A catalyst for hydrodenitrogenation of residual oil, its preparation method and application

Abstract

This invention discloses a hydrodenitrification catalyst for residue oil, its preparation method, and its application. The catalyst includes a support and a second active metal component. The support comprises a first active metal phosphide, a first active metal carbide, and alumina. The molar ratio of the first active metal phosphide to the first active metal carbide, calculated as the first active metal, is 1:0.20–0.40. This hydrodenitrification catalyst exhibits good macromolecular diffusion properties, strong denitrification capacity, strong metal-containing capacity, and good resistance to coking. This hydrodenitrification catalyst is particularly suitable for residue oil hydrodenitrification processes, demonstrating excellent demetallization and denitrification activity as well as good activity stability.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation, specifically relating to a residue oil hydrodenitrification 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 more pronounced, posing a severe challenge to processing low-quality crude oil. Residue hydrotreating technology is mainly used to provide feedstock for catalytic cracking processes. Increased nitrogen oxides and carbon residue in residue feedstock lead to decreased catalyst activity in downstream catalytic cracking units and worsen product distribution. Therefore, it is necessary to develop more active hydrodenitrogenation catalysts to improve the hydrodenitrogenation and carbon residue removal rates of residue feedstock.

[0003] Due to limitations in the properties of existing residue hydrodenitrogenation catalysts, these catalysts generally only have good denitrification capabilities but weak demetallization capabilities. They can only utilize the outer surface of the catalyst for demetallization reactions, with metal precipitates settling in the pores. Therefore, in residue hydrodenitrogenation catalysts, the demetallizing agent must remove metals to the maximum extent possible during denitrification, ensuring that the metal content is as low as possible when it enters the hydrodenitrogenation catalyst bed, thus enabling the hydrodenitrogenation catalyst to meet the requirements for long-term operation.

[0004] CN1098433A discloses a method for preparing a hydrorefining catalyst. This method involves mixing powdered basic nickel carbonate during the extrusion process of alumina monohydrate to provide the required Ni content for the catalyst, along with a small amount of powdered industrial-grade ammonium molybdate. The catalyst is then prepared by a single impregnation with a molybdenum-ammonia aqueous solution. The catalyst prepared by this method exhibits high hydrorefining performance, but the small pore size hinders the diffusion of large molecules and prevents metal precipitation within the pores. CN1257103A discloses a method for preparing a hydrotreated catalyst. This method optimizes the mixing process of alumina monohydrate and metal salts to promote metal dispersion. After a single mixing process to form a plastic body, the material is extruded and activated at high temperature using steam-air to produce the catalyst. However, the catalyst prepared by this method has too small a pore size to produce a bifunctional catalyst that possesses both denitrification performance and high tolerance for metal impurities.

[0005] Generally, the smaller the pore size, the higher the catalytic activity of the catalyst. This is because smaller pores can increase the surface area of ​​the catalyst, increasing the contact area between the catalyst and the reactants, thereby increasing the reaction rate. However, with the deterioration of hydrogenation feedstocks, supports with larger pore structures are needed to prepare hydrogenation catalysts with good mass transfer and diffusion performance. Therefore, for large molecular reactants such as heavy oil and residual oil, the catalyst should not only have an appropriate specific surface area to ensure high dispersion of active centers, but also a suitable pore structure to accommodate reactant diffusion. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrodenitrogenation catalyst for residue oil, its preparation method, and its application. This hydrodenitrogenation catalyst possesses characteristics such as good macromolecular diffusion performance, strong denitrification capacity, strong metal-containing capacity, and good resistance to carbon deposition. This hydrodenitrogenation catalyst is particularly suitable for residue oil hydrodenitrogenation processes, exhibiting excellent demetallization and denitrification activity as well as good activity stability.

[0007] The first aspect of the present invention provides a residue oil hydrodenitrification catalyst, comprising a support and a second active metal component. The support comprises a first active metal phosphide, a first active metal carbide and alumina, wherein the molar ratio of the first active metal phosphide to the first active metal carbide, calculated as the first active metal, is 1:0.20 to 0.40.

[0008] 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.

[0009] 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.

[0010] According to the present invention, the second active metal exists in the catalyst in the form of an oxide.

[0011] According to the present invention, the carrier further includes carbon, and the carbon content of the alumina carrier is 0.5% to 14% by mass, preferably 2% to 9%.

[0012] According to the present invention, based on the mass of the carrier, the mass content of alumina is 83% to 96%, and the content of the first active metal, calculated as metal oxide, is 2% to 8%.

[0013] According to the present invention, based on the mass of the catalyst, the mass content of the support is 74% to 85%, the content of Group VIII metals in the second active metal as oxides is 2% to 6%, and the content of Group VIB metals in the second active metal as oxides is 13% to 24%.

[0014] According to the present invention, the catalyst has the following properties: a specific surface area of ​​170–280 m². 2 / g, pore volume is 0.5~1.3mL / g, average pore size is 9~15nm, and mechanical strength is 110~150N / 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 8% of the total pore volume, the pore volume of pores with a diameter of 10 to 20 nm accounts for 63% to 69% of the total pore volume, and the pore volume of pores with a diameter >20 nm accounts for 25% to 30% of the total pore volume.

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

[0017] (1) Dissolve the surfactant, organic acid and first active metal source in water to obtain material I;

[0018] (2) Mix the pseudo-boehmite, material I obtained in step (1), and adhesive into a mold, and dry to obtain a carrier intermediate;

[0019] (3) The carrier intermediate described in step (2) is mixed with a phosphorus source and heated under the protection of an inert gas to obtain a carrier;

[0020] (4) The impregnation solution II containing the second active metal is impregnated into the carrier described in step (3), and after conditioning, drying and calcination, the residue oil hydrodenitrification catalyst is obtained.

[0021] According to the present invention, the surfactant in step (1) is one or more of long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylolamides, and polyethers; further, the surfactant has 30 to 50 carbon atoms. The organic acid is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid.

[0022] According to the present invention, in step (1), 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. The first active metal source is derived from at least one of soluble salts, such as nitrates, citrates, carbonates, or acetates.

[0023] According to the present invention, in step (1), the mass ratio of surfactant: organic acid: first active metal source (calculated as first active metal oxide): water is 10-50:1-10:20-100:100, preferably 30-50:5-10:40-70:100.

[0024] According to the present invention, in step (2), the molding can be carried out using conventional molding methods, such as extrusion molding, and the molded shape is a conventional shape, such as a cylinder, clover, four-leaf clover, etc. The mass ratio of the amount of boehmite added in step (2) based on alumina to the mass ratio of the first active metal source in material I based on oxide is 1:0.03 to 0.08. The adhesive can be at least one of nitric acid, acetic acid, and citric acid. Molding aids, such as extrusion aids, can also be added during the molding process. The extrusion aid can be guar gum powder. The amount of adhesive and extrusion aid added is added according to the actual molding needs. The present invention does not have special requirements. For example, the amount of adhesive added is 0.5wt% to 5wt% of the mass of boehmite. The amount of extrusion aid added is 0.5wt% to 6wt% of the mass of boehmite. Water can also be added during the molding process, depending on the actual molding needs. For example, the amount of water added is 80wt% to 130wt% of the mass of boehmite, preferably 90wt% to 120wt%.

[0025] According to the present invention, the drying conditions in step (2) are: drying at 100-160°C for 1-8 hours.

[0026] According to the present invention, the phosphorus source in step (3) is a substance containing phosphorus, which can be selected from substances that provide phosphorus under heating conditions, including but not limited to at least one of red phosphorus, phosphine, phosphoric acid, phosphate, hypophosphite, phosphonic acid, hypophosphite and its derivatives, and phosphine and its derivatives. The inert atmosphere can be at least one of nitrogen, helium, neon, argon and xenon, preferably nitrogen. The temperature of the heating treatment is 250-425°C, preferably 325-375°C, more preferably 350-375°C; the heating treatment time is 1-24 h, preferably 2-6 h. After the heating treatment, the gas can be purged, preferably a mixture of O2 and an inert gas (such as Ar), wherein the oxygen volume fraction is 0.1%-1%, and the purging time is 0.5-2 h.

[0027] According to the present invention, the molar ratio of the phosphorus source (in terms of P) to the carrier intermediate (in terms of the first active metal) in step (3) is 1:1 to 30:1, preferably 10:1 to 20:1.

[0028] According to the present invention, in step (4), 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. In the impregnation solution of step (4), the second active metal, calculated as a 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. When preparing the impregnation solution, the molybdenum source can be one or more of molybdenum trioxide, molybdate, and paramolybdate, preferably molybdenum trioxide; the tungsten source can be tungstate or tungsten oxide, preferably ammonium metatungstate; the nickel source can be one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, preferably basic nickel carbonate; the cobalt source can be one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, preferably basic cobalt carbonate.

[0029] According to the present invention, the impregnation solution containing the second active metal 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 30–50 g / L, calculated as phosphorus.

[0030] 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.

[0031] 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. The calcination conditions are calcination at 450–650°C for 3–7 hours, preferably calcination at 480–600°C for 4–7 hours. The calcination atmosphere is an oxygen-containing gas, such as air.

[0032] According to the present invention, the catalyst described in step (4) has the following properties: a specific surface area of ​​170–280 m². 2 The catalyst has a pore volume of 0.5–1.3 mL / g, an average pore size of 9–15 nm, and a mechanical strength of 110–150 N / cm. The pore distribution of the catalyst is as follows: pores with a diameter <10 nm account for 5%–8% of the total pore volume; pores with a diameter 10–20 nm account for 63%–69% of the total pore volume; and pores with a diameter >20 nm account for 25%–30% of the total pore volume.

[0033] The third aspect of the present invention provides the application of the above-mentioned residue hydrodenitrification catalyst or the residue hydrodenitrification catalyst prepared by the above-mentioned preparation method in residue hydrotreating.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] 1. The hydrodenitrification catalyst of this invention comprises a support and an active metal component, wherein the support contains phosphides and carbides of a first active metal and has a suitable pore structure. This catalyst is suitable for the hydroconversion of nitrogen compounds in asphaltene during the hydrotreating of residual oil, exhibiting strong hydrodemetallization capability, high hydrodenitrification activity, and good stability.

[0036] 2. In the preparation process of the hydrodenitrification catalyst of the present invention, the surfactant helps the first active metal salt to be uniformly distributed on the support surface, and also helps the support to be formed and extruded; the organic acid can form a complex with nickel, which is conducive to the formation of Ni3C during carbonization, and can delay part of the nickel sulfidation, which is conducive to the easier formation of Ni-Mo-S active phase in the catalyst. In addition, during the reaction process, the carbonization of the surfactant and organic acid, as well as the phosphating of the first active metal, generate the first active metal phosphide and the first active metal carbide, which interact synergistically, not only increasing the surface area of ​​the support. The increased number of acid sites allows for the creation of more coordinated unsaturated sites and enables the catalyst to form a suitable macroporous structure. This hydrodenitrification catalyst, used in the hydrotreating of residual oil, exhibits strong hydrodemetallization capability, high hydrodenitrification activity, and good stability.

[0037] In the preparation process of the hydrodenitrification catalyst of the present invention, by doping P and C elements on the catalyst support, Ni-Al, Ni-P and C 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, coke deposition and phase transformation, thereby better playing an important role in regulating the performance of the catalyst.

[0038] 3. The hydrodenitrification catalyst of the present invention is used in the hydrotreating process of residual oil and has the characteristics of strong hydrodemetallization ability, high hydrodenitrification activity and good stability. Detailed Implementation

[0039] 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.

[0040] In this invention, unless otherwise specified, % refers to mass fraction.

[0041] In this invention, the specific surface area, pore volume, and pore distribution were measured using an ASAP2420 fully automated physical adsorption instrument 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, and the pore volume and pore distribution were calculated using the BJH method.

[0042] 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 1.3 mm and a length of 4.0 mm.

[0043] In this invention, the catalyst composition was determined using spectrophotometry. The testing instrument was a Lambda 365 UV spectrophotometer.

[0044] In this invention, the room temperature described in each example is 25°C.

[0045] Example 1

[0046] (1) Take 135g of nickel nitrate hexahydrate and 6.5g of citric acid and add them to 80g of water. After they are completely dissolved, add 32g of dodecyl fatty alcohol polyoxyethylene ether to obtain material I.

[0047] (2) Take 172g of pseudoboehmite (alumina content of 69.2%), 52g of material I, 6g of guar gum powder, 4.5g of nitric acid (mass concentration of 67%), add 186g of water, mix and knead into shape, and dry at 120℃ for 3 hours to obtain catalyst support intermediate A-1.

[0048] (3) According to the molar ratio of phosphorus source (P) to support intermediate (first active metal) of 10.15:1, weigh the obtained catalyst support intermediate A-1 and sodium hypophosphite and place them in a quartz tube. After purging with argon (100 mL / min) for 30 min, use a vacuum pump to evacuate the reaction system to a vacuum, seal it, raise the temperature to 350℃, maintain it for 3 h, lower it to room temperature and release the pressure, and purge with O2 / Ar (O2 volume fraction of 0.5%) for 1 h to obtain the support.

[0049] (4) 36g of molybdenum oxide, 17.3g of basic nickel carbonate, and 10.8g of phosphoric acid were mixed to form a 90mL impregnation 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 catalyst CA-1.

[0050] In the catalyst support, the molar ratio of the first active metal phosphide (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.36.

[0051] Example 2

[0052] (1) Take 140g of nickel nitrate hexahydrate and 5.4g of citric acid and add them to 80g of water. After they are completely dissolved, add 31.5g of dodecyl fatty alcohol polyoxyethylene ether to obtain material I.

[0053] (2) Take 202g of boehmite (alumina content of 69.2%), 73g of material I, 6g of guar gum powder, 6g of nitric acid (mass concentration of 67%), add 223g of water, mix and knead into shape, and dry at 120℃ for 3 hours to obtain catalyst support intermediate B-1.

[0054] (3) According to the molar ratio of phosphorus source (P) to support intermediate (first active metal) of 10.38:1, weigh the obtained catalyst support intermediate B-1 and sodium hypophosphite and place them in a quartz tube. After purging with nitrogen (100 mL / min) for 30 min, use a vacuum pump to evacuate the reaction system to a vacuum, seal it, raise the temperature to 350℃, maintain it for 2 h, lower it to room temperature and release the pressure, and purge with O2 / Ar (O2 volume fraction of 0.5%) for 1 h to obtain the support.

[0055] (4) 38g of molybdenum oxide, 14.62g of basic nickel carbonate, and 10.25g of phosphoric acid were mixed to prepare a 95mL impregnation solution. The above impregnation solution was sprayed onto 100g of carrier. 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 catalyst CB-1.

[0056] In the catalyst support, the molar ratio of the first active metal phosphide (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.25.

[0057] Example 3

[0058] (1) Take 135g of nickel nitrate hexahydrate and 6.5g of citric acid and add them to 80g of water. After they are completely dissolved, add 32g of nonylphenol polyoxyethylene ether OP-10 to obtain material I.

[0059] (2) Take 172g of pseudoboehmite (alumina mass content of 69.2%), 52g of material I, 6g of guar gum powder, 4.5g of nitric acid (mass concentration of 67%), add 186g of water, mix and knead into shape, and dry at 120℃ for 3 hours to obtain catalyst support intermediate C-1.

[0060] (3) According to the molar ratio of phosphorus source (P) to support intermediate (first active metal) of 10.33:1, weigh the obtained catalyst support intermediate C-1 and red phosphorus and place them in a quartz tube. After purging with argon (100 mL / min) for 30 min, use a vacuum pump to evacuate the reaction system to a vacuum, seal it, raise the temperature to 350℃, maintain it for 2 h, lower it to room temperature and release the pressure, and purge with O2 / Ar (O2 volume fraction of 0.5%) for 1 h to obtain the support.

[0061] (4) 36g of molybdenum oxide, 17.3g of basic nickel carbonate, and 10.8g of phosphoric acid were mixed to form a 90mL impregnation 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 550℃ for 4 hours to obtain catalyst CC-1.

[0062] In the catalyst support, the molar ratio of the first active metal phosphide (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.27.

[0063] Example 4

[0064] (1) Take 200g of nickel nitrate hexahydrate and 5.6g of citric acid and add them to 80g of water. After they are completely dissolved, add 24g of dodecyl fatty alcohol polyoxyethylene ether to obtain material I.

[0065] (2) Take 202g of pseudoboehmite (alumina mass content of 69.2%), 42g of material I, 7g of guar gum powder, 8g of nitric acid (mass concentration of 67%), add 201g of water, mix and knead into shape, and dry at 120℃ for 3 hours to obtain catalyst support intermediate D-1.

[0066] (3) Weigh the obtained catalyst support intermediate D-1 and sodium hypophosphite in a quartz tube according to the molar ratio of phosphorus source (P) to support intermediate (first active metal) of 14.85:1. Purge with nitrogen (100 mL / min) for 30 min, then use a vacuum pump to evacuate the reaction system to a vacuum, seal it, raise the temperature to 350℃, maintain it for 2 h, lower it to room temperature and release the pressure, and purge with O2 / Ar (O2 volume fraction of 0.5%) for 1 h to obtain the support.

[0067] (4) 36g of molybdenum oxide, 17.3g of basic nickel carbonate, and 10.8g of phosphoric acid were mixed to form a 90mL impregnation 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 catalyst CD-1.

[0068] In the catalyst support, the molar ratio of the first active metal phosphide (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.34.

[0069] Comparative Example 1

[0070] Compared with Example 1, the difference is that step (1) of preparing material I is omitted, and step (2) is changed to: 27.7g nickel nitrate hexahydrate, 1.3g citric acid, 6.6g dodecyl fatty alcohol polyoxyethylene ether, 172g boehmite (alumina mass content of 69.2%), 6g guar gum powder, 4.5g nitric acid (mass concentration of 67%), and 202.4g water are added and kneaded into shape, and then dried at 120°C for 3 hours to obtain the catalyst support intermediate.

[0071] Steps (3) and (4) are the same as in Example 1.

[0072] A comparative hydrodenitrification catalyst, DCA-1, was prepared.

[0073] In the catalyst support, the molar ratio of the first active metal phosphide (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.6.

[0074] Comparative Example 2

[0075] Compared with Example 1, the difference is that no organic acid is added when preparing material I in step (1).

[0076] A comparative hydrodenitrification catalyst, DCA-2, was prepared.

[0077] In the catalyst support, the molar ratio of the first active metal phosphide (calculated as the first active metal) to the first active metal carbide (calculated as the first active metal) is 1:0.19.

[0078] Comparative Example 3

[0079] Compared with Example 1, in step (3), the support does not undergo phosphating but is only heated in an inert gas Ar for 3 hours at 350°C. After cooling to room temperature, the pressure is released, and the support is purged with O2 / Ar (O2 volume fraction of 0.5%) for 1 hour to obtain the support.

[0080] A comparative hydrodenitrification catalyst, DCA-3, was prepared.

[0081] Table 1. Composition and properties of the catalysts obtained in each example.

[0082]

[0083] Application examples

[0084] 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.

[0085] Table 2. Properties of feedstock oil and reaction conditions

[0086]

[0087]

[0088] Table 3. Activity evaluation results of each catalyst example.

[0089] Removal rate Operating time, h Example 1 Example 2 Example 3 Example 4 HDN, % 200 95.3 96.1 94.6 95.1 HDN, % 2000 90.6 89.8 91.4 90.5 HDM, % 200 78.2 81.5 82.3 79.4 HDM, % 2000 71.7 75.2 73.8 72.8

[0090] Continued from Table 3

[0091] Removal rate Operating time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 HDN, % 200 71.8 74.2 76.4 HDN, % 2000 42.8 47.3 45.1 HDM, % 200 64.5 63.2 65.3 HDM, % 2000 32.2 33.5 34.1

[0092] 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 method for preparing a residue oil hydrodenitrogenation catalyst, comprising: (1) Dissolve the surfactant, organic acid and first active metal source in water to obtain material I; (2) Mix the pseudoboehmite, material I obtained in step (1), and adhesive into a mold, and dry to obtain a carrier intermediate; (3) The carrier intermediate described in step (2) is mixed with a phosphorus source and heated under the protection of an inert gas to obtain a carrier; (4) The impregnation solution II containing the second active metal is impregnated into the carrier described in step (3), and after conditioning, drying and calcination, a residue oil hydrodenitrification catalyst is obtained. The residue hydrodenitrification catalyst includes a support and a second active metal component. The support includes a first active metal phosphide, a first active metal carbide, and alumina. The molar ratio of the first active metal phosphide to the first active metal carbide, calculated as the first active metal, is 1:0.20~0.

40. The first active metal is a Group VIII metal, selected from one or more of Fe, Co, and Ni.

2. The preparation method according to claim 1, characterized in that, The surfactant mentioned in step (1) is one or more of the following: long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkylolamides, and polyethers. And / or, the organic acid is one or more of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid.

3. The preparation method according to claim 1 or 2, characterized in that, In step (1), the mass ratio of surfactant: organic acid: first active metal source (calculated as first active metal oxide): water is 10~50:1~10:20~100:

100.

4. The preparation method according to claim 1, characterized in that, The mass ratio of the amount of boehmite added in step (2) as alumina to the mass ratio of the first active metal source in material I as oxide is 1:0.03~0.

08.

5. The preparation method according to claim 1, characterized in that, The temperature of the heat treatment in step (3) is 250~425℃; the heat treatment time is 1~24h.

6. The preparation method according to claim 5, characterized in that, The temperature of the heat treatment in step (3) is 325~375℃; the heat treatment time is 2~6h.

7. The preparation method according to claim 5, characterized in that, The temperature of the heat treatment in step (3) is 350~375℃.

8. The preparation method according to claim 1, characterized in that, In step (3), the molar ratio of phosphorus source (P) to carrier intermediate (first active metal) is 1:1 to 30:

1.

9. The preparation method according to claim 8, characterized in that, In step (3), the molar ratio of phosphorus source (P) to carrier intermediate (first active metal) is 10:1 to 20:

1.

10. The preparation method according to claim 1, characterized in that, The impregnation solution containing the second active metal in step (4) contains phosphorus compounds.

11. The preparation method according to claim 10, characterized in that, The phosphorus-containing compound in step (4) is phosphoric acid.

12. The preparation method according to claim 10, characterized in that, In step (4), the concentration of phosphorus in the impregnation solution is 20~80g / L, calculated as phosphorus.

13. The preparation method according to claim 10, characterized in that, In step (4), the concentration of phosphorus in the impregnation solution is 30~50g / L, calculated as phosphorus.

14. A residue hydrodenitrification catalyst prepared by any one of claims 1 to 13, comprising a support and a second active metal component, wherein the support comprises a first active metal phosphide, a first active metal carbide and alumina; the molar ratio of the first active metal phosphide to the first active metal carbide, based on the first active metal, is 1:0.20 to 0.

40. The first active metal is a Group VIII metal, selected from one or more of Fe, Co, and Ni.

15. The catalyst according to claim 14, characterized in that, The first active metal is at least one of Co and Ni.

16. The catalyst according to claim 14, characterized in that, The first active metal is Ni.

17. The catalyst according to claim 14, characterized in that, The second active metal includes at least one metal component selected from Group VIII and at least one metal component selected from Group VIB.

18. The catalyst according to claim 17, characterized in that, The Group VIII metals are nickel and / or cobalt, and the Group VIB metals are molybdenum and / or tungsten.

19. The catalyst according to claim 14, characterized in that, The catalyst has the following properties: specific surface area of ​​170~280 m². 2 / g; And / or, the pore volume is 0.5~1.3mL / g; And / or, the mechanical strength is 110~150 N / cm; And / or, the pore distribution of the catalyst is as follows: the pore volume of pores with a diameter <10 nm accounts for 5%~8% of the total pore volume, the pore volume of pores with a diameter of 10~20 nm accounts for 63%~69% of the total pore volume, and the pore volume of pores with a diameter >20 nm accounts for 25%~30% of the total pore volume; And / or, the average pore size of the catalyst is 9~15 nm.

20. The application of the residue hydrodenitrification catalyst prepared by any one of claims 1 to 13 or the catalyst described in any one of claims 14 to 19 in residue hydrotreatment.

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