Hydrodesulfurization catalyst as well as preparation method and application thereof

Abstract

The invention discloses a hydrodesulfurization catalyst as well as 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 (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1: (0.15-0.25). The hydrodesulfurization catalyst has the characteristics of good macromolecular diffusion performance, high desulfurization capacity, good carbon deposition resistance and the like. The hydrodesulfurization catalyst is especially suitable for a residual oil hydrodesulfurization treatment process, and has good desulfurization activity and stability.

Description

Technical Field

[0001] The invention belongs to the field of catalyst preparation, and specifically relates to a hydrodesulfurization catalyst and a preparation method and application thereof. Background Art

[0002] In recent years, crude oil resources have shown a clear trend towards heavier and inferior quality, and processing inferior crude oil faces severe challenges. 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, colloids and asphaltene. The hydrodesulfurization process can convert organic sulfur compounds in oil products into easily removed hydrogen sulfide by reacting with hydrogen, thereby achieving a deep desulfurization process. In recent years, environmental protection regulations have become increasingly stringent, and the market's requirements for product quality have also become higher and higher. Therefore, the hydrodesulfurization technology for residual oil needs to be further improved.

[0003] CN1458236A discloses a method for preparing a heavy oil hydrodemetallization and desulfurization catalyst. The catalyst preparation method uses two different forms of aluminum-containing materials, one is calcined aluminum oxide, and the other is aluminum hydroxide dry rubber powder, with alkali metal and / or alkaline earth metal elements as additives, the additives are partially premixed with the aluminum hydroxide dry rubber powder, and partially loaded on the catalyst by impregnation, so that the additives are unevenly distributed on the catalyst. The average pore size of the catalyst obtained by this method is 15-19nm, which is still too small for asphaltene micelles, is not conducive to residual oil hydrodesulfurization and hydrodemetallization reactions, and its activity and stability need to be further improved.

[0004] In summary, the residue hydrodesulfurization catalysts prepared by the existing methods have defects such as poor macromolecular diffusion performance, weak desulfurization ability, and poor anti-coking performance to varying degrees, which need to be further improved. Summary of the invention

[0005] In view of the deficiencies of the prior art, the present invention provides a hydrodesulfurization catalyst and a preparation method and application thereof. The hydrodesulfurization catalyst has the characteristics of good macromolecular diffusion performance, strong desulfurization ability, good anti-coking performance, etc. The hydrodesulfurization catalyst is particularly suitable for the residual oil hydrodesulfurization treatment process and has good desulfurization activity and stability.

[0006] The first aspect of the present invention provides a hydrodesulfurization catalyst. The 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 and the first active metal carbide to 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 is present in the catalyst in the form of an oxide.

[0010] According to the present invention, the carrier further comprises 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 aluminum oxide is 84.0% to 90.0%, the content of the first active metal in terms of 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 carrier is 72% to 87%, the content of Group VIII metal in the second active metal in terms of oxide is 3% to 8%, and the content of Group VIB metal in the second active metal in terms of oxide is 10% to 20%.

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

[0014] According to the present invention, the properties of the catalyst are as follows: the specific surface area is 160 to 220 m 2 / g, the pore volume is 0.7~1.3mL / g, the average pore diameter is 10~30nm, and the 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 pore diameter of less than 10 nm accounts for 5% to 10% of the total pore volume, the pore volume of pores with a pore diameter of 10 to 20 nm accounts for 70% to 80% of the total pore volume, and the pore volume of pores with a pore diameter of more than 20 nm accounts for 10% to 25% of the total pore volume.

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

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

[0018] (2) mixing and kneading the pseudo-boehmite, material I, and an adhesive, and drying to obtain a carrier intermediate;

[0019] (3) heating the carrier intermediate described in step (2) in an atmosphere containing ammonia to obtain a carrier;

[0020] (4) impregnating the carrier described in step (3) with an impregnation solution containing a second active metal source, and preparing a hydrodesulfurization catalyst through curing, drying and calcining.

[0021] According to the present invention, the first active metal source in step (1) 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 from at least one of soluble salts, such as nitrates, citrates, monohydrogen phosphates, dihydrogen phosphates, etc. Preferably, when preparing the impregnation solution, it can be carried out under heating conditions, such as heating at 40 to 90° C. for 0.5 to 2 hours.

[0022] According to the present invention, in the impregnation solution of step (1), the mass ratio of boric acid to 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 2000-3000m 2 / g, with a particle size of 2 to 15 μm; the amount of the impregnation liquid in step (1) is 80% to 95% of the saturated water absorption capacity of the activated carbon, by volume; the impregnation in step (1) is preferably carried out by spraying.

[0024] According to the present invention, further, in step (1), the boric acid introduced into the activated carbon accounts for 10wt% to 20wt% of the activated carbon in terms of 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 performed in a conventional molding manner, such as extrusion molding, and the molding shape is a conventional shape, such as a cylinder, a clover, a four-leaf clover, etc. In step (2), the mass ratio of pseudo-boehmite in terms of alumina to material I in terms of 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 molding needs, and the extrusion aid can be field sesbania powder. The amount of the adhesive and the extrusion aid added is added according to the actual molding needs, and the present invention has no special requirements. For example, the amount of the adhesive added is 0.5wt% to 5wt% of the mass of the pseudo-boehmite and material I used in step (2). The amount of the extrusion aid added is 0.5wt% to 6wt% of the mass of the pseudo-boehmite and material I used in step (2). In step (2), water may be added according to the molding requirements, wherein the amount of water added is 80 wt% to 100 wt% of the mass of the pseudo-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 the ammonia-containing atmosphere in step (3) is carried out in a closed environment. The pressure of the closed environment is not particularly limited and can be an autogenous pressure. The volume fraction of ammonia in the ammonia-containing atmosphere is 5wt% to 15wt%, and the rest can be at least one of an inert gas, nitrogen, water vapor or carbon dioxide.

[0029] According to the present invention, the conditions of the heating 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) includes 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 is calculated as metal oxide, wherein the content of Group VIB metal is 150-450 g / L, preferably 300-400 g / L, and the content of Group VIII metal is 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, and the phosphorus-containing compound is preferably phosphoric acid. The concentration of phosphorus in the impregnation solution is 20 to 80 g / L, preferably 40 to 60 g / L, calculated as phosphorus.

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

[0033] According to the present invention, the curing in step (4) is to place the sample after impregnation under a closed condition of 10-30°C for 6-12 hours, and the curing pressure is not particularly limited, and can be autogenous pressure; and / or, the drying condition is drying at 100-160°C for 1-8 hours, and the roasting condition is constant temperature at 450-650°C for 3-7 hours, preferably constant temperature at 480-600°C for 4-7 hours. The roasting atmosphere is an oxygen-containing gas, such as air.

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

[0035] The third aspect of the present invention provides the use of the above hydrodesulfurization catalyst in residual oil hydroprocessing.

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

[0037] 1. The hydrodesulfurization catalyst of the present invention 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 and the first active metal carbide to the first active metal is 1:0.15-0.25. The carrier of the present invention is a nitrogen-boron doped material containing active metals and has a suitable pore structure. The catalyst of the present invention is suitable for the hydrogenation conversion process of sulfides in asphaltene during the hydrotreatment of residual oil, and has high hydrodesulfurization activity and good stability.

[0038] 2. In the preparation process of the hydrodesulfurization catalyst of the present invention, by nitriding the active metal, not only the electronic structure of the active metal is improved, but also the catalyst containing Ni3N can provide more active sites and better material transfer capacity; at the same time, the Ni-B component can serve as an effective electron conduction bridge, promote the rapid transfer of electrons between metals, and effectively weaken the adsorption and bonding between the active metal and the carrier.

[0039] In addition, in the preparation process of the hydrodesulfurization catalyst of the present invention, by doping N and B elements on the catalyst carrier, Ni-Al, Ni-P and Ni-B can interact synergistically, which can reduce the interaction between the active metal and alumina and improve the dispersibility of the metal on the one hand, and effectively inhibit metal agglomeration, carbon deposition, phase change and other deactivation factors on the other hand.

[0040] 3. The hydrodesulfurization catalyst of the present invention is used in the process of hydrodesulfurization of residual oil and has good desulfurization activity and stability. DETAILED DESCRIPTION

[0041] The technical scheme and effects of the present invention are further illustrated by examples below, but the following examples do not constitute a limitation to the method of the present invention.

[0042] In the present invention, % refers to mass fraction unless otherwise specified.

[0043] In the present invention, the specific surface area, pore volume, average pore diameter and pore distribution are measured by using an ASAP2420 fully automatic physical adsorption instrument from the American Micromeritics Instrument Company, and the measuring method is as follows: after the sample is treated at 300°C and 0.1MPa for 4 hours, liquid N2 is used as the adsorbent, the adsorption temperature is -196°C, and the sample is accurately weighed and analyzed and tested. The specific surface area is calculated according to the BET method, and the pore volume, average pore diameter and pore distribution are calculated according to the BJH method.

[0044] In the present invention, the mechanical strength is measured by using a ZQJ-III particle strength tester produced by Dalian Intelligent Testing Machine Factory. The catalyst in each embodiment and comparative example is formed into an extruded strip with a diameter of 1.4 mm and a length of 5.0 mm.

[0045] In the present invention, the catalyst composition is tested by spectrophotometry, and the testing instrument is a Lambda 365 ultraviolet spectrophotometer.

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

[0047] The specific surface area of ​​each activated carbon in the present invention is 2650 m 2 / g, particle size is 4μm.

[0048] Example 1

[0049] (1) 9.0 g of boric acid and 15.7 g of nickel nitrate hexahydrate were weighed and placed in an appropriate amount of water and heated at 60° C. for 1 h until completely dissolved, and the volume was fixed to obtain 22.5 ml of impregnation solution. 25 g of activated carbon with a particle size of 4 μm was placed in a spraying drum, and the activated carbon in the drum was unsaturatedly sprayed with the impregnation solution in an atomized manner while rotating, and dried at 110° C. for 3 h to obtain material I, wherein the amount of the impregnation solution used was 90% of the saturated water absorption capacity of the activated carbon.

[0050] (2) Material I was mixed with 348 g of pseudo-boehmite (with an aluminum oxide content of 69.1%), 7.2 g of sesbania powder, 3.58 g of nitric acid and 350 g of water to form a mixture, and then dried at 120° C. for 3 hours to obtain a carrier intermediate.

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

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

[0053] In the obtained hydrodesulfurization catalyst carrier, the molar ratio of the first active metal nitride to the first active metal carbide is 1:0.17.

[0054] Example 2

[0055] (1) 9.0 g of boric acid and 16.2 g of nickel nitrate hexahydrate were weighed and placed in an appropriate amount of water and heated at 40° C. for 2 h until completely dissolved, and the volume was fixed to obtain 27.0 ml of impregnation solution. 30 g of activated carbon with a particle size of 4 μm was placed in a spraying drum, and the activated carbon in the drum was unsaturatedly sprayed with the impregnation solution in an atomized manner while rotating, and dried at 120° C. for 2.5 h to obtain material I, wherein the amount of the impregnation solution used was 90% of the saturated water absorption capacity of the activated carbon.

[0056] (2) Material I was mixed with 404 g of pseudo-boehmite (with an aluminum oxide mass content of 69.1%), 9 g of sesbania powder, 4 g of nitric acid and 400 g of water, and kneaded into a mixture, and then dried at 130° C. for 2.5 hours to obtain a carrier intermediate.

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

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

[0059] In the obtained hydrodesulfurization catalyst carrier, the molar ratio of the first active metal nitride to the first active metal carbide is 1:0.21.

[0060] Example 3

[0061] (1) Weigh 10.0 g of boric acid and 8.0 g of nickel nitrate hexahydrate, put them into appropriate amount of water, heat them at 85° C. for 0.5 h until they are completely dissolved, and adjust the volume to obtain 25.5 ml of impregnation solution. Put 30 g of activated carbon with a particle size of 4 μm in a spraying drum, spray the activated carbon in the drum with the impregnation solution in an atomized manner while rotating, and dry it at 120° C. for 3 h to obtain material I, wherein the amount of the impregnation solution used is 85% of the saturated water absorption capacity of the activated carbon.

[0062] (2) Material I was mixed with 380 g of pseudo-boehmite (with an aluminum oxide mass content of 69.1%), 8.5 g of sesbania powder, 7.0 g of nitric acid and 400 g of water, and kneaded into a mixture, and then dried at 100° C. for 6 hours to obtain a carrier intermediate.

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

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

[0065] In the obtained hydrodesulfurization catalyst carrier, the molar ratio of the first active metal nitride to the first active metal and the first active metal carbide to the first active metal is 1:0.19.

[0066] Example 4

[0067] (1) 9.0 g of boric acid and 15.7 g of nickel nitrate hexahydrate were weighed and placed in an appropriate amount of water and heated at 50° C. for 1.5 h until completely dissolved, and the volume was fixed to obtain 22.5 ml of impregnation solution. 25 g of activated carbon with a particle size of 4 μm was placed in a spraying drum, and the activated carbon in the drum was unsaturatedly sprayed with the impregnation solution in an atomized manner while rotating, and dried at 110° C. for 4 h to obtain material I, wherein the amount of the impregnation solution used was 90% of the saturated water absorption capacity of the activated carbon.

[0068] (2) Material I was mixed with 350 g of pseudo-boehmite (with an aluminum oxide mass content of 69.1%), 8.0 g of sesbania powder, 5.5 g of nitric acid and 400 g of water, and kneaded into a mixture, and then dried at 120° C. for 3 hours to obtain a carrier intermediate.

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

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

[0071] In the obtained hydrodesulfurization catalyst carrier, the molar ratio of the first active metal nitride to the first active metal and the first active metal carbide to 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: 15.7 g of nickel nitrate hexahydrate, 9.0 g of boric acid, 25 g of activated carbon and 348 g of pseudo-boehmite (alumina mass content is 69.1%), 7.2 g of sesbania powder, 3.58 g of nitric acid and 350 g of water are added and kneaded into shape, and then dried at 120°C for 3 hours to obtain a 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 carrier, 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 difference is that no boric acid is added in step (1), and a comparative hydrodesulfurization catalyst DCA-2 is prepared. The rest is the same as Example 1.

[0079] In the catalyst carrier, 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 a carrier. Other steps are the same as in Example 1.

[0082] A comparative hydrodesulfurization catalyst DCA-3 was prepared. No metal nitride was generated in the catalyst composition of this example.

[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 for residual oil hydrogenation reaction using the feedstock oil shown in Table 2. The properties of the feedstock oil and the reaction conditions are shown in Table 2. The evaluation results are shown in Table 3.

[0088] Table 2 Raw oil properties and reaction conditions

[0089] project nature Raw oil properties <![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 / ℃ 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 various catalysts

[0091]

[0092]

[0093] The above describes the specific implementation of the present invention in detail, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the various technical features being combined in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A hydrodesulfurization catalyst, comprising 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 is 1:0.15-0.

25.

2. The catalyst according to claim 1, characterized in that 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; And / or, 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.

3. The catalyst according to claim 1, characterized in that Based on the mass of the carrier, the mass content of aluminum oxide is 84.0% to 90.0%, the content of the first active metal in terms of metal oxide is 1.0% to 3.0%, and the content of boron oxide is 1.0% to 3.0%.

4. The catalyst according to claim 1 or 2, characterized in that Based on the mass of the catalyst, the mass content of the carrier 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%.

5. The catalyst according to claim 1, characterized in that The pore distribution of the catalyst is as follows: the pore volume of pores with a pore diameter of less than 10 nm accounts for 5% to 10% of the total pore volume, the pore volume of pores with a pore diameter of 10 to 20 nm accounts for 70% to 80% of the total pore volume, and the pore volume of pores with a pore diameter of more than 20 nm accounts for 10% to 25% of the total pore volume.

6. A method for preparing the catalyst according to any one of claims 1 to 5, comprising: (1) impregnating activated carbon with an impregnation solution containing boric acid and a first active metal source, and drying to obtain material I; (2) mixing and kneading the pseudo-boehmite, material I, and an adhesive, and drying to obtain a carrier intermediate; (3) heating the carrier intermediate described in step (2) in an atmosphere containing ammonia to obtain a carrier; (4) impregnating the carrier described in step (3) with an impregnation solution containing a second active metal source, and preparing a hydrodesulfurization catalyst through curing, drying and calcining.

7. The preparation method according to claim 6, characterized in that: In step (1), the boric acid introduced into the activated carbon accounts for 10 wt% to 20 wt% of the activated carbon mass in terms of oxide.

8. The preparation method according to claim 6, characterized in that: In step (2), the mass ratio of pseudo-boehmite calculated as alumina to material I calculated as activated carbon is 2:1 to 10:

1.

9. The preparation method according to claim 6, characterized in that: The volume fraction of ammonia in the ammonia-containing atmosphere is 5wt% to 15wt%, and the rest can be at least one of inert gas, nitrogen, water vapor or carbon dioxide.

10. The preparation method according to claim 6, characterized in that: The conditions of the heating treatment described in step (3) are as follows: temperature is 400-800° C., and the treatment time is 3-8 hours.

11. The preparation method according to claim 6, characterized in that: The curing in step (4) is to place the sample after immersion in a closed condition at 10 to 30° C. for 6 to 12 hours; And / or, the calcination condition is 450-650° C. for 3-7 hours, preferably 480-600° C. for 4-7 hours.

12. Use of the catalyst according to any one of claims 1 to 5 or the hydrodesulfurization catalyst according to any one of claims 6 to 11 in residual oil hydroprocessing.

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