Hydrodesulfurization catalyst, method for preparing the same, and use thereof

Abstract

The application discloses a hydrodesulfurization catalyst and a preparation method and application thereof. The hydrodesulfurization catalyst comprises a carrier and a second active metal component; the carrier comprises a first active metal nitride, a first active metal carbide, boron oxide and aluminum oxide; wherein the molar ratio of the first active metal nitride to the first active metal carbide, in terms of the first active metal, is 1:0.15-0.25. The hydrodesulfurization catalyst has the characteristics of good macromolecular diffusion performance, strong desulfurization capacity and good carbon deposition resistance. The hydrodesulfurization catalyst is particularly suitable for a residual oil hydrodesulfurization treatment process and has good desulfurization activity and stability.

Description

Technical Field

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

[0002] In recent years, the trend of crude oil resources becoming heavier and of lower quality has become evident, posing a severe challenge to processing low-quality crude oil. Most of the sulfur in crude oil exists in the form of sulfides (30wt%–40wt%) and thiophenes (60wt%–70wt%) in residual oil, mainly distributed in aromatics, gums, and asphaltenes. Hydrodesulfurization technology can react organic sulfur compounds in oil with hydrogen to convert them into easily removed hydrogen sulfide, thus achieving deep desulfurization. With increasingly stringent environmental regulations and higher market demands for product quality in recent years, residual oil hydrodesulfurization technology needs further improvement.

[0003] CN1458236A discloses a method for preparing a catalyst for the hydrodemetallization and desulfurization of heavy oil. This method uses two different forms of aluminum-containing materials: calcined alumina and aluminum hydroxide dry powder. Alkali metals and / or alkaline earth metals are used as additives. Part of the additive is premixed with the aluminum hydroxide dry powder, and the other part is loaded onto the catalyst via impregnation, resulting in a non-uniform distribution of the additive on the catalyst. The catalyst obtained by this method has an average pore size of 15–19 nm, which is still too small for asphaltene micelles, hindering the hydrodesulfurization and hydrodemetallization reactions of residual oil. Its activity and stability need further improvement.

[0004] In summary, existing methods for preparing hydrodesulfurization catalysts for residue oil have various defects, such as poor macromolecular diffusion performance, weak desulfurization capacity, and poor resistance to carbon deposition, which need to be further improved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a hydrodesulfurization catalyst, its preparation method, and its application. The hydrodesulfurization catalyst possesses characteristics such as good macromolecular diffusion performance, strong desulfurization capacity, and good resistance to carbon deposition. This hydrodesulfurization catalyst is particularly suitable for hydrodesulfurization processes in residual oil, exhibiting excellent desulfurization activity and stability.

[0006] The first aspect of this invention provides a hydrodesulfurization catalyst. The catalyst includes a support and a second active metal component; the support includes a first active metal nitride, a first active metal carbide, boron oxide, and aluminum oxide; wherein the molar ratio of the first active metal nitride (based on the first active metal) to the first active metal carbide (based on the first active metal) is 1:0.15-0.25.

[0007] According to the present invention, the first active metal is a Group VIII metal selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni.

[0008] According to the present invention, the second active metal comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten.

[0009] According to the present invention, the second active metal exists in the catalyst in the form of an oxide.

[0010] According to the present invention, the carrier further includes carbon, and the carbon content in the carrier is 8.0% to 10.0% by mass.

[0011] According to the present invention, based on the mass of the carrier, the mass content of alumina is 84.0% to 90.0%, the content of the first active metal as metal oxide is 1.0% to 3.0%, and the content of boron oxide is 1.0% to 3.0%.

[0012] According to the present invention, based on the mass of the catalyst, the mass content of the support is 72% to 87%, the content of Group VIII metal in the second active metal as oxide is 3% to 8%, and the content of Group VIB metal in the second active metal as oxide is 10% to 20%.

[0013] According to the present invention, the catalyst further contains phosphorus, and the phosphorus content is 2.0% to 6.0% based on the mass of the catalyst and calculated as phosphorus pentoxide.

[0014] According to the present invention, the catalyst has the following properties: a specific surface area of ​​160–220 m². 2 / g, pore volume is 0.7~1.3mL / g, average pore size is 10~30nm, and mechanical strength is 130~180N / cm.

[0015] According to the present invention, the pore distribution of the catalyst is as follows: the pore volume of pores with a diameter <10 nm accounts for 5% to 10% of the total pore volume, the pore volume of pores with a diameter of 10 to 20 nm accounts for 70% to 80% of the total pore volume, and the pore volume of pores with a diameter >20 nm accounts for 10% to 25% of the total pore volume.

[0016] A second aspect of the present invention provides a method for preparing the above-mentioned hydrodesulfurization catalyst, comprising:

[0017] (1) Impregnate activated carbon with an impregnation solution containing boric acid and a first active metal source, and dry to obtain material I;

[0018] (2) Mix and knead the pseudoboehmite, material I and adhesive into a mold, and dry to obtain the carrier intermediate;

[0019] (3) The carrier intermediate described in step (2) is heated in an ammonia-containing atmosphere to obtain the carrier;

[0020] (4) The impregnation solution containing the second active metal source is impregnated into the carrier described in step (3), and the catalyst is obtained by curing, drying and calcining.

[0021] According to the present invention, in step (1), the first active metal source is a Group VIII metal salt solution, selected from one or more of Fe, Co, and Ni, preferably at least one of Co and Ni, and more preferably Ni; the Group VIII metal salt solution is derived from at least one of soluble salts, such as nitrates, citrates, monohydrogen phosphates, dihydrogen phosphates, etc. Preferably, the preparation of the impregnation solution can be carried out under heating conditions, such as heating at 40–90°C for 0.5–2 hours.

[0022] According to the present invention, in the impregnation solution of step (1), the mass ratio of boric acid and the first active metal source, calculated as the first active metal oxide, is 2 to 5:1.

[0023] According to the present invention, the specific surface area of ​​the activated carbon in step (1) is 2000-3000 m². 2 / g, with a particle size of 2-15μm; the amount of impregnation solution used in step (1) is 80%-95% of the saturated water absorption capacity of activated carbon, by volume; the impregnation in step (1) is preferably carried out by spray impregnation.

[0024] According to the present invention, in step (1), boric acid is introduced into the activated carbon at a concentration of 10 wt% to 20 wt% of the activated carbon as an oxide.

[0025] According to the present invention, in step (1), the drying conditions are: drying at 100-140°C for 2-4 hours.

[0026] According to the present invention, in step (2), the molding can be carried out by conventional molding methods, such as extrusion molding, and the molded shape is a conventional shape, such as a cylinder, clover, four-leaf clover, etc. In step (2), the mass ratio of boehmite (calculated as alumina) to material I (calculated as activated carbon) is 2:1 to 10:1. The adhesive can be at least one of nitric acid, acetic acid, and citric acid. In step (2), an extrusion aid can also be added according to the molding requirements. The extrusion aid can be guar gum powder. The amount of adhesive and extrusion aid added is added according to the actual molding requirements. The present invention does not have any special requirements. For example, the amount of adhesive added is 0.5wt% to 5wt% of the mass of boehmite and material I used in step (2). The amount of extrusion aid added is 0.5wt% to 6wt% of the mass of boehmite and material I used in step (2). In step (2), water may be added as needed for molding. The amount of water added is 80wt% to 100wt% of the mass of the boehmite and material I used in step (2).

[0027] According to the present invention, in step (2), the drying conditions are: drying at 100-160°C for 2-8 hours.

[0028] According to the present invention, the heat treatment in step (3) under an ammonia-containing atmosphere is carried out in a closed environment. The pressure of the closed environment is not particularly limited and can be autogenous pressure. The volume fraction of ammonia in the ammonia-containing atmosphere is 5wt% to 15wt%, and the remainder can be at least one of inert gas, nitrogen, water vapor or carbon dioxide.

[0029] According to the present invention, the conditions for the heat treatment in step (3) are as follows: the temperature is 400 to 800°C and the treatment time is 3 to 8 hours.

[0030] According to the present invention, the active metal in step (4) comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten. In the impregnation solution in step (4), the active metal, calculated as metal oxide, has a Group VIB metal content of 150–450 g / L, preferably 300–400 g / L, and a Group VIII metal content of 10–120 g / L, preferably 40–60 g / L. The molybdenum source is one or more of molybdenum trioxide, molybdate, and paramolybdate, preferably molybdenum trioxide; the tungsten source is tungstate or tungsten oxide, preferably ammonium metatungstate; the nickel source is one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, preferably basic nickel carbonate; the cobalt source is one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, preferably basic cobalt carbonate.

[0031] According to the present invention, the impregnation solution in step (4) contains a phosphorus-containing compound, preferably phosphoric acid. The concentration of phosphorus in the impregnation solution is 20–80 g / L, preferably 40–60 g / L, calculated as phosphorus.

[0032] According to the present invention, the impregnation in step (4) can be carried out by spray impregnation, and the impregnation can be carried out by saturated impregnation or supersaturated impregnation.

[0033] According to the present invention, the conditioning in step (4) involves placing the impregnated sample under sealed conditions at 10–30°C for 6–12 hours. The conditioning pressure is not particularly limited and can be autogenous pressure. And / or, the drying conditions are drying at 100–160°C for 1–8 hours, and the calcination conditions are constant temperature at 450–650°C for 3–7 hours, preferably constant temperature at 480–600°C for 4–7 hours. The calcination atmosphere is an oxygen-containing gas, such as air.

[0034] According to the present invention, the catalyst described in step (4) has the following properties: a specific surface area of ​​160–220 m². 2 / g, pore volume is 0.7~1.3mL / g, average pore size is 10~30nm, and mechanical strength is 130~180N / cm.

[0035] The third aspect of this invention provides the application of the above-mentioned hydrodesulfurization catalyst in the hydrotreating of residual oil.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] 1. The hydrodesulfurization catalyst of this invention comprises a support and a second active metal component; the support comprises a first active metal nitride, a first active metal carbide, boron oxide, and alumina; wherein the molar ratio of the first active metal nitride (based on the first active metal) to the first active metal carbide (based on the first active metal) is 1:0.15-0.25. The support of this invention is a nitrogen-boron doped material containing active metal and has a suitable pore structure. The catalyst of this invention is suitable for the hydroconversion of sulfides in asphaltene during the hydrotreating of residual oil, exhibiting high hydrodesulfurization activity and good stability.

[0038] 2. In the preparation process of the hydrodesulfurization catalyst of the present invention, the nitriding of the active metal not only improves the electronic structure of the active metal, but also provides more active sites and better mass transport capabilities for the Ni3N-containing catalyst; at the same time, the Ni-B component can serve as an effective electron conduction bridge, promoting the rapid transfer of electrons between metals and effectively weakening the adsorption and bonding between the active metal and the support.

[0039] In addition, during the preparation of the hydrodesulfurization catalyst of the present invention, by doping N and B elements on the catalyst support, Ni-Al, Ni-P and Ni-B can interact synergistically. On the one hand, this can reduce the interaction between the active metal and alumina and improve the metal dispersion. On the other hand, it can effectively suppress deactivation factors such as metal agglomeration, carbon deposition and phase transformation.

[0040] 3. The hydrodesulfurization catalyst of the present invention has good desulfurization activity and stability when used in the hydrodesulfurization process of residual oil. Detailed Implementation

[0041] The technical solutions and effects of the present invention will be further illustrated by the following embodiments, but the following embodiments do not constitute a limitation on the method of the present invention.

[0042] Unless otherwise specified, all percentages in this invention refer to mass fractions.

[0043] In this invention, the specific surface area, pore volume, average pore size, and pore distribution were measured using an ASAP2420 fully automated physical adsorption analyzer from Micron Instruments, Inc. The measurement method is as follows: the sample was treated at 300℃ and 0.1 MPa for 4 hours, with liquid N2 as the adsorbate at an adsorption temperature of -196℃. The sample was accurately weighed and then analyzed. The specific surface area was calculated using the BET method, while the pore volume, average pore size, and pore distribution were calculated using the BJH method.

[0044] In this invention, the mechanical strength was measured using a ZQJ-III type particle strength tester manufactured by Dalian Intelligent Testing Machine Factory. In all embodiments and comparative examples, the catalyst was formed by extrusion molding, with a diameter of 1.4 mm and a length of 5.0 mm.

[0045] In this invention, the catalyst composition was determined using spectrophotometry. The testing instrument was a Lambda 365 UV spectrophotometer.

[0046] In this invention, the room temperature described in each example is 25°C.

[0047] In this invention, the specific surface area of ​​the activated carbon in each example is 2650 m². 2 / g, with a particle size of 4μm.

[0048] Example 1

[0049] (1) Weigh 9.0g of boric acid and 15.7g of nickel nitrate hexahydrate and add them to an appropriate amount of water. Heat at 60°C for 1 hour until completely dissolved, and make up to a final volume to obtain 22.5ml of impregnation solution. Place 25g of activated carbon with a particle size of 4μm in a spray impregnation pot. While rotating, spray the unsaturated impregnation solution onto the activated carbon in the pot in a misting manner and dry at 110°C for 3 hours to obtain material I. The amount of impregnation solution used is 90% of the saturated water absorption capacity of the activated carbon.

[0050] (2) Material I was mixed with 348g of pseudoboehmite (alumina content of 69.1%), 7.2g of guar gum powder, 3.58g of nitric acid and 350g of water, kneaded and shaped, and dried at 120℃ for 3 hours to obtain the carrier intermediate.

[0051] (3) The carrier intermediate was treated at 500°C for 6 hours in a mixed atmosphere of ammonia and nitrogen (ammonia volume concentration of 10%) to obtain the carrier.

[0052] (4) 36g of molybdenum oxide, 9.9g of basic nickel carbonate and 13.5g of phosphoric acid were mixed to form a 90mL solution. The above impregnation solution was impregnated on 100g of carrier by spraying. After being placed in a closed container at room temperature for 6 hours, it was dried at 120℃ for 4 hours and finally calcined at 500℃ for 4 hours to obtain the hydrodesulfurization catalyst.

[0053] In the obtained hydrodesulfurization catalyst support, the molar ratio of the first active metal nitride (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.17.

[0054] Example 2

[0055] (1) Weigh 9.0g of boric acid and 16.2g of nickel nitrate hexahydrate and add them to an appropriate amount of water. Heat at 40°C for 2 hours until completely dissolved, and make up to a final volume to obtain 27.0ml of impregnation solution. Place 30g of activated carbon with a particle size of 4μm in a spray impregnation pot. While rotating, spray the unsaturated impregnation solution onto the activated carbon in the pot in a misting manner and dry at 120°C for 2.5 hours to obtain material I. The amount of impregnation solution used is 90% of the saturated water absorption capacity of the activated carbon.

[0056] (2) Material I was mixed with 404g of pseudoboehmite (alumina content of 69.1%), 9g of guar gum powder, 4g of nitric acid and 400g of water, kneaded and shaped, and dried at 130℃ for 2.5 hours to obtain the carrier intermediate.

[0057] (3) The carrier intermediate was treated at 600°C for 4 hours in a mixed atmosphere of ammonia and argon (ammonia volume concentration of 12%) to obtain the carrier.

[0058] (4) 36g of molybdenum oxide, 10.2g of basic nickel carbonate and 16.2g of phosphoric acid were mixed to form a 90mL solution. The above impregnation solution was impregnated on 100g of carrier by spraying. After being placed in a closed container at room temperature for 6 hours, it was dried at 120℃ for 4 hours and finally calcined at 530℃ for 6 hours to obtain the hydrodesulfurization catalyst.

[0059] In the obtained hydrodesulfurization catalyst support, the molar ratio of the first active metal nitride (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.21.

[0060] Example 3

[0061] (1) Weigh 10.0g of boric acid and 8.0g of nickel nitrate hexahydrate and add them to an appropriate amount of water. Heat at 85°C for 0.5h until completely dissolved, and make up to a final volume to obtain 25.5ml of impregnation solution. Place 30g of activated carbon with a particle size of 4μm in a spray impregnation pot. While rotating, spray the unsaturated impregnation solution onto the activated carbon in the pot in a misting manner and dry at 120°C for 3h to obtain material I. The amount of impregnation solution used is 85% of the saturated water absorption capacity of the activated carbon.

[0062] (2) Material I was mixed with 380g of pseudoboehmite (alumina content of 69.1%), 8.5g of guar gum powder, 7.0g of nitric acid and 400g of water, kneaded and shaped, and dried at 100℃ for 6 hours to obtain the carrier intermediate.

[0063] (3) The carrier intermediate was treated at 700°C for 3 hours in a mixed atmosphere of ammonia and carbon dioxide (ammonia volume concentration of 10%) to obtain the carrier.

[0064] (4) 36g of molybdenum oxide, 10.2g of basic nickel carbonate and 14.8g of phosphoric acid were mixed to form a 90mL solution. The above impregnation solution was impregnated on 100g of carrier by spraying. After being placed in a closed container at room temperature for 12 hours, it was dried at 120℃ for 5 hours and finally calcined at 510℃ for 5 hours to obtain the hydrodesulfurization catalyst.

[0065] In the obtained hydrodesulfurization catalyst support, the molar ratio of the first active metal nitride (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.19.

[0066] Example 4

[0067] (1) Weigh 9.0g of boric acid and 15.7g of nickel nitrate hexahydrate and add them to an appropriate amount of water. Heat at 50°C for 1.5h until completely dissolved, and make up to a final volume to obtain 22.5ml of impregnation solution. Place 25g of activated carbon with a particle size of 4μm in a spray impregnation pot. While rotating, spray the unsaturated impregnation solution onto the activated carbon in the pot in a misting manner and dry at 110°C for 4h to obtain material I. The amount of impregnation solution used is 90% of the saturated water absorption capacity of the activated carbon.

[0068] (2) Material I was mixed with 350g of pseudoboehmite (alumina content of 69.1%), 8.0g of guar gum powder, 5.5g of nitric acid and 400g of water, kneaded and shaped, and dried at 120℃ for 3 hours to obtain the carrier intermediate.

[0069] (3) The carrier intermediate was treated at 500°C for 4 hours in a mixed atmosphere of ammonia and nitrogen (ammonia volume concentration of 10%) to obtain the carrier.

[0070] (4) 32g of molybdenum oxide, 8.9g of basic nickel carbonate and 13.0g of phosphoric acid were mixed to form a 90mL solution. The above impregnation solution was impregnated on 100g of carrier by spraying. After being placed in a closed container at room temperature for 6 hours, it was dried at 120℃ for 4 hours and finally calcined at 490℃ for 6 hours to obtain the hydrodesulfurization catalyst.

[0071] In the obtained hydrodesulfurization catalyst support, the molar ratio of the first active metal nitride (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.18.

[0072] Comparative Example 1

[0073] Compared with Example 1, the difference is that step (1) of preparing material I is omitted, and step (2) is changed to: 15.7g nickel nitrate hexahydrate, 9.0g boric acid, 25g activated carbon and 348g boehmite (alumina mass content is 69.1%), 7.2g guar gum powder, 3.58g nitric acid and 350g water are added, mixed and kneaded, and then dried at 120℃ for 3 hours to obtain the carrier intermediate.

[0074] Steps (3) and (4) are the same as in Example 1.

[0075] A comparative hydrodesulfurization catalyst, DCA-1, was prepared.

[0076] In the catalyst support, the molar ratio of the first active metal nitride (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.45.

[0077] Comparative Example 2

[0078] Compared with Example 1, the only difference is that boric acid is not added in step (1), and the comparative hydrodesulfurization catalyst DCA-2 is obtained. Everything else is the same as in Example 1.

[0079] In the catalyst support, the molar ratio of the first active metal nitride (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.27.

[0080] Comparative Example 3

[0081] Compared with Example 1, the difference is that in step (3), the carrier intermediate is treated at 500°C for 6 hours under a nitrogen atmosphere to obtain the carrier. The rest is the same as in Example 1.

[0082] A comparative hydrodesulfurization catalyst, DCA-3, was prepared. No metal nitrides were formed in this catalyst composition.

[0083] Table 1. Composition and properties of the catalysts obtained in each example.

[0084]

[0085]

[0086] Application examples

[0087] The catalysts obtained in the examples and comparative examples were evaluated using the feedstocks shown in Table 2. The properties of the feedstocks and reaction conditions are shown in Table 2, and the evaluation results are shown in Table 3.

[0088] Table 2. Properties of feedstock oil and reaction conditions

[0089] project nature properties of crude oil <![CDATA[Density / kg·m -3 > 970.0 S / wt% 2.2 <![CDATA[Ni+V / μg·g -1 ]]> 72 N / wt% 0.54 Reaction conditions Reaction temperature / °C 350 Pressure / MPa 7.5 <![CDATA[Space velocity per hour -1 > 0.5 Hydrogen-to-oil volume ratio 550

[0090] Table 3. Activity evaluation results of each catalyst example.

[0091]

[0092]

[0093] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrodesulfurization catalyst comprising a support and a second active metal component; the support comprising a first active metal nitride, a first active metal carbide, boron oxide, and aluminum oxide; wherein, The molar ratio of the first active metal nitride to the first active metal carbide is 1:0.15-0.25; The ratio of the pore volume of the pores with a diameter of <10 nm to the total pore volume is 5%-10%, the ratio of the pore volume of the pores with a diameter of 10-20 nm to the total pore volume is 70%-80%, and the ratio of the pore volume of the pores with a diameter of >20 nm to the total pore volume is 10%-25%. The first active metal is a Group VIII metal selected from one or more of Fe, Co, and Ni.

2. The catalyst of claim 1, wherein The first active metal is at least one of Co and Ni. The second active metal comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB.

3. The catalyst of claim 2, wherein The first active metal is Ni.

4. The catalyst of claim 2, wherein In the second active metal, the Group VIII metal is nickel and / or cobalt, and the Group VIB metal is molybdenum and / or tungsten.

5. The catalyst of claim 1 wherein, The mass content of the alumina is 84.0%-90.0%, the content of the first active metal in terms of metal oxide is 1.0%-3.0%, and the content of the boron oxide is 1.0%-3.0%, based on the mass of the carrier.

6. The catalyst according to claim 1 or 2, characterized in that, The mass content of the carrier is 72%-87%, the content of the Group VIII metal in the second active metal in terms of oxide is 3%-8%, and the content of the Group VIB metal in the second active metal in terms of oxide is 10%-20%, based on the mass of the catalyst.

7. A method for preparing the catalyst of any one of claims 1-6, comprising: (1) impregnating activated carbon with an impregnation solution containing boric acid and a source of the first active metal, and drying to obtain material I; (2) mixing and kneading pseudoboehmite, material I, and a binder to form a carrier intermediate, and drying to obtain a carrier; (3) heating the carrier intermediate of step (2) in an atmosphere containing ammonia to obtain a carrier; (4) impregnating the carrier of step (3) with an impregnation solution containing a source of the second active metal, and aging, drying, and calcining to obtain a hydrodesulfurization catalyst.

8. The preparation method according to claim 7, characterized in that, In step (1), the content of boric acid in the activated carbon is 10wt%-20wt% based on the mass of the activated carbon.

9. The preparation method according to claim 7, characterized in that, In step (2), the mass ratio of pseudoboehmite to material I is 2:1-10:1 based on the mass of alumina and activated carbon.

10. The preparation method according to claim 7, characterized in that, The volume fraction of ammonia in the atmosphere containing ammonia is 5wt%-15wt%, and the remainder is at least one of an inert gas, nitrogen, water vapor, or carbon dioxide.

11. The preparation method according to claim 7, characterized in that, In step (3), the heating treatment is performed under the following conditions: a temperature of 400-800°C and a treatment time of 3-8 hours.

12. The preparation method according to claim 7, characterized in that, In step (4), the aging is performed by placing the impregnated sample in a closed environment at 10-30°C for 6-12 hours. In step (4), the calcination is performed under the following conditions: a constant temperature of 450-650°C for 3-7 hours.

13. The preparation method according to claim 7, characterized in that, In step (4), the calcination is performed under the following conditions: a constant temperature of 480-600°C for 4-7 hours.

14. Use of the hydrodesulfurization catalyst of any one of claims 1-6 or prepared by the method of any one of claims 7-13 in residual oil hydroprocessing.

Images