represents mass fraction.

[0038] The microstructure of the alumina support was characterized using scanning electron microscopy. The specific operation was as follows: The microstructure of the support was characterized using a JSM-7500F scanning electron microscope with an accelerating voltage of 5KV, an accelerating current of 20µA, and a working distance of 8mm.

[0039] The active metal content in the catalyst microregions was determined using a scanning electron microscope equipped with an energy dispersive spectrometer (EDAX). Five microregions to be measured were randomly selected for composition determination and the average value was taken. The accelerating voltage was 30 kV and the working distance was 8 mm.

[0040] The contents of MoO3 and NiO in the catalyst, and the molybdenum-nickel content in the bulk catalyst were determined according to the method described in the literature, "Determination of Metal Element Content in Molybdenum-Nickel Series Hydrogenation Catalysts by ICP-AES," Guangzhou Chemical Industry, 2021, 49, (17): 129-130. The cobalt content in the bulk catalyst was determined according to the standard SHT0345-1992-Determination of Cobalt Content in Hydrogenation Refining Catalysts.

[0041] The active metal content in the micron-sized pores refers to the active metal content in the pores formed after the micron-sized activated carbon balls in the catalyst are calcined. During the determination, the catalyst particles are cut and adhered to the scanning electron microscope sample stage, so that the cross-section of the catalyst particles is perpendicular to the direction of the electron beam of the scanning electron microscope. The composition of this region is determined by using a scanning electron microscope equipped with an energy dispersive spectroscopy (EDS).

[0042] Preparation of micron-sized spherical activated carbon:

[0043] The micron-sized spherical activated carbon used in this invention is prepared according to the method described in the literature: Dai Linlin, Li Wei, Wu Qiong, et al. Preparation of micron-sized spherical activated carbon by hydrothermal carbonization-CO2 activation of carboxymethyl cellulose [J]. Chemistry and Industry of Forest Products, 2015, 35(4): 21-27. The diameter of the prepared micron-sized spherical activated carbon is 1-5 microns.

[0044] Example 1 (1) Weigh 100 g of the above-mentioned micron-sized spherical activated carbon, soak the activated carbon in an ammonium phosphate solution with a phosphorus concentration of 2.3% for 1 hour, filter the soaked activated carbon, and dry it at 160°C for 4 hours. Then, impregnate the activated carbon with a molybdenum-cobalt-nickel solution with a molybdenum oxide concentration of 5 g / 100 mL, a cobalt oxide concentration of 1.3 g / 100 mL, and a nickel oxide concentration of 0.8 g / 100 mL for 1 hour. After impregnation, filter the material and dry it at 170°C for 4 hours to obtain modified micron-sized spherical activated carbon.

[0045] (2) Weigh 500g of pseudoboehmite, 42g of modified micron-sized spherical activated carbon from step (1), add 3300g of deionized water, and mechanically stir the mixture for 2 hours. After stirring, the material is separated into liquid and solid. The solid material is dried at 120℃ for 6 hours. Then, 3g of guar gum powder is added to the dried material and mixed evenly. An appropriate amount of 0.5% acetic acid solution is added and kneaded evenly. The mixture is then extruded into strips and dried at 140℃ for 6 hours. The strips are then calcined at 550℃ in an oxygen atmosphere for 5 hours to obtain the first alumina carrier. The scanning electron microscope image of the surface of the alumina carrier is shown in the figure. Figure 1 Cross-sectional scanning electron microscope image is shown below. Figure 2 .

[0046] (3) Weigh 100 g of the first alumina carrier from step (2), add 650 g of a 5.6% propylene oxide aqueous solution, transfer the mixture into a high-pressure reactor, seal it, and place the high-pressure reactor in an oven. First, seal it at 70°C for 3 hours, then raise the temperature to 145°C and seal it for 10.5 hours. After cooling, wash and filter the material. Dry the solid material at 120°C for 6 hours and calcine it at 600°C for 5 hours to obtain the second alumina carrier. The scanning electron microscope image of the outer surface of the carrier is shown in the figure. Figure 3 Cross-sectional scanning electron microscope image is shown below. Figure 4 .

[0047] (4) The second alumina support from step (3) was placed in a spray impregnation pot and impregnated with an active component impregnation solution with a molybdenum oxide concentration of 15.5 g / 100 mL and a nickel oxide concentration of 3.9 g / 100 mL in a saturated impregnation manner. The impregnated material was dried at 120 °C for 5 hours and calcined at 500 °C for 5 hours to obtain catalyst Cat-1. The properties of the catalyst are shown in Table 1. Example 1

[0048] Same as Example 1, except that in step (1), the phosphorus content in the phosphate solution is 1.8%, the molybdenum oxide concentration in the molybdenum-cobalt-nickel solution is 4.2 g / 100 mL, the cobalt oxide concentration is 1 g / 100 mL, and the nickel oxide concentration is 0.6 g / 100 mL; in step (2), the amount of modified micron-sized spherical activated carbon added is 33 g; in step (3), the concentration of propylene oxide is 6.5%, the amount of solution used is 530 g, and during hydrothermal treatment, it is first sealed and treated at 80°C for 2 hours, and then the temperature is raised to 155°C for 9.5 hours; in step (4), the molybdenum oxide concentration in the active component impregnation solution is 13 g / 100 mL, the nickel oxide concentration is 3.5 g / 100 mL, and the catalyst Cat-2 is prepared. The properties of the catalyst are shown in Table 1. Example 2

[0049] Same as Example 1, except that in step (1), the phosphorus content in the phosphate solution is 3.3%, the molybdenum oxide concentration in the molybdenum-cobalt-nickel solution is 6 g / 100 mL, the cobalt oxide concentration is 1.5 g / 100 mL, and the nickel oxide concentration is 1 g / 100 mL; in step (2), the amount of modified micron-sized spherical activated carbon added is 50 g; in step (3), the concentration of propylene oxide is 4.6%, the solution volume is 720 g, and during hydrothermal treatment, it is first sealed at 60°C for 4 hours, and then heated to 135°C for 11.5 hours; in step (4), the molybdenum oxide concentration in the active component impregnation solution is 16 g / 100 mL, the nickel oxide concentration is 4.2 g / 100 mL, and the catalyst Cat-3 is prepared. The properties of the catalyst are shown in Table 1. Example 3

[0050] Same as Example 1, except that in step (1) the phosphorus content in the phosphate solution is 2.8%, the molybdenum oxide concentration in the molybdenum-cobalt-nickel solution is 7 g / 100 mL, the cobalt oxide concentration is 1.7 g / 100 mL, and the nickel oxide concentration is 1.2 g / 100 mL; in step (2) the amount of modified micron-sized spherical activated carbon added is 28 g; in step (3) the concentration of propylene oxide is 7.1%, the solution volume is 450 g, and during hydrothermal treatment, it is first sealed at 90°C for 1.5 hours, and then heated to 160°C for 8.5 hours; in step (4) the molybdenum oxide concentration in the active component impregnation solution is 14.5 g / 100 mL, the nickel oxide concentration is 3.7 g / 100 mL, and the catalyst Cat-4 is prepared. The properties of the catalyst are shown in Table 1.

[0051] Comparative Example 1

[0052] Same as Example 1, except that the propylene oxide aqueous solution in step (3) was replaced with an ammonia aqueous solution of the same mass concentration to prepare catalyst Cat-5. The properties of the catalyst are shown in Table 1.

[0053] Comparative Example 2

[0054] Same as Example 1, except that the propylene oxide aqueous solution in step (3) was replaced with an ethylene oxide solution of the same concentration to prepare catalyst Cat-6. The properties of the catalyst are shown in Table 1, and the corresponding scanning electron microscope images of the support surface are shown in Table 1. Figure 5 Cross-sectional scanning electron microscope image is shown below. Figure 6 .

[0055] Comparative Example 3

[0056] Same as Example 1, except that the concentration of propylene oxide in step (3) is 1.2%, and the catalyst Cat-7 is prepared. The properties of the catalyst are shown in Table 1.

[0057] Comparative Example 4

[0058] Same as Example 1, except that in step (1), the micron-sized spherical activated carbon was not impregnated with ammonium phosphate and active metal solution I, but the same amount of ammonium phosphate and active metal solution were added during the support molding process to obtain the comparative catalyst Cat-8. The properties of the catalyst are shown in Table 1.

[0059] Table 1 Catalyst Properties

[0060] Example 4

[0061] The hydrodesulfurization and demetallization catalysts Cat-1 to Cat-4 prepared according to this invention and the comparative examples prepared Cat-5 to Cat-8 were respectively packed into a fixed-bed hydrotreating reactor. The feedstocks processed (see Table 2) were tested under the following conditions: reaction temperature 380℃, hydrogen-to-oil volume ratio 800, and liquid hourly space velocity 0.5 h⁻¹.-1 The hydrogen partial pressure was 14.5 MPa, and the impurity removal properties were obtained after 2000 hours of continuous operation. See Table 3 for the properties of the impurity removal.

[0062] Table 2 Properties of Crude Oil

[0063]

[0064] Table 3 Evaluation results of the catalyst

[0065] Hydrogenation protects catalyst Cat-1 Cat-2 Cat-3 Cat-4 Cat-5 Cat-6 Cat-7 Cat-8 Relative Ni and V removal rates, % 145 137 146 143 100 105 109 129 Relative desulfurization rate, % 131 129 139 134 100 101 106 120

Claims

1. A hydrodesulfurization and demetallization catalyst, characterized in that: The catalyst comprises an alumina support with a spherical cavity, hydrogenation active metals molybdenum, nickel, cobalt, and phosphorus as an auxiliary agent; wherein lamellar alumina is grown in situ inside the spherical cavity and on the outer surface of the support, the lamellar alumina filling rate in the spherical cavity is 40%-80%, and the lamellar alumina coverage rate on the outer surface of the support is 50%-80%; the size of the spherical cavity is 1~5μm, and the size of the lamellar alumina grains is 100-500nm; the content of active metal MoO3 in the spherical cavity is 16.5wt%-21.5wt%, the content of NiO is 4.0wt%-6.0wt%, and the content of CoO is 1.5wt%-3.5wt%; the preparation method of the hydrogenation desulfurization and demetallization catalyst includes the following: (1) using a phosphorus-containing solution, (1) Impregnate micron-sized spherical activated carbon with molybdenum-cobalt-nickel impregnation solution to obtain modified micron-sized spherical activated carbon; (2) Mix modified micron-sized spherical activated carbon, pseudoboehmite and water into a slurry, separate solid and liquid, dry the solid material, knead, shape, dry and calcine to obtain the first alumina carrier; (3) Immerse the first alumina carrier in propylene oxide aqueous solution for sealed heat treatment, after treatment the material is separated from solid and liquid, dry and calcine the solid material to obtain the second alumina carrier; (4) Impregnate the second alumina carrier with molybdenum-nickel impregnation solution, dry and calcine to obtain the catalyst; The mass percentage concentration of the propylene oxide aqueous solution in step (3) is 2.5%-12%, and the mass ratio of the amount of propylene oxide aqueous solution to the mass ratio of the alumina carrier precursor is 3:1-10:

1.

2. The catalyst according to claim 1, characterized in that: Based on the total weight of the catalyst, the MoO3 is 13.0wt%-18.5wt%, NiO is 3.5wt%-5.0wt%, CoO is 0.1wt%-0.5wt%, phosphorus (as elemental phosphorus) is 0.2wt%-0.8wt%, and alumina support is 75.2wt%~83.2wt%.

3. The catalyst according to claim 1, characterized in that: In the micron-sized spherical cavity of the alumina carrier, the stacking of sheet-like alumina forms channels of 30-80 nm.

4. The catalyst according to claim 1, characterized in that: The sheet-like alumina forms pores of 30-150 nm on the outer surface of the carrier.

5. A method for preparing a hydrodesulfurization and demetallization catalyst according to any one of claims 1 to 4, characterized in that... The process includes the following: (1) Impregnating micron-sized spherical activated carbon with a phosphorus-containing solution and a molybdenum-cobalt-nickel impregnation solution to obtain modified micron-sized spherical activated carbon; (2) Mixing the modified micron-sized spherical activated carbon, boehmite and water into a slurry, separating the solid and liquid phases, drying the solid phase material, kneading and molding, drying and calcining to obtain the first alumina support; (3) Immersing the first alumina support in an aqueous solution of propylene oxide and sealing it for heat treatment, separating the solid and liquid phases after treatment, drying and calcining the solid phase material to obtain the second alumina support; (4) Impregnating the second alumina support with a molybdenum-nickel impregnation solution, drying and calcining to obtain the catalyst.

6. The method according to claim 5, characterized in that: The phosphorus-containing solution in step (1) is a phosphate aqueous solution, wherein the phosphate is one or more of ammonium phosphate, diammonium hydrogen phosphate and diammonium dihydrogen phosphate, the concentration of the phosphate aqueous solution is 1.5%-3.5% based on elemental P, and the immersion time is 0.5-4 hours.

7. The method according to claim 5, characterized in that: The molybdenum-cobalt-nickel impregnation solution described in step (1) contains 3.5-7.5 g / 100 mL of molybdenum (calculated as molybdenum oxide), 1.0-2.5 g / 100 mL of cobalt (calculated as cobalt oxide), and 0.6-1.5 g / 100 mL of nickel (calculated as nickel oxide), and the impregnation time is 0.5-4 hours.

8. The method according to claim 5, characterized in that: The modified micron-sized spherical activated carbon and pseudoboehmite in step (2) have a mass ratio of 1:9 to 1:19, and the liquid-solid mass ratio of the slurry is 5:1 to 10:

1.

9. The method according to claim 5, characterized in that: The drying temperature in step (2) is 100-160℃ and the drying time is 4-10 hours; the calcination temperature is 450-700℃ and the calcination time is 4-6 hours, and the calcination is carried out in an oxygen-containing atmosphere.

10. The method according to claim 5, characterized in that: The mass percentage concentration of the propylene oxide aqueous solution in step (3) is 2.5%-12%, and the mass ratio of the propylene oxide aqueous solution to the alumina carrier precursor is 3:1-10:

1.

11. The method according to claim 5, characterized in that: The sealing heat treatment process described in step (3) is as follows: first, treat at 60-100℃ for 1-4 hours, and then treat at 110-180℃ for 8-12 hours.

12. The method according to claim 5, characterized in that: The drying temperature in step (3) is 100-160℃ and the drying time is 2-8 hours; the calcination temperature is 500-750℃ and the calcination time is 4-6 hours, and the calcination is carried out in an oxygen-containing atmosphere.

13. The method according to claim 5, characterized in that: In step (4), the molybdenum-nickel impregnation solution contains 10-20 g / 100 mL of Mo (calculated as metal oxide) and 2.5-5 g / 100 mL of Ni (calculated as metal oxide).

14. The method according to claim 5, characterized in that: The drying conditions for step (4) are: drying temperature 100~180℃, drying time 1~10 hours; the calcination conditions are: calcination temperature 400~500℃, calcination time 2~8 hours.

15. The application of a hydrodesulfurization and demetallization catalyst according to any one of claims 1 to 4 in the hydrotreating process of inferior heavy oil.

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