A heavy residue hydrodemetallization catalyst and a method for preparing the same

Abstract

The application discloses a heavy residual oil hydrogenation demetallization catalyst and a preparation method thereof, wherein the percentage of the spherical cavity area in the cross section of the alumina carrier is 40-60%; the volume percentage of the flaky alumina in the spherical cavity is 40-80%; the MoO3 content in the spherical cavity is 13.0-15.5%, the NiO content is 2.8-4.5%, and the V2O5 content is 2.0-3.5%; the preparation method is as follows: (1) micron spherical activated carbon is impregnated with a first impregnation solution containing Mo, Ni and V to obtain modified micron spherical activated carbon; (2) the modified micron spherical activated carbon, pseudoboehmite and water are mixed to form a slurry, and the slurry is filtered and dried to obtain a first alumina carrier containing spherical cavity holes; (3) the first alumina carrier is sealed and heat-treated in an epoxy propane aqueous solution to obtain a second alumina carrier; and (4) then Mo and Ni are loaded to obtain the catalyst. The hydrogenation demetallization catalyst has strong metal impurity and carbon deposition resistance, high hydrogenation demetallization activity and activity stability, and is suitable for the field of heavy residual oil hydrogenation demetallization.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst preparation, and particularly relates to a heavy oil hydrodemetallization catalyst and a preparation method thereof. BACKGROUND

[0002] The fixed bed residual oil hydrogenation process technology is mature and widely used, and is an effective means to realize efficient conversion of heavy oil at present. Residual oil is rich in most of the impurities such as sulfur, nitrogen, metals (mainly nickel and vanadium) in crude oil. Residual oil hydrogenation removes metal, sulfur, nitrogen and other impurities under the action of a catalyst at high temperature and high pressure, providing high-quality raw materials for downstream catalytic cracking. However, due to the high viscosity, high impurity content and complex molecular composition of residual oil, the hydrogenation reaction is difficult, and a single catalyst cannot effectively remove metal, sulfur, nitrogen and carbon residue impurities in residual oil. At present, residual oil hydroprocessing catalysts usually include protective catalysts, demetallization catalysts, desulfurization catalysts and denitrification catalysts. The role of the residual oil hydrodemetallization catalyst is to remove Ni, V and other metals in the residual oil, and to protect the desulfurization catalyst. It not only removes metal impurities in the feedstock, but also must accommodate as much metal and coke impurities as possible.

[0003] CN114425374A discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The catalyst includes a catalyst body composed of a carrier and an active component supported on the carrier, and has a carbon film on the outer surface of the catalyst body. The carbon film covers the surface active center, so that during the residual oil hydrogenation process, the carbon deposition, sulfides and iron, calcium and other deposits produced after the intense reaction of the residual oil on the catalyst surface active site are prevented from blocking the catalyst pores and covering the active sites, and the catalyst has good anti-coking performance. However, the hydrogenation demetallization catalyst prepared by this method has small surface pores, which is not conducive to the diffusion of residual oil reactant molecules to the inside of the catalyst.

[0004] CN104646008A discloses a poor-quality heavy oil hydrodesulfurization and demetallization catalyst and a preparation method thereof. The catalyst uses alumina as the carrier, and VIB and VIII elements, especially Ni-Mo, as the active component. The catalyst has a pore volume of 0.61-0.70 mL / g, a specific surface area of 155-200 m 2 / g, and an average pore diameter of 13.0-18.0 nm. The preparation method of the catalyst is to treat the carrier particles after molding and calcination with an acid solution with continuously increasing concentration, so as to improve the pore structure of the carrier and the hydrogenation demetallization catalyst. This method needs to be further improved to increase the content of large pores of the alumina carrier, especially the large pores on the surface.

[0005] CN110935461A discloses a preparation method of a heavy oil hydrodemetallization catalyst. The preparation method of the catalyst comprises: (1) mixing and kneading a physical pore expander, pseudo-boehmite and an active metal component to form a modified alumina carrier SI; (2) unsaturatedly spraying and impregnating the SI with a hydroactive component impregnation solution I, and then drying and calcining to obtain a modified alumina carrier SII; (3) mixing the SII, ammonium bicarbonate and water, and then performing sealed heat treatment, and then drying and calcining the material after heat treatment to obtain a carrier SIII; (4) supersaturatingly impregnating the carrier SIII with a hydroactive component impregnation solution II, and then drying and calcining to obtain the catalyst. The catalyst prepared by the method has a rod-shaped structure on the surface, the formed pore channel is open, the metal deposition resistance and the carbon deposition resistance of the catalyst are improved, but the rod-shaped alumina grown on the surface is easy to fall off, and the bonding degree with the main body alumina needs to be further improved. SUMMARY

[0006] In view of the deficiencies in the prior art, the present application provides a preparation method of a heavy oil hydrodemetallization catalyst. The hydrodemetallization catalyst has an open surface pore channel, which is beneficial to the diffusion of reactant molecules, a good internal pore channel penetration, and a strong metal impurity and carbon deposition resistance. The hydrodemetallization catalyst has high hydrodemetallization activity and stability, and is suitable for the field of heavy oil hydrodemetallization.

[0007] The heavy oil hydrodemetallization catalyst of the present application comprises, based on the total weight of the catalyst, 80%-90% of an alumina carrier containing spherical cavities, 9.5%-13.5% of MoO3, 2.3%-3.3% of NiO, and 0.1%-0.8% of V2O5. The percentage of the spherical cavity area in the cross-section of the alumina carrier is 40%-60%. Flaky alumina grains are grown in situ in the spherical cavities, and the grain size is 100-600 nm. The volume fraction (filling rate) of the flaky alumina in the spherical cavities is 40%-80%. The content of the hydrogenation active metals Mo, Ni and V in the spherical cavities is calculated as MoO3, NiO and V2O5, and the content is 13.0%-15.5%, 2.8%-4.5% and 2.0%-3.5%, respectively. Flaky alumina grains are grown in situ on the outer surface of the alumina carrier, and the area fraction (coverage rate) of the flaky alumina on the outer surface is 85%-100%.

[0008] The preparation method of the heavy oil hydrodemetallization catalyst of the present application comprises the following contents:

[0009] (1) impregnating micron spherical activated carbon with a first impregnation solution containing Mo, Ni and V, and obtaining modified micron spherical activated carbon after drying the impregnated activated carbon;

[0010] (2) mixing the modified microspherical activated carbon, pseudo-boehmite and water to form a slurry, filtering and drying the slurry, mixing and shaping the dried material, drying and calcining the shaped material to obtain a first alumina carrier containing spherical cavity pores;

[0011] (3) sealingly treating the first alumina carrier in an aqueous propylene oxide solution, separating the treated material into solid and liquid phases, drying and calcining the solid phase material to obtain a second alumina carrier;

[0012] (4) impregnating the second alumina carrier with a second impregnation solution containing Mo and Ni, drying and calcining the impregnated material to obtain a heavy oil hydrodemetallization catalyst.

[0013] In the method, the Mo, Ni and V-containing impregnation solution in step (1) contains 2.5-6.0 g / 100 mL of Mo in the form of molybdenum oxide, 1.2-2.4 g / 100 mL of V in the form of vanadium pentoxide and 0.5-1.5 g / 100 mL of Ni in the form of nickel oxide, and the solution is used in an amount sufficient to completely impregnate the microspherical activated carbon, and the impregnation time is 0.5-4 hours.

[0014] In the method, the microspherical activated carbon in step (1) has a diameter of 1-8 microns, and the microspherical activated carbon can be prepared by a conventional method or purchased, the drying temperature is 120-180°C, and the drying time is 4-10 hours.

[0015] In the method, the mass ratio of the active metal-modified activated carbon to the pseudo-boehmite in step (2) is 1:4-1:2, and the liquid-to-solid mass ratio of the slurry is 5:1-10:1.

[0016] In the method, the kneading and shaping in step (2) is performed by a conventional method in the art, and an extrusion aid and a peptizing agent are added as needed during the shaping. The extrusion aid is amaranth powder, and the amount of the amaranth powder added is 0.1wt%-0.5wt% of the weight of the final alumina carrier. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid, and the amount of the peptizing agent added is 0.1wt%-1.5wt% of the weight of the alumina carrier, and the final amount is determined according to the shaping effect. The drying temperature is 100-160°C, and the drying time is 4-10 hours. The calcination temperature is 450-700°C, preferably 450-600°C, and the calcination time is 4-6 hours. The calcination is performed in an oxygen-containing atmosphere.

[0017] In the method, the aqueous propylene oxide solution in step (3) has a mass percentage concentration of 2.5%-12%, preferably 4%-8%, and the mass ratio of the aqueous propylene oxide solution to the first alumina carrier is 3:1-10:1, preferably 4:1-8:1.

[0018] The sealing heat treatment in step (3) is preferably carried out in a sealed autoclave, and is preferably two-step sealing heat treatment, i.e. first low-temperature sealing heat treatment at 60-100 ℃ for 1-4 hours, and then sealing heat treatment at 110-180 ℃, preferably 120-160 ℃, for 14-20 hours.

[0019] In the method of the present application, the drying temperature in step (3) is 100-160 ℃, 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, preferably an air atmosphere.

[0020] In the second impregnation solution containing Mo and Ni in step (4), the Mo content is 8.5%-12.5 g / 100 mL as metal oxide, and the Ni content is 2.2-4.5 g / 100 mL as metal oxide.

[0021] In the method of the present application, the drying temperature in step (4) is 100-160 ℃, and the drying time is 2-8 hours, and the calcination temperature is 450-550 ℃, and the calcination time is 4-6 hours.

[0022] The application of the heavy oil hydrodemetallization catalyst of the present application in a heavy oil hydroprocessing process is generally under the following reaction conditions: reaction temperature 350-440 ℃, hydrogen / oil volume ratio 500-1000, liquid hourly space velocity 0.5-1.5 h -1 , and operating pressure 12.5-15.5 MPa.

[0023] Compared with the prior art, the present application has the following advantages:

[0024] The present application first prepares an alumina carrier containing a large number of spherical cavities, in which a certain amount of Mo, Ni and V metals are directionally loaded, and then grows flaky particles in situ on the alumina cavities and outer surfaces through specific hydrothermal conditions and environment, so that the carrier surface is stacked to form open channels of 40-300 nm in size. This channel structure is beneficial to the diffusion of reactants, especially large-sized heavy oil reactants, into the interior of the catalyst, while the spherical cavities form more through 50-100 nm channels, which are beneficial to the diffusion of reactant molecules. In combination with high metal content of the hydrogenation active metals, the metal capacity, carbon deposition resistance and metal supporting capacity in the spherical cavities are improved, and the catalyst has high activity and activity stability. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 SEM image of the surface of the alumina carrier precursor prepared in Example 1.

[0026] Figure 2SEM image of cross section of alumina support precursor prepared for example 1

[0027] Figure 3 SEM image of cross section of alumina support prepared for example 1. DETAILED DESCRIPTION

[0028] The technical solutions and technical effects of the present application are further illustrated below in combination with examples, but are not limited to the following examples. In the present application, wt% represents mass fraction.

[0029] The microstructure of the alumina support is characterized by a scanning electron microscope, and the specific operation is as follows: the microstructure of the support is characterized by a JSM-7500F scanning electron microscope, the acceleration voltage is 5KV, the acceleration current is 20µA, and the working distance is 8mm.

[0030] The bulk active metal content refers to the content of metal MoO3 and NiO in the whole catalyst, and the determination method is determined according to the method of ICP-AES determination of metal elements in molybdenum-nickel series hydrogenation catalyst, Guangzhou Chemical Industry, 2021, 49, (17): 129-130.

[0031] The micro-area active metal content of the catalyst is determined by a scanning electron microscope equipped with an energy dispersive X-ray spectrometer (EDAX company), and when determining, 20 micro-areas to be determined are randomly selected for composition determination and taking the average value, the acceleration voltage is 30KV, and the working distance is 8mm.

[0032] The active metal content at the micron-scale pore is the active metal content at the pore formed after the micron-scale active carbon ball is calcined, and when determining, the catalyst particles are cut and adhered to the scanning electron microscope sample table, so that the cross section of the catalyst particles is perpendicular to the electron beam direction of the scanning electron microscope, and the composition of the region is determined by a scanning electron microscope equipped with an energy dispersive X-ray spectrometer.

[0033] Preparation of micron spherical activated carbon:

[0034] The micron spherical activated carbon used in the method of the present application is prepared according to the method in the literature: Dalin, Li Wei, Wu Qiong, et al. Preparation of micron spherical activated carbon by carboxymethyl cellulose hydrothermal carbonization-CO2 activation [J]. Forest Products Chemistry and Industry, 2015, 35 (4): 21-27. The prepared micron spherical activated carbon has a diameter of 1-8 microns. Example 1

[0035] (1) 100 grams of the above micron spherical activated carbon is weighed, and molybdenum oxide with a concentration of 3.2g / 100mL, oxygen

[0036] The molybdenum-nickel-vanadium solution with the concentration of 0.7 g / 100 mL of nickel and 2.1 g / 100 mL of vanadium pentoxide is used for impregnation for 2 hours. After impregnation, the material is filtered, and the spherical activated carbon is dried at 165 ℃ for 5 hours to obtain the active metal modified microspherical activated carbon.

[0037] (2) 100 grams of the active metal modified microspherical activated carbon in step (1) and 275 grams of pseudoboehmite are weighed, and 6000 grams of deionized water is added. The mixture is mechanically stirred for 2 hours. After stirring, the solid material is dried at 120 ℃ for 6 hours. Then, 2.0 grams of sesbania powder is added to the dried material and mixed uniformly. A proper amount of 0.5% acetic acid solution is kneaded uniformly, and the material is extruded into a strip. The formed material is dried at 130 ℃ for 8 hours and calcined at 550 ℃ in an oxygen atmosphere for 5 hours to obtain the active metal modified alumina carrier precursor S0. The surface scanning electron microscope image of the alumina carrier precursor is shown in Figure 1 , and the cross-sectional scanning electron microscope image is shown in Figure 2 .

[0038] (3) 100 grams of the active metal modified alumina carrier precursor in step (2) is weighed, and 560 grams of propylene oxide aqueous solution with a mass concentration of 6.5% is added. The mixture is transferred into an autoclave, which is sealed and placed in an oven. First, the sealed treatment is carried out at 85 ℃ for 2.5 hours, and then the sealed treatment is carried out at 150 ℃ for 17 hours. After cooling, the material is washed, filtered, and the solid material is dried at 120 ℃ for 6 hours. The alumina carrier is obtained by calcining at 650 ℃ for 5 hours. The cross-sectional scanning electron microscope image of the carrier is shown in Figure 3 .

[0039] (4) 100 grams of the alumina carrier in step (3) is placed in a spray impregnation pot, and the alumina carrier is saturatedly impregnated by spraying impregnation with an active component impregnating solution with a concentration of 11 g / 100 mL of molybdenum oxide and 3.8 g / 100 mL of nickel oxide. The impregnated material is dried at 120 ℃ for 5 hours and calcined at 500 ℃ for 5 hours to obtain the hydrogen demetallization catalyst Cat-1 of the application. The properties of the catalyst are shown in Table 1. Example 2

[0040] The same as example 1, except that in step (1), the concentration of molybdenum oxide is 4.1 g / 100 mL, the concentration of nickel oxide is 0.9 g / 100 mL, and the concentration of vanadium pentoxide is 1.7 g / 100 mL; in step (2), the amount of pseudoboehmite added is 300 g; in step (3), the concentration of propylene oxide is 5.4%, and the amount of solution used is 620 g; during hydrothermal treatment, first, the solution is treated at 65°C for 3.5 hours, then the temperature is raised to 140°C, and the treatment time is 18.5 hours; in step (4), the concentration of molybdenum oxide in the active component impregnation solution is 10 g / 100 mL, and the concentration of nickel oxide is 2.5 g / 100 mL, thereby obtaining the hydrogen demetallization catalyst Cat-2 of the present application, and the properties of the catalyst are shown in Table 1. Example 3

[0041] The same as example 1, except that in step (1), the concentration of molybdenum oxide is 2.7 g / 100 mL, the concentration of nickel oxide is 0.6 g / 100 mL, and the concentration of vanadium pentoxide is 2.5 g / 100 mL; in step (2), the amount of pseudoboehmite added is 250 g; in step (3), the concentration of propylene oxide is 7.5%, and the amount of solution used is 450 g; during hydrothermal treatment, first, the solution is treated at 95°C for 1.5 hours, then the temperature is raised to 130°C, and the treatment time is 19.5 hours; in step (4), the concentration of molybdenum oxide in the active component impregnation solution is 11.5 g / 100 mL, and the concentration of nickel oxide is 3 g / 100 mL, thereby obtaining the hydrogen demetallization catalyst Cat-3 of the present application, and the properties of the catalyst are shown in Table 1. Example 4

[0042] The same as example 1, except that in step (1), the concentration of molybdenum oxide is 4.6 g / 100 mL, the concentration of nickel oxide is 1.0 g / 100 mL, and the concentration of vanadium pentoxide is 1.4 g / 100 mL; in step (2), the amount of pseudoboehmite added is 350 g; in step (3), the concentration of propylene oxide is 4.3%, and the amount of solution used is 760 g; during hydrothermal treatment, first, the solution is treated at 75°C for 2 hours, then the temperature is raised to 160°C, and the treatment time is 15.5 hours; in step (4), the concentration of molybdenum oxide in the active component impregnation solution is 9.5 g / 100 mL, and the concentration of nickel oxide is 2.3 g / 100 mL, thereby obtaining the hydrogen demetallization catalyst Cat-4 of the present application, and the properties of the catalyst are shown in Table 1.

[0043] Comparative Example 1

[0044] The same as example 1, except that in step (3), the propylene oxide aqueous solution is replaced by an aqueous ammonia solution of the same mass concentration, thereby obtaining the comparative hydrogen demetallization catalyst Cat-5, and the properties of the catalyst are shown in Table 1.

[0045] Comparative Example 2

[0046] The same as Example 1 except that the propylene oxide aqueous solution in step (3) is replaced by an ethylene oxide solution of the same concentration to prepare a comparative hydrogen demetallization catalyst Cat-6, and the catalyst properties are shown in Table 1.

[0047] Comparative Example 3

[0048] The same as Example 1 except that the propylene oxide concentration in step (3) is 0.8% to prepare a comparative hydrogen demetallization catalyst Cat-7, and the catalyst properties are shown in Table 1.

[0049] Comparative Example 4

[0050] The same as Example 1 except that the micron spherical activated carbon in step (1) is not modified with active metals but the same amount of active metal solution is added to the carrier during molding to prepare a comparative hydrogen demetallization catalyst Cat-8, and the catalyst properties are shown in Table 1.

[0051] Table 1 Catalyst properties

[0052]

[0053] As can be seen from the data in Table 1 and the accompanying drawings, the hydrogen demetallization catalyst prepared by the method of the present application has larger surface pores, the pores are wide, and the accumulation of sheet particles in the micron pores forms more 50-100 nm pores. The active metal component in the micron pores of the catalyst is Mo-Ni-V multiple components, and the content of the active metal component in the micro area is high. Example 5

[0054] The hydrogen demetallization catalysts Cat-1 to Cat-4 prepared by the present application and the comparative hydrogen demetallization catalysts Cat-5 to Cat-8 are respectively loaded into a fixed bed hydrogenation reactor, the treated raw materials (see Table 2), and the test conditions are as follows: reaction temperature 380°C, hydrogen / oil volume ratio 650, liquid hourly space velocity 1.0 h -1 , hydrogen partial pressure 15.0 MPa, continuous operation 2000 hours, and the impurity removal properties are shown in Table 3.

[0055] Table 2 Raw material properties

[0056]

[0057] Table 3 Evaluation results of the catalysts

[0058] Catalyst Cat-1 Cat-2 Cat-3 Cat-4 Cat-5 Cat-6 Cat-7 Cat-8 Relative Ni removal, % 139 135 142 131 100 98 107 121 Relative V removal, % 137 134 136 128 100 106 111 125

[0059] As can be seen from the results in Table 3, the hydrogen demetallization catalyst prepared by the method of the present application has a high Ni and V removal rate and good activity stability.

Claims

1. A heavy residue hydrodemetallization catalyst characterized by: The area of the spherical cavity in the cross section of the alumina carrier accounts for 40-60% of the cross section area; the flaky alumina grains with a size of 100-600 nm are in situ grown in the spherical cavity, and the volume of the flaky alumina in the spherical cavity accounts for 40-80%; the flaky alumina grains are in situ grown on the outer surface of the alumina carrier, and the area of the flaky alumina on the outer surface accounts for 85-100%; the content of the alumina carrier containing the spherical cavity accounts for 80-90%, the content of MoO3 accounts for 9.5-13.5%, the content of NiO accounts for 2.3-3.3%, and the content of V2O5 accounts for 0.1-0.8% based on the total weight of the catalyst, and the sum of the contents of the components is 100%; the preparation method of the heavy residual oil hydrodemetallization catalyst comprises the following contents: (1) impregnating the micron spherical activated carbon with a first impregnation solution containing Mo, Ni and V, and obtaining modified micron spherical activated carbon after drying the impregnated activated carbon; (2) mixing the modified micron spherical activated carbon, pseudoboehmite and water to form a slurry, and performing filtration and drying treatment, and obtaining the first alumina carrier containing spherical cavity pores by mixing and kneading the dried material, drying and calcining; (3) sealing and heat-treating the first alumina carrier in a propylene oxide aqueous solution, and performing solid-liquid separation on the treated material, and obtaining the second alumina carrier by drying and calcining the solid-phase material; (4) impregnating the second alumina carrier with a second impregnation solution containing Mo and Ni, and obtaining the heavy residual oil hydrodemetallization catalyst by drying and calcining the impregnated material; 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 first alumina carrier is 3:1-10:1; the sealing heat treatment in step (3) is carried out in a sealed autoclave, and the sealing heat treatment is two-step sealing heat treatment, that is, first sealing heat treatment at a low temperature of 60-100 ℃ for 1-4 hours, and then sealing heat treatment at 110-180 ℃ for 14-20 hours; the impregnation solution containing Mo, Ni and V in step (1) contains 2.5-6.0 g / 100 mL of Mo calculated as molybdenum oxide, 1.2-2.4 g / 100 mL of V calculated as divanadium pentoxide, and 0.5-1.5 g / 100 mL of Ni calculated as nickel oxide; the second impregnation solution containing Mo and Ni in step (4) contains 8.5-12.5 g / 100 mL of Mo calculated as metal oxide, and 2.2-4.5 g / 100 mL of Ni calculated as metal oxide.

2. A process for the preparation of the heavy residue hydrodemetallization catalyst of claim 1, characterized by It comprises the following contents: (1) impregnating microspherical activated carbon with a first impregnating solution containing Mo, Ni and V, and obtaining modified microspherical activated carbon after drying the impregnated activated carbon; (2) mixing the modified microspherical activated carbon, pseudo-boehmite and water to form a slurry, and performing filtration and drying treatment, then mixing and kneading the dried material to form, drying and calcining to obtain a first alumina carrier containing spherical cavity pores; (3) sealing and heat treating the first alumina carrier in an aqueous propylene oxide solution, and performing solid-liquid separation on the treated material, then drying and calcining the solid-phase material to obtain a second alumina carrier; (4) impregnating the second alumina carrier with a second impregnating solution containing Mo and Ni, and drying and calcining the impregnated material to obtain a heavy oil hydrodemetallization catalyst.

3. The method of claim 2, wherein: In step (1), the Mo content in the impregnating solution is 2.5-6.0 g / 100 mL (calculated as molybdenum oxide), the V content is 1.2-2.4 g / 100 mL (calculated as vanadium pentoxide), and the Ni content is 0.5-1.5 g / 100 mL (calculated as nickel oxide), and the solution is used in an amount sufficient to completely impregnate the microspherical activated carbon, and the impregnation time is 0.5-4 hours.

4. The method of claim 2, wherein: In step (1), the microspherical activated carbon has a diameter of 1-8 microns, and is prepared by an existing method or purchased; the drying temperature is 120-180°C, and the drying time is 4-10 hours.

5. The method of claim 2, wherein: In step (2), the mass ratio of the active metal modified activated carbon to pseudo-boehmite is 1:4-1:2, and the liquid-solid mass ratio of the slurry is 5:1-10:

1.

6. The method of claim 2, wherein: In step (3), the mass percentage concentration of the aqueous propylene oxide solution is 2.5%-12%, and the mass ratio of the aqueous propylene oxide solution to the first alumina carrier is 3:1-10:

1.

7. The method of claim 2, wherein: In step (3), the sealing and heat treatment is performed in a sealed autoclave, and is a two-step sealing and heat treatment, i.e., first performing low-temperature sealing and heat treatment at 60-100°C for 1-4 hours, and then performing sealing and heat treatment at 110-180°C for 14-20 hours.

8. The method of claim 2, wherein: In step (3), the drying temperature is 100-160°C, the drying time is 2-8 hours, the calcination temperature is 500-750°C, and the calcination time is 4-6 hours.

9. The method of claim 2, wherein: In step (4), the Mo content in the second impregnating solution is 8.5%-12.5 g / 100 mL (calculated as metal oxide), and the Ni content is 2.2-4.5 g / 100 mL (calculated as metal oxide).

10. The method of claim 2, wherein: In step (4), the drying temperature is 100-160°C, the drying time is 2-8 hours, the calcination temperature is 450-550°C, and the calcination time is 4-6 hours.

11. Use of the heavy residue hydrodemetallization catalyst of claim 1 in a heavy residue hydroprocessing process under the following reaction conditions: a reaction temperature of 350-440°C, a hydrogen to oil volume ratio of 500-1000, a liquid hourly space velocity of 0.5-1.5 h -1 , and an operating pressure of 12.5-15.5 MPa.

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