A hydroprocessing catalyst, its preparation method and use

Abstract

This invention discloses a hydrotreating catalyst, its preparation method, and its application. The method includes: supersaturating an alumina-based support with an impregnation solution containing dopamine, a protective agent, and a hydrotreating active metal; adjusting the pH of the system to allow dopamine to self-polymerize on the pore surface of the alumina-based support; and then washing and heat-treating to obtain the hydrotreating catalyst. The hydrotreating catalyst prepared by this method exhibits significantly improved desulfurization and denitrification activity, as well as improved stability.

Description

Technical Field

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

[0002] Regardless of the future scenario and pace of energy transition, fossil fuels, represented by oil, will continue to be the primary energy source for decades to come. Therefore, hydrotreating catalysts for the clean reprocessing of petroleum products will remain among the most important catalysts on the market.

[0003] γ-Al₂O₃, due to its suitable mechanical strength, acidity, and pore structure, has been widely used as a support or in the preparation of hydrorefining catalysts and hydrocracking catalysts. With increasingly stringent environmental regulations, the development of highly active hydrotreatment catalysts has become essential, and the requirements for their performance and stability have become more complex. Improving the dispersion and loading of the active component in the catalyst is one of the effective ways to develop high-performance catalysts. The interaction force between the active metal on the surface of pure Al₂O₃ and the support is relatively strong. Excessive interaction forces lead to a strong interaction between the active metal and the support in the final catalyst, ultimately hindering the full sulfidation of the active metal oxide in the catalyst, resulting in unsatisfactory catalyst activity. Currently, the support can be modified by adding organic promoters. Acidic functional groups can fully occupy the coordination unsaturated centers on the alumina surface of the support, effectively preventing the strong interaction between the metal and the support, and increasing the number of active centers generated in the catalyst; alternatively, coating the alumina surface with a carbon layer can achieve the same effect.

[0004] CN108067243B discloses a hydrotreating catalyst, its preparation method, and its application. The method includes: modifying an alumina support with a nitrogen-containing organic acid solution or an aromatic carboxylic acid solution, followed by low-temperature drying; then impregnating it with an active component solution or an active metal and additives, and finally subjecting it to high-temperature heat treatment to obtain the hydrotreating catalyst.

[0005] CN107442126B discloses a method for preparing a hydrotreating catalyst. The method includes preparing a carbon-modified alumina-based support, loading a hydrotreating active metal component using an impregnation method, and drying to obtain the hydrotreating catalyst. The preparation method of the carbon-modified alumina-based support includes: sequentially or simultaneously introducing water-soluble silicone oil, a soluble additive, and a carbon precursor into the alumina-based support, followed by heat treatment to obtain the carbon-modified alumina-based support.

[0006] CN110935464B discloses a method for preparing a carbon-containing hydrodemetallization catalyst. The method involves immersing alumina powder in an ammonium bicarbonate aqueous solution and sealing it for heat treatment. After heat treatment, solid-liquid separation is performed, and the solid phase is dried. The dried material is then soaked in a carbon-containing precursor solution I, followed by solid-liquid separation and further drying to obtain modified rod-shaped alumina clusters. These modified alumina clusters are then mixed with boehmite and kneaded into a mold. The molded material is dried and sprayed with a carbon-containing precursor solution II, then dried again. Subsequently, it undergoes carbonization and microwave treatment under an inert atmosphere to obtain a carbon-containing alumina support. The hydrogenation active component is then loaded onto the carbon-containing alumina support to obtain the hydrodemetallization catalyst.

[0007] The drawback of the aforementioned technology is that it may result in insufficiently weak interaction between the active component and the support, making the active component prone to flow and aggregation during the reaction. This leads to continuously increasing active particle size, reducing the dispersion of the active component in the catalyst, and consequently decreasing the catalyst activity and significantly shortening its lifespan. Therefore, a hydrotreating catalyst that balances "weakening the interaction between the metal and the support" and "preventing metal aggregation" is needed, which would greatly contribute to improving its activity and stability. Summary of the Invention

[0008] To overcome the shortcomings of existing technologies, this invention provides a hydrotreating catalyst, its preparation method, and its application. The hydrotreating catalyst prepared by the method of this invention exhibits significantly improved desulfurization and denitrification activity, as well as improved stability.

[0009] The first aspect of this invention provides a method for preparing a hydrogenation catalyst, comprising:

[0010] An alumina-based support is supersaturated and impregnated in an impregnation solution containing dopamine, a protective agent, and a hydrogenation active metal. The pH value of the system is adjusted to allow dopamine to self-polymerize on the surface of the alumina-based support pores. After washing and heat treatment, a hydrogenation catalyst is obtained.

[0011] In the method of this invention, the alumina-based carrier can be a commercially available product or prepared using conventional methods. The preparation method of the alumina-based carrier can include: mixing aluminum hydroxide dry adhesive powder, molding, and then drying and calcining to obtain the alumina-based carrier. During the mixing process, conventional molding aids such as extrusion aids, binders, and solvents can be added as needed. The alumina-based carrier may contain auxiliary components, such as at least one of silicon, phosphorus, titanium, zirconium, and magnesium, with the auxiliary component's mass content in the carrier being less than 15%.

[0012] In the method of this invention, the alumina-based support has a pore volume of 0.3–1.5 mL / g and a specific surface area of ​​150–450 m². 2 / g.

[0013] In the method of this invention, the shape of the alumina-based carrier can be spherical, strip-shaped (cylindrical, butterfly-shaped, clover-shaped, or four-leaf clover-shaped strip), etc. The shape of the carrier can be selected according to specific needs.

[0014] In the method of the present invention, the amount of dopamine added to the impregnation solution is 2 wt% to 40 wt%, preferably 4 wt% to 24 wt%, based on the mass of the alumina-based carrier. The solvent used in the solution containing dopamine, the protective agent, and the hydrogenated active metal is at least one of water, methanol, or ethanol.

[0015] In the method of the present invention, the protective agent is a water-soluble olefin, preferably one or more of sodium N-isopropylacrylamide p-styrene sulfonate, sodium methyl allyl sulfonate, sodium allyl sulfonate, isopentenol, 3-methyl-3-buten-1-ol, and allyl alcohol, and more preferably one or more of sodium N-isopropylacrylamide p-styrene sulfonate, sodium methyl allyl sulfonate, and sodium allyl sulfonate.

[0016] In the method of the present invention, the amount of the protective agent added to the impregnation solution is 0.5wt% to 8wt% of the alumina-based carrier, preferably 1wt% to 5wt%.

[0017] In the method of this invention, the hydrogenation active metal includes Group VIII metals and Group VIB metals, wherein the Group VIII metals are preferably Ni and / or Co, and the Group VIB metals are preferably Mo. When preparing the impregnation solution, the molybdenum source can be selected from one or more of molybdenum oxide, ammonium molybdate, ammonium tetrathiomolybdate, and ammonium paramolybdate; the nickel source can be selected from one or more of nickel nitrate, basic nickel carbonate, nickel oxalate, nickel chloride, and nickel acetate; and the cobalt source can be selected from one or more of cobalt nitrate, cobalt oxalate, basic cobalt carbonate, and cobalt chlorate.

[0018] In the method of the present invention, the amount of hydrogenated active metal added in the impregnation solution, based on the mass of the alumina-based support, is 12wt% to 36wt%, preferably 18wt% to 32wt%.

[0019] In the method of the present invention, the impregnation solution may further contain auxiliary components, which may be selected from one or more of phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium, and vanadium. The amount of auxiliary component added to the impregnation solution is 0.5 wt% to 5 wt% of the alumina-based carrier, preferably 1 wt% to 3 wt%.

[0020] In the method of the present invention, the impregnation is supersaturated impregnation, wherein the volume of the impregnation liquid is 1.5 to 4.5 times the saturated water absorption capacity of the alumina-based carrier, preferably 1.8 to 4.0 times.

[0021] In the method of the present invention, the immersion temperature is 10-80℃, preferably 30-60℃, and the immersion time is 1-30h, preferably 5-20h.

[0022] In the method of the present invention, the reagent for adjusting the pH value of the system is selected from one or more of ethylenediamine, ammonium carbonate, diethanolamine, triethanolamine, and Tris buffer.

[0023] In the method of this invention, adjusting the pH value of the system involves immersing the carrier in the impregnation solution, shaking for 5-10 minutes, adding a pH adjusting reagent, and continuing shaking until the pH value of the system reaches 8-10. After adding the pH adjusting reagent, the pH value of the system is at least 0.5 higher than before adding the pH adjusting reagent.

[0024] In the method of the present invention, after the impregnation solution impregnates the carrier, it is dried under conditions not exceeding the decomposition temperature of the generated polydopamine. The drying temperature is generally 30℃ to 200℃, preferably 50℃ to 120℃; the drying time is 0.5h to 20h, preferably 2h to 10h.

[0025] The hydrogenation catalyst prepared by the method of this invention uses an alumina-based support and Group VIII and Group VIB metals as the active metal components for hydrogenation. The Group VIII metals are preferably Co and / or Ni, and the Group VIB metals are preferably Mo. Based on the mass of the alumina-based support, the content of the Group VIII metals, calculated as oxides, is 1 wt% to 10 wt%, preferably 2 wt% to 8 wt%, and the content of the Group VIB metals, calculated as oxides, is 10 wt% to 25 wt%, preferably 15 wt% to 23 wt%.

[0026] In the hydrogenation catalyst prepared by the method of the present invention, the mass content of dopamine is 1% to 10%, preferably 2% to 6%, based on the mass of the alumina-based support.

[0027] A second aspect of the present invention provides a hydrogenation catalyst prepared by the above method.

[0028] The third aspect of this invention provides the application of the hydrotreating catalyst prepared by the above method in the hydrotreating of heavy distillate oil.

[0029] Furthermore, the heavy distillate oil feedstock has a distillation range of 270–580°C, and the heavy distillate oil feedstock is at least one of coking wax oil, vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil, and coal tar.

[0030] Furthermore, the hydrogenation treatment conditions are as follows: the reaction temperature is 350–430°C, preferably 360–390°C; the reaction pressure is 4–16 MPa, preferably 6–14 MPa; and the hydrogen-to-oil volume ratio is 600:1–1500:1, preferably 800:1–1000:1.

[0031] Furthermore, the purpose of the hydrogenation treatment is to perform hydrodesulfurization and / or hydrodenitrification.

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] This invention first modifies the surface of an alumina-based support with dopamine and a protective agent. By subsequently adjusting the pH of the solution, dopamine is induced to self-polymerize on the support surface into polydopamine, effectively blocking the direct interaction between the hydrogenated active metal and the support. This forms a "network" structure on the support surface that facilitates efficient dispersion and anchoring of the active component, thereby effectively "anchoring" the hydrogenated active metal and preventing its flow and aggregation. The protective agent introduced simultaneously with dopamine can cover some acidic sites before dopamine polymerization, preventing the covering of active centers during metal "anchoring." This achieves an effective match between acidic centers and hydrogenation centers and also helps prevent excessive polymerization of dopamine, ensuring the permeability of the catalyst channels and thus improving the activity and stability of the catalyst. Detailed Implementation

[0034] The present invention will be described in detail below through embodiments, but the present invention is not limited to the following embodiments. Furthermore, unless otherwise specified, all percentages in the present invention refer to weight percentages.

[0035] In this invention, the alumina support used in the examples and comparative examples has the following properties: pore volume of 0.85 mL / g and specific surface area of ​​213 m². 2 / g.

[0036] In this invention, the impregnation solution is prepared as follows: (1) an aqueous solution of the active metal component is prepared using basic nickel carbonate, molybdenum oxide, and phosphoric acid; (2) dopamine and a protective agent are added to the aqueous solution of the active metal component to obtain the impregnation solution.

[0037] Example 1

[0038] (1) Prepare 200 mL of impregnation solution containing Mo, Ni, P, 4 g dopamine and 1 g allyl alcohol; the impregnation solution contains 20 wt% Mo and 4 wt% Ni as active metal components (calculated as oxides) based on the mass of the alumina-based carrier. The pH value of the impregnation solution is 6.0.

[0039] (2) Add 100g of alumina support to the impregnation solution, shake for 5min, add ethylenediamine, adjust the pH of the solution to about 8.0, impregnate at 30℃ for 20h, and then dry at 80℃ for 6h to obtain the catalyst of the present invention, denoted as C1.

[0040] Example 2

[0041] (1) Prepare 300 mL of impregnation solution containing Mo, Ni, P, 30 g of dopamine and 5 g of sodium methyl allyl sulfonate; in the impregnation solution, based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) Mo content is 20 wt% and the Ni content is 4 wt%. The pH value of the impregnation solution is 8.0.

[0042] (2) Add 100g of alumina support to the impregnation solution, shake for 5min, add diethanolamine, adjust the pH of the solution to about 9, impregnate at 50℃ for 6h, and then dry at 120℃ for 3h to obtain the catalyst C2 of the present invention.

[0043] Example 3

[0044] (1) Prepare 400 mL of impregnation solution containing Mo, Ni, P, 20 g of dopamine and 4 g of N-isopropylacrylamide sodium styrene sulfonate; in the impregnation solution, based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) Mo content is 20 wt% and the Ni content is 4 wt%. The pH value of the impregnation solution is 7.5.

[0045] (2) Add 100g of alumina support to the impregnation solution, shake for 5min, add Tris buffer, adjust the pH of the solution to about 8.5, impregnate at 40℃ for 10h, and then dry at 100℃ for 4h to obtain the catalyst C3 of the present invention.

[0046] Example 4

[0047] (1) Prepare 250 mL of impregnation solution containing Mo, Ni, P, 5 g dopamine and 3 g isopentenol; in the impregnation solution, based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) Mo content is 20 wt% and the Ni content is 4 wt%. The pH value of the impregnation solution is 7.0.

[0048] (2) Add 100g of alumina support to the impregnation solution, shake for 5min, add Tris buffer, adjust the pH of the solution to about 8.5, impregnate at 30℃ for 15h, and then dry at 120℃ for 4h to obtain the catalyst C4 of the present invention.

[0049] Example 5

[0050] (1) Prepare 300 mL of impregnation solution containing Mo, Ni, P, 18 g of dopamine and 5 g of sodium allyl sulfonate; in the impregnation solution, based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) Mo content is 20 wt% and the Ni content is 4 wt%. The pH value of the impregnation solution is 8.0.

[0051] (2) Add 100g of alumina support to the impregnation solution, shake for 5min, add diethanolamine, adjust the pH of the solution to about 9.5, impregnate at 60℃ for 20h, and then dry at 110℃ for 6h to obtain the catalyst C5 of the present invention.

[0052] Comparative Example 1

[0053] (1) Prepare an aqueous solution of nickel nitrate, ammonium molybdate, and phosphoric acid as an impregnation solution. Based on the mass of the alumina-based support, the active metal component (calculated as oxide) Mo content is 20wt% and the Ni content is 4wt%. Impregnate 100g of the support with an equal volume and dry at 120℃ for 4 hours to obtain the comparative catalyst DC1.

[0054] Comparative Example 2

[0055] (1) Prepare 300 mL of impregnation solution containing Mo, Ni, P and 18 g of dopamine; the impregnation solution contains 20 wt% Mo and 4 wt% Ni as active metal components (calculated as oxides) based on the mass of the alumina-based carrier. The pH value of the impregnation solution is 5.5.

[0056] (2) 100g of alumina support was added to the impregnation solution and aged in a water vapor saturated atmosphere for 12h. Then, it was vacuum dried at 40℃ for 2h to obtain the comparative catalyst DC2.

[0057] Comparative Example 3

[0058] (1) Prepare 100 mL of a solution containing 6 g of dopamine; place 100 g of the carrier in a beaker and slowly impregnate the carrier with the prepared solution. The impregnated carrier is then aged in a steam-saturated atmosphere for 12 hours, and then dried in an oven at 90 °C for 20 hours to obtain the modified carrier.

[0059] (2) Prepare 100 mL of impregnation solution containing Mo, Ni and P. Based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) Mo content is 20 wt% and Ni content is 4 wt%.

[0060] (3) The modified support was added to the impregnation solution and aged in a water vapor saturated atmosphere for 12 hours, and then vacuum dried at 40°C for 2 hours to obtain the comparative catalyst DC3.

[0061] Comparative Example 4

[0062] Compared to Example 5, sodium allyl sulfonate was not added to prepare the impregnation solution. The comparative catalyst DC4 was obtained.

[0063] Comparative Example 5

[0064] Compared to Example 5, diethanolamine was not added, and the pH value was adjusted as follows:

[0065] (1) Prepare 300 mL of impregnation solution containing Mo, Ni, P, 18 g of dopamine and 5 g of sodium allyl sulfonate; in the impregnation solution, based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) Mo content is 20 wt% and the Ni content is 4 wt%. The pH value of the impregnation solution is 8.0.

[0066] (2) 100g of alumina support was added to the impregnation solution and impregnated at 60℃ for 20h, and then dried at 110℃ for 6h to obtain the comparative catalyst DC5.

[0067] Example 6

[0068] The catalysts of the above embodiments and comparative examples were subjected to activity evaluation tests in a microreactor. Before evaluation, a cyclohexane solution of CS2 was used as a sulfidation solution to treat the hydrotreating catalyst. The concentration of CS2 in the cyclohexane solution was 4 wt%, the sulfidation temperature was 330 °C, the sulfidation pressure was 14.0 MPa, the sulfidation time was 6 h, and the corresponding volume ratio of hydrogen to sulfidation solution was 550.

[0069] The feedstock was catalytic diesel oil, with properties shown in Table 1. The reaction hydrogen pressure was 14.0 MPa, the hydrogen-to-oil volume ratio was 1000:1, and the volume hourly space velocity (VHSV) was 1.0 h⁻¹. -1 The reaction temperature is 370℃.

[0070] Table 1 Properties of Crude Oil

[0071] <![CDATA[Density (20 °C) / g·cm -3 > 0.9267 Distillation range / ℃ IBP / 10% 276 / 364 30％ / 50％ 407 / 428 70％ / 90％ 473 / 529 95% / EBP 553 / 575 <![CDATA[S / μg·g -1 ]]> 29600 <![CDATA[N / μg·g -1 ]]> 1540

[0072] The hydrodesulfurization and denitrification activities of the catalyst are expressed as relative to the reference (Comparative Example 1), and the relative hydrodesulfurization activity (RVA(S)) and relative hydrodenitrification activity (RVA(N)) of the catalyst are calculated according to Equations (1) and (2), respectively:

[0073]

[0074]

[0075] In the formula, k(S) and k(N) represent the hydrodesulfurization and hydronitrogenation activities of the catalyst, respectively, and k(DS) and k(DN) represent the hydrodesulfurization and hydronitrogenation activities of the reference (Comparative Example 1), respectively.

[0076] In the formula, Ssp is the sulfur content in the reaction product of the evaluation catalyst used; Ssf is the sulfur content in the reaction feedstock used; Sdp is the sulfur content in the reaction product of the reference reagent; Nsp is the nitrogen content in the reaction product of the evaluation catalyst used; Nsf is the nitrogen mass percentage in the reaction feedstock used; and Ndp is the nitrogen content in the reaction product of the reference reagent.

[0077] The hydrorefining evaluation results of the catalysts prepared in each example and comparative example are shown in Table 2.

[0078] Table 2 Evaluation Results

[0079]

[0080] As can be seen from Table 2, compared with the comparative catalyst, the hydrotreating catalyst prepared by the method of the present invention has higher hydrodesulfurization and denitrification activity, and is particularly suitable for the hydrotreating process of heavy feedstocks.

Claims

1. A method for preparing a hydrotreating catalyst, comprising: An alumina-based support is supersaturated and impregnated in an impregnation solution containing dopamine, a protective agent, and a hydrogenation active metal. The pH value of the system is adjusted to allow dopamine to self-polymerize on the surface of the pores of the alumina-based support. After washing, the catalyst is dried under conditions not exceeding the decomposition temperature of the generated polydopamine to obtain the hydrogenation-treated catalyst. In the impregnation solution, based on the mass of the alumina-based carrier, the amount of dopamine added is 2wt% to 40wt%. The protective agent is one or more of the following: sodium N-isopropylacrylamide p-styrene sulfonate, sodium methyl allyl sulfonate, sodium allyl sulfonate, isopentenol, 3-methyl-3-buten-1-ol, and allyl alcohol. In the impregnation solution, the amount of the protective agent added is 0.5wt% to 8wt% of the alumina-based carrier; The pH adjuster for adjusting the pH of the system is selected from one or more of ethylenediamine, ammonium carbonate, diethanolamine, triethanolamine, and Tris buffer.

2. The preparation method according to claim 1, characterized in that, The properties of the alumina-based support are as follows: the pore volume of the alumina-based support is 0.3~1.5mL / g, and the specific surface area is 150~450m². 2 / g.

3. The preparation method according to claim 1, characterized in that, In the impregnation solution, based on the mass of the alumina-based carrier, the amount of dopamine added is 4wt% to 24wt%.

4. The preparation method according to claim 1, characterized in that, The protective agent is one or more of N-isopropylacrylamide sodium p-styrene sulfonate, sodium methyl allyl sulfonate, and sodium allyl sulfonate.

5. The preparation method according to claim 1 or 4, characterized in that, In the impregnation solution, the amount of the protective agent added accounts for 1 wt% to 5 wt% of the alumina-based carrier.

6. The preparation method according to claim 1, characterized in that, The hydrogenated active metals include Group VIII metals and Group VIB metals.

7. The preparation method according to claim 6, characterized in that, Group VIII metals are Ni and / or Co, and Group VIB metals are Mo.

8. The preparation method according to claim 1, characterized in that, In the impregnation solution, based on the mass of the alumina-based support, the amount of hydrogenated active metal added, calculated as oxide, is 12wt%~36wt%.

9. The preparation method according to claim 8, characterized in that, In the impregnation solution, based on the mass of the alumina-based support, the amount of hydrogenated active metal added, calculated as oxide, is 18wt%~32wt%.

10. The preparation method according to claim 1, characterized in that, The impregnation solution also contains auxiliary components, which are selected from one or more of phosphorus, titanium, silicon, zinc, copper, zirconium, boron, fluorine, lanthanum, cerium, and vanadium. The amount of auxiliary components added to the impregnation solution is 0.5wt% to 5wt% of the alumina-based carrier.

11. The preparation method according to claim 10, characterized in that, The amount of the additive added to the impregnation solution is 1 wt% to 3 wt% of the alumina-based carrier.

12. The preparation method according to claim 1, characterized in that, The volume of the impregnation solution is 1.5 to 4.5 times the saturated water absorption capacity of the alumina-based carrier.

13. The preparation method according to claim 12, characterized in that, The volume of the impregnation solution is 1.8 to 4.0 times the saturated water absorption capacity of the alumina-based carrier.

14. The preparation method according to claim 1, characterized in that, The immersion temperature is 10~80℃, and the immersion time is 1~30 h.

15. The preparation method according to claim 14, characterized in that, The immersion temperature is 30~60℃, and the immersion time is 5~20 h.

16. The preparation method according to claim 1, characterized in that, To adjust the pH of the system, the carrier is immersed in the impregnation solution, shaken for 5-10 minutes, and then a pH adjuster is added and the shaking continues until the pH of the system reaches 8-10.

17. The preparation method according to claim 16, characterized in that, After adding the pH adjuster, the pH of the system increased by at least 0.5 compared to before the pH adjuster was added.

18. The preparation method according to claim 1, characterized in that, The drying temperature is 30℃~200℃, and the drying time is 0.5h~20h.

19. The preparation method according to claim 18, characterized in that, The drying temperature is 50~120℃, and the drying time is 2~10h.

20. The preparation method according to claim 1, characterized in that, The hydrogenation catalyst prepared by the method has a content of 1 wt% to 10 wt% of Group VIII metals as oxides and a content of 10 wt% to 25 wt% of Group VIB metals as oxides, based on the mass of the alumina-based support.

21. The preparation method according to claim 20, characterized in that, The hydrogenation catalyst prepared by the method has a content of 2wt% to 8wt% of Group VIII metals as oxides and a content of 15wt% to 23wt% of Group VIB metals as oxides, based on the mass of the alumina-based support.

22. The hydrogenation catalyst prepared by any one of claims 1-21.

23. The application of the hydrotreating catalyst according to claim 22 in the hydrotreating of heavy distillate oil, characterized in that, The purpose of the hydrogenation treatment is to perform hydrodesulfurization and / or hydrodenitrification.

24. The application according to claim 23, characterized in that, The heavy distillate oil feedstock has a distillation range of 270~580℃ and is at least one of coking wax oil, vacuum gas oil, deasphalted oil, catalytic cracking cycle oil, shale oil, and coal tar.

25. The application according to claim 24, characterized in that, The hydrotreating conditions are: reaction temperature of 350~430℃, reaction pressure of 4~16MPa, and hydrogen-to-oil volume ratio of 600:1~1500:

1.

26. The application according to claim 25, characterized in that, The hydrotreating conditions are: reaction temperature of 360~390℃, reaction pressure of 6~14 MPa, and hydrogen-to-oil volume ratio of 800:1~1000:1.

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