Preparation method of hydrogenation protective agent

Abstract

The present invention discloses a method for preparing a hydrogenation protective agent, comprising the following steps: (1) immersing an alumina carrier precursor in an aqueous propylene oxide solution for sealed heat treatment, subjecting the treated material to solid-liquid separation, and drying and calcining the solid phase material to obtain an alumina carrier; and (2) sequentially impregnating the alumina carrier of step (1) with a low-concentration hydrogenation active component impregnation solution and a high-concentration hydrogenation active component impregnation solution, drying and calcining the impregnated material to obtain a hydrogenation protective agent. The hydrogenation protective agent has a gradient active metal distribution and open channels formed between flaky alumina grains. It is used in the hydrogenation treatment process of heavy residual oil and has a high ability to remove metal impurities such as Ca and Fe, as well as a high ability to remove metals such as Ni and V.

Description

Technical Field

[0001] The invention belongs to the field of catalytic material preparation, and particularly relates to a method for preparing a hydrogenation protective agent. Background Art

[0002] Deep processing of heavy oil, including residual oil, is not only beneficial to improving the utilization rate of heavy oil and alleviating the tense trend of energy supply, but also reduces environmental pollution and achieves clean energy utilization. Compared with distillate oil, heavy oil such as residual oil has a high content of metal atoms such as nickel (Ni), vanadium (V), iron (Fe) and calcium (Ca), and iron will be concentrated in the heavy oil in the form of iron cyclohexane in some heavy oils with a high cyclohexane acid content. Metal impurities such as Ni, V, Fe, and Ca can easily cause scaling and clogging of the catalyst bed during the hydrogenation process of residual oil, resulting in the device being forced to shut down due to excessive pressure drop. One of the effective ways to solve this problem is to load a protective agent with hydrogenation activity (i.e., a hydrogenation protective agent) on the upper part of the hydrogenation catalyst.

[0003] CN106622307A discloses a hydrogenation protective agent and its preparation method and application. The protective agent contains an active metal component and a modified hydrogenation catalyst support. The modified hydrogenation catalyst support is a hydrothermally treated support that is repeatedly impregnated and dried in sequence, and the dried product obtained in the last step is calcined. The impregnation liquid used in each impregnation process contains the same or different acidic auxiliary compound, the number of repetitions n≥2, and when n≥3, in the process from the second impregnation to the n-1th impregnation, the drying temperature after each impregnation is 20-150°C higher than the drying temperature after the adjacent previous impregnation, and the drying time after each impregnation is 1-10 hours longer than the drying time after the adjacent previous impregnation. This method can obtain a modified hydrogenation catalyst support with a layered distribution of the acidic auxiliary, but the pores on the support surface are not open, which is not conducive to the diffusion of residual oil macromolecular reactants.

[0004] CN111821990A discloses a residual oil hydrogenation protective agent carrier, catalyst, and preparation method thereof. The carrier is a modified alumina-based carrier containing a modifying element and a first hydrogenation-active metal component. The modified alumina-based carrier comprises a main modified alumina and rod-shaped modified alumina. The main modified alumina is alumina having micron-sized pores, wherein at least a portion of the rod-shaped modified alumina is distributed on the outer surface of the main modified alumina and within the micron-sized pores with a pore diameter D of 5-10 μm. The modifying element is vanadium, and the first hydrogenation-active metal component is molybdenum. The alumina carrier prepared by this method has good pore penetration, but the bond between the surface-grown rod-shaped alumina and the main alumina needs to be further improved. Summary of the Invention

[0005] In response to the deficiencies in the prior art, the present invention provides a method for preparing a hydrogenation protective agent. The hydrogenation protective agent has a gradient distribution of active metals and open channels formed between flaky alumina grains. The hydrogenation protective agent is used in the hydrogenation process of heavy residual oil and has a high ability to remove metal impurities such as Ca and Fe while also having a high ability to remove metals such as Ni and V.

[0006] The preparation method of the hydrogenation protective agent of the present invention comprises the following contents:

[0007] (1) Immersing the alumina carrier precursor in a propylene oxide aqueous solution for sealed heat treatment, separating the treated material into solid and liquid, and drying and calcining the solid phase material to obtain the alumina carrier;

[0008] (2) The alumina support of step (1) is impregnated sequentially with a low-concentration hydrogenation active component impregnation solution and a high-concentration hydrogenation active component impregnation solution. The impregnated material is dried and calcined to obtain a hydrogenation protective agent.

[0009] In the method of the present invention, the alumina carrier precursor in step (1) is γ-phase alumina, which can be purchased or homemade. The shape of the alumina carrier precursor can be the shape of a conventional alumina carrier, such as a sphere, and its particle size is generally 2-8.0 mm, such as a cylindrical bar, a clover, a four-leaf clover, etc., with a diameter of about 0.2-3.0 mm and a length of about 3-8.0 mm. The γ-phase alumina carrier preferably has a specific surface area of ​​120-260 m 2 / g, pore volume 0.5-1.0mL / g, the pore volume of pores with a diameter less than 10nm accounts for less than 30% of the total pore volume, and the pore volume of pores with a diameter of 10-30nm accounts for 40%-60% of the total pore volume.

[0010] In the method of the present invention, the γ-phase alumina carrier precursor described in step (1) is usually prepared by the following method: kneading, forming, drying and calcining pseudo-boehmite. The kneading and forming is carried out by conventional methods in the art. During the forming process, an extrusion aid, a physical pore expander and a peptizer can be added as needed. The extrusion aid is sesbania powder, and the addition amount is 0.1wt%-0.5wt% of the weight of the alumina carrier. The physical pore expander is a substance such as starch, activated carbon, and crop straw particles, and the addition amount is 1wt%-5wt% of the weight of the alumina carrier. The peptizer is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, etc., and the addition amount of the peptizer is 0.5wt%-1.5wt% of the weight of the alumina carrier. The drying temperature is 100-160°C, and the drying time is 6-10 hours; the calcination temperature is 450-600°C, and the calcination time is 4-6 hours; the calcination is carried out in an oxygen-containing atmosphere, preferably in air.

[0011] In the method of the present invention, the mass percentage concentration of the propylene oxide aqueous solution in step (1) is 2.5%-12%, preferably 4%-8%, and the mass ratio of the propylene oxide aqueous solution to the alumina carrier precursor is 3:1-10:1, preferably 4:1-8:1.

[0012] In the method of the present invention, the sealed heat treatment in step (1) is carried out in a sealed container, which is preferably an autoclave. The sealed heat treatment is a two-step sealed heat treatment, i.e., first, a sealed heat treatment at 60-100°C for 1-4 hours, and then a treatment at 110-180°C, preferably 120-160°C, for 14-20 hours, preferably 16-20 hours.

[0013] In the method of the present invention, the drying temperature in step (1) is 100-160°C, the drying time is 2-8 hours, the roasting temperature is 750-950°C, the roasting time is 4-6 hours, and the roasting is carried out in an oxygen-containing atmosphere, preferably in an air atmosphere.

[0014] In the method of the present invention, the alumina carrier obtained in step (1) comprises a main alumina and flaky alumina grains grown in situ on the outer surface of the main alumina. The flaky alumina grains have a parallelepiped structure and a grain size of 100-400 nm. The flaky alumina grains accumulate on the outer surface of the main alumina to form pores of 40-300 nm. The coverage of the flaky alumina grains on the outer surface of the main alumina is 85%-100%, where the coverage refers to the percentage of the surface area occupied by the flaky alumina grains on the outer surface of the main alumina.

[0015] In the method of the present invention, the low-concentration hydrogenation active component impregnation solution and the high-concentration hydrogenation active component impregnation solution described in step (2) can use the active metal components used in conventional residue oil hydrotreating catalysts, generally Group VIB metals and / or Group VIII metals, with Group VIB metals preferably being Mo and / or W, and Group VIII metals preferably being Co and / or Ni. The content of Group VIB metals in the low-concentration hydrogenation active component impregnation solution, calculated as metal oxide, is 6.5%-15.0 g / 100 mL, and the content of Group VIII metals, calculated as metal oxide, is 1.5%-6.0 g / 100 mL. The amount of the low-concentration hydrogenation active component impregnation solution used is 70%-90% of the saturated water absorption capacity of the alumina support. The high-concentration hydrogenation active component impregnation solution contains 4.5%-8.5g of Group VIB metals (calculated as metal oxides) per 100mL, and 1.2-3.5g of Group VIII metals (calculated as metal oxides) per 100mL. The dosage of the high-concentration hydrogenation active component impregnation solution is 25%-35% of the saturated water absorption capacity of the alumina support. The low-concentration hydrogenation active component impregnation solution and the high-concentration hydrogenation active component impregnation solution may contain the same or different hydrogenation active components. The sum of the dosages of the low-concentration hydrogenation active component impregnation solution and the high-concentration hydrogenation active component impregnation solution is equal to the saturated water absorption capacity of the alumina support.

[0016] In the method of the present invention, the drying temperature in step (2) is 100-160°C, the drying time is 2-8 hours, the roasting temperature is 450-550°C, and the roasting time is 4-6 hours.

[0017] The hydrogenation protective agent prepared by the method of the present invention is suitable for the hydrogenation treatment process of heavy residual oil.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] (1) The pores on the surface of the alumina carrier used in the hydrogenation protective agent of the present invention are formed by stacking flaky alumina particles. On the one hand, the flaky particles are easy to contact with the residual oil reaction raw materials, thereby improving the reaction activity of the catalyst. On the other hand, the pore structure formed by the interwoven stacking of the flaky particles is open, which is conducive to the diffusion of large molecular reactants into the carrier. At the same time, the flaky alumina particles have a uniform structure and strong bonding with the carrier surface, forming a strong pore. In addition, the preparation process of the alumina carrier used is simple and easy to industrialize.

[0020] (2) The present invention sequentially impregnates the carrier with active component impregnation solutions of varying concentrations, resulting in a catalyst with a relatively high active metal content in the center and a relatively low active metal content in the surface layer. During the hydrogenation reaction, the flaky particles on the surface and the channels formed by the accumulation of flaky particles can effectively remove metallic impurities such as Ca and Fe from the residual oil feedstock, while the channels within the catalyst are conducive to the removal of metallic impurities such as Ni and V from the residual oil feedstock. The catalyst has a high ability to remove metallic impurities such as Ca and Fe, while also having a high ability to remove metallic Ni and V. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG1 is a low-magnification SEM image of the alumina support prepared in Example 3.

[0022] Figure 2 This is a high-magnification SEM image of the alumina support prepared in Example 3.

[0023] FIG3 is a low-magnification SEM image of the alumina support prepared in Comparative Example 2.

[0024] FIG4 is a high-magnification SEM image of the alumina support prepared in Comparative Example 2. DETAILED DESCRIPTION

[0025] The technical solutions and effects of the present invention are further described below with reference to the following examples, but are not limited to the following examples. In the present invention, wt% represents mass fraction.

[0026] BET method: N2 physical adsorption-desorption was used to characterize the pore structure of the carriers used in the examples and comparative examples. The specific procedure was as follows: The sample pore structure was characterized using an ASAP-2420 N2 physical adsorption-desorption instrument. A small amount of sample was vacuum-treated at 300°C for 3-4 hours. Finally, the product was subjected to nitrogen adsorption-desorption testing at low temperatures (-200°C) in liquid nitrogen. The specific surface area was calculated using the BET equation, while the pore volume and the distribution ratio of pore diameters below 30 nm were calculated using the BJH model.

[0027] Scanning electron microscopy was used to characterize the microstructure of the alumina support. The specific operation was as follows: a JSM-7500F scanning electron microscope was used to characterize the microstructure of the support with an accelerating voltage of 5 KV, an accelerating current of 20 µA, and a working distance of 8 mm.

[0028] Most probable pore size determination: The pore size differential distribution curve is obtained with the material pore size as the horizontal coordinate and the rate of change of pore volume with pore size as the vertical coordinate. The peak value in the curve is the most probable pore size.

[0029] Alumina support precursor preparation:

[0030] Weigh 500 g of pseudo-boehmite (prepared by alcohol aluminum method), add 3 g of sesbania powder and 5 g of carbon black powder, mix well, then add an appropriate amount of 0.5% acetic acid solution to the mixture and knead evenly, extrusion molding, drying the molding material at 120 ° C for 8 hours, and calcining at 550 ° C for 5 hours to obtain an alumina carrier precursor S0, the alumina carrier precursor has a specific surface area of ​​145 m 2 / g, the pore volume is 0.87mL / g, the pore volume of pores with diameters less than 10nm accounts for 28% of the total pore volume, and the pore volume of pores with diameters of 15-30nm accounts for 51% of the total pore volume.

[0031] Example 1

[0032] (1) Weigh 100 g of the alumina carrier precursor S0, add 520 g of propylene oxide solution with a mass concentration of 6.5%, and transfer the mixed material into an autoclave. After sealing, the autoclave is placed in an oven at 75°C for 3 hours, then heated to 145°C for 18 hours. After treatment, the material is cooled, washed, and filtered. The solid material is dried at 120°C for 8 hours and calcined at 850°C for 5 hours to obtain the alumina carrier S1. The scanning electron microscope image of the carrier outer surface is shown in FIG. Figure 1 、 Figure 2 .

[0033] (2) Weigh 50 g of the alumina support S1 and place it in a spray drum. Spray and impregnate the alumina support with 25 mL of active component impregnation solution I with a molybdenum oxide concentration of 9.1 g / 100 mL and a nickel oxide concentration of 2.4 g / 100 mL. Then continue to spray and impregnate the alumina support with active component impregnation solution II with a molybdenum oxide concentration of 6.0 g / 100 mL and a nickel oxide concentration of 1.4 g / 100 mL until the support is saturated with adsorption. The impregnated material is dried at 120 ° C for 5 hours and calcined at 450 ° C for 5 hours to obtain hydrogenation protective agent Cat-1. The catalyst properties are shown in Table 1.

[0034] Example 2

[0035] The same method as Example 1 was used, except that in step (1), the concentration of propylene oxide was 5.3%, the amount of solution used was 640 g, the hydrothermal treatment was first performed at 85°C for 2 hours, then at 135°C for 19 hours, and the carrier calcination temperature was 900°C. In step (2), the molybdenum oxide concentration in the active component impregnation solution I was 10.1 g / 100 mL, the nickel oxide concentration was 2.6 g / 100 mL, the amount of solution used was 24 mL, and the molybdenum oxide concentration in the active component impregnation solution II was 5.5 g / 100 mL, the nickel oxide concentration was 1.3 g / 100 mL. Hydrogenation protective agent Cat-2 was obtained. The catalyst properties are shown in Table 1.

[0036] Example 3

[0037] The same method as Example 1 was used, except that in step (1), the concentration of propylene oxide was 4.2%, the amount of solution used was 750 g, the hydrothermal treatment was first performed at 65°C for 4 hours, then at 120°C for 20 hours, and the carrier calcination temperature was 950°C. In step (2), the molybdenum oxide concentration in the active component impregnation solution I was 9.6 g / 100 mL, the nickel oxide concentration was 2.5 g / 100 mL, the amount of solution used was 22.5 mL, and the molybdenum oxide concentration in the active component impregnation solution II was 5.0 g / 100 mL, the nickel oxide concentration was 1.2 g / 100 mL. Hydrogenation protective agent Cat-3 was obtained. The catalyst properties are shown in Table 1.

[0038] Example 4

[0039] The same method as Example 1 was used, except that in step (1), the concentration of propylene oxide was 7.5%, the amount of solution used was 430 g, and the hydrothermal treatment was first performed at 95°C for 1.5 hours and then at 155°C for 16.5 hours. In step (2), the molybdenum oxide concentration in the active component impregnation solution I was 8.5 g / 100 mL, the nickel oxide concentration was 2.3 g / 100 mL, the amount of solution used was 27 mL, and the molybdenum oxide concentration in the active component impregnation solution II was 6.5 g / 100 mL, the nickel oxide concentration was 1.5 g / 100 mL. Hydrogenation protective agent Cat-4 was obtained. The catalyst properties are shown in Table 1.

[0040] Comparative Example 1

[0041] The same method as Example 1 was used, except that in step (1), the propylene oxide solution was replaced with an aqueous ammonia solution of the same mass concentration to prepare a comparative hydrogenation protective agent Cat-5. The catalyst properties are shown in Table 1.

[0042] Comparative Example 2

[0043] The same as Example 1, except that the propylene oxide solution in step (1) was replaced with an ethylene oxide solution of the same concentration, the scanning electron microscope image of the outer surface of the obtained alumina carrier is shown in FIG. Figure 3 、 Figure 4 , a comparative hydrogenation protective agent Cat-6 was prepared, and the catalyst properties are shown in Table 1.

[0044] Comparative Example 3

[0045] The same method as Example 1 was used, except that the concentration of propylene oxide in step (1) was 1%. A comparative hydrogenation protective agent Cat-7 was prepared. The catalyst properties are shown in Table 1.

[0046] Comparative Example 4

[0047] The same as Example 1, except that the hydrothermal treatment in step (1) is a one-step hydrothermal treatment, the heat treatment temperature is 90°C, and the treatment time is 22 hours, to obtain a comparative hydrogenation protective agent Cat-8. The catalyst properties are shown in Table 1.

[0048] Table 1 Properties of hydrogenation protective agent

[0049]

[0050] Example 5

[0051] The hydrogenation protection catalysts Cat-1, Cat-2, Cat-3, and Cat-4 prepared in the present invention and the hydrogenation protection catalysts Cat-5, Cat-6, Cat-7, and Cat-8 prepared in the comparative example were respectively loaded into a fixed-bed hydrogenation reactor. The processed raw materials (see Table 2) were tested under the following conditions: reaction temperature 385°C, hydrogen-to-oil volume ratio 785, liquid hourly volume space velocity 1.0h -1 , hydrogen partial pressure 15.5MPa, continuous operation 2000 hours, impurity removal properties are shown in Table 3.

[0052] Table 2 Properties of crude oil

[0053]

[0054] Table 3 Catalyst evaluation results

[0055]

[0056] From the results in Table 3, it can be seen that compared with the comparative hydrogenation protective agent, the hydrogenation protective catalyst prepared by the method of the present invention has higher removal rates of Ca, Fe, Ni, and V while having good stability.

Claims

1. A method for preparing a hydrogenation protective agent, characterized in that The following contents are included: (1) The preparation method of the alumina carrier precursor S0 is as follows: 500 g of pseudo-boehmite is weighed, 3 g of sesbania powder and 5 g of carbon black powder are added, and the mixture is evenly mixed. Then, an appropriate amount of acetic acid solution with a mass concentration of 0.5% is added to the mixture and kneaded evenly. The extruded material is formed, and the formed material is dried at 120°C for 8 hours and calcined at 550°C for 5 hours to obtain the alumina carrier precursor S0. The specific surface area of ​​the alumina carrier precursor is 145 m 2 / g, the pore volume is 0.87mL / g, the pore volume of pores with a pore diameter of less than 10nm accounts for 28% of the total pore volume, and the pore volume of pores with a pore diameter of 15-30nm accounts for 51% of the total pore volume; (2) Weigh 100g of the alumina carrier precursor S0, add 520g of propylene oxide solution with a mass concentration of 6.5%, transfer the mixed material into an autoclave, seal the autoclave and place it in an oven at 75℃ for 3 hours, then heat it to 145℃ for 18 hours, cool, wash and filter the treated material, dry the solid material at 120℃ for 8 hours, and calcine at 850℃ for 5 hours to prepare Obtain alumina carrier S1; (3) Weigh 50 g of alumina carrier S1, place the carrier in a spray drum, spray and impregnate the alumina carrier with 25 mL of active component impregnation solution I with a molybdenum oxide concentration of 9.1 g / 100 mL and a nickel oxide concentration of 2.4 g / 100 mL, then continue to spray and impregnate the alumina carrier with active component impregnation solution II with a molybdenum oxide concentration of 6.0 g / 100 mL and a nickel oxide concentration of 1.4 g / 100 mL, so that the carrier is saturated with adsorption, dry the impregnated material at 120°C for 5 hours, and calcine at 450°C for 5 hours to obtain hydrogenation protective agent Cat-1.

2. A method for preparing a hydrogenation protective agent, characterized in that The following contents are included: (1) The preparation method of the alumina carrier precursor S0 is as follows: 500 g of pseudo-boehmite is weighed, 3 g of sesbania powder and 5 g of carbon black powder are added, and the mixture is evenly mixed. Then, an appropriate amount of acetic acid solution with a mass concentration of 0.5% is added to the mixture and kneaded evenly. The extruded material is formed, and the formed material is dried at 120°C for 8 hours and calcined at 550°C for 5 hours to obtain the alumina carrier precursor S0. The specific surface area of ​​the alumina carrier precursor is 145 m 2 / g, the pore volume is 0.87mL / g, the pore volume of pores with a pore diameter less than 10nm accounts for 28% of the total pore volume, and the pore volume of pores with a pore diameter of 15-30nm accounts for 51% of the total pore volume; (2) Weigh 100g of the alumina carrier precursor S0, add 640g of propylene oxide solution with a mass concentration of 5.3%, transfer the mixed material into an autoclave, seal the autoclave and place it in an oven at 85℃ for 2 hours, then heat it to 135℃ and seal it for 19 hours. After treatment, the material is cooled, washed and filtered, the solid material is dried at 120℃ for 8 hours, and calcined at 900℃ for 5 hours. Prepare an alumina carrier; (3) weigh 50 g of the alumina carrier, place the carrier in a spray immersion drum, spray and impregnate the alumina carrier with 24 mL of active component impregnation solution I with a molybdenum oxide concentration of 10.1 g / 100 mL and a nickel oxide concentration of 2.6 g / 100 mL, and then continue to spray and impregnate the alumina carrier with active component impregnation solution II with a molybdenum oxide concentration of 5.5 g / 100 mL and a nickel oxide concentration of 1.3 g / 100 mL to saturate the carrier with adsorption. The impregnated material is dried at 120°C for 5 hours and calcined at 450°C for 5 hours to obtain a hydrogenation protective agent Cat-2.

3. A method for preparing a hydrogenation protective agent, characterized in that The following contents are included: (1) The preparation method of the alumina carrier precursor S0 is as follows: 500 g of pseudo-boehmite is weighed, 3 g of sesbania powder and 5 g of carbon black powder are added, and the mixture is evenly mixed. Then, an appropriate amount of acetic acid solution with a mass concentration of 0.5% is added to the mixture and kneaded evenly. The extruded material is formed, and the formed material is dried at 120°C for 8 hours and calcined at 550°C for 5 hours to obtain the alumina carrier precursor S0. The specific surface area of ​​the alumina carrier precursor is 145 m 2 / g, the pore volume is 0.87mL / g, the pore volume of pores with a pore diameter of less than 10nm accounts for 28% of the total pore volume, and the pore volume of pores with a pore diameter of 15-30nm accounts for 51% of the total pore volume; (2) Weigh 100g of the alumina carrier precursor S0, add 750g of propylene oxide solution with a mass concentration of 4.2%, transfer the mixed material into an autoclave, seal the autoclave and place it in an oven at 65℃ for 4 hours, then heat it to 120℃ and seal it for 20 hours. After treatment, the material is cooled, washed and filtered, the solid material is dried at 120℃ for 8 hours, and calcined at 950℃ for 5 hours. Prepare an alumina carrier; (3) weigh 50 g of the alumina carrier, place the carrier in a spray immersion drum, spray and impregnate the alumina carrier with 22.5 mL of active component impregnation solution I with a molybdenum oxide concentration of 9.6 g / 100 mL and a nickel oxide concentration of 2.5 g / 100 mL, and then continue to spray and impregnate the alumina carrier with active component impregnation solution II with a molybdenum oxide concentration of 5.0 g / 100 mL and a nickel oxide concentration of 1.2 g / 100 mL to saturate the carrier with adsorption. The impregnated material is dried at 120°C for 5 hours and calcined at 450°C for 5 hours to obtain a hydrogenation protective agent Cat-3.

4. A method for preparing a hydrogenation protective agent, characterized in that The following contents are included: (1) The preparation method of the alumina carrier precursor S0 is as follows: 500 g of pseudo-boehmite is weighed, 3 g of sesbania powder and 5 g of carbon black powder are added, and the mixture is evenly mixed. Then, an appropriate amount of acetic acid solution with a mass concentration of 0.5% is added to the mixture and kneaded evenly. The extruded material is formed, and the formed material is dried at 120°C for 8 hours and calcined at 550°C for 5 hours to obtain the alumina carrier precursor S0. The specific surface area of ​​the alumina carrier precursor is 145 m 2 / g, the pore volume is 0.87mL / g, the pore volume of pores with a pore diameter of less than 10nm accounts for 28% of the total pore volume, and the pore volume of pores with a pore diameter of 15-30nm accounts for 51% of the total pore volume; (2) Weigh 100g of the alumina carrier precursor S0, add 430g of propylene oxide solution with a mass concentration of 7.5%, transfer the mixed material into an autoclave, seal the autoclave and place it in an oven at 95℃ for 1.5 hours, then heat it to 155℃ for 16.5 hours, cool, wash and filter the treated material, dry the solid material at 120℃ for 8 hours, and calcine it at 850℃ for 5 hours. hours to obtain an alumina carrier; (3) weighing 50 g of the alumina carrier, placing the carrier in a spray immersion drum, spraying and impregnating the alumina carrier with 27 mL of active component impregnation solution I with a molybdenum oxide concentration of 8.5 g / 100 mL and a nickel oxide concentration of 2.3 g / 100 mL, and then continuing to spray and impregnate the alumina carrier with active component impregnation solution II with a molybdenum oxide concentration of 6.5 g / 100 mL and a nickel oxide concentration of 1.5 g / 100 mL to saturate the carrier with adsorption, drying the impregnated material at 120 ° C for 5 hours, and calcining at 450 ° C for 5 hours to obtain a hydrogenation protective agent Cat-4.

5. Use of the hydrogenation protective agent prepared according to any one of claims 1 to 4 in the hydrotreating process of heavy residue oil.

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