Hydroprocessing catalyst, method for its preparation and use

Abstract

The application discloses a kind of hydroprocessing catalyst and its preparation method and application.The method comprises the following steps: the alumina-based carrier is oversaturated and impregnated in the impregnation solution containing dopamine, protective agent and hydrogenation active metal, the pH value of system is adjusted, so that dopamine is self-polymerized on the pore channel surface of alumina-based carrier, then washed, dried, pre-carbon deposition, calcination, to obtain a hydroprocessing catalyst.The hydrogenation catalyst prepared by the method of the application is obviously improved in desulfurization and denitrification activity and 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] Most supported catalysts are prepared by impregnation, such as various hydrogenation catalysts. When preparing hydrogenation catalysts by impregnation, the catalyst activity is closely related to the dispersion of the active metal (such as Mo) on the surface and its interaction with the support (such as alumina support). Improving the dispersion of the active metal on the support surface while weakening the strong metal-support interaction is key to preparing highly active hydrogenation catalysts.

[0003] CN106669786A discloses a catalytic diesel hydrocracking catalyst and its preparation method. The main method involves preparing a catalyst support by mixing modified molecular sieves, amorphous silica-alumina and / or alumina, then impregnating or adsorbing unsaturated olefins onto the support, reacting and carbonizing under an inert atmosphere, and then removing some of the carbon deposits by calcination to obtain a carbon-containing support. After loading the active metal, the catalyst is dried to obtain the catalyst.

[0004] CN 101940930A discloses a method for preparing a hydrogenation catalyst. The method mainly involves impregnating a carbon-containing precursor with a catalyst precursor, mixing organic matter, soluble silicone oil, and additives, and then introducing the mixture into a support, followed by heat treatment to obtain a carbon-modified alumina support.

[0005] CN101940929A discloses a method for preparing a hydrogenation catalyst. This method involves introducing a carbon precursor into the catalyst in one step by adding it to a metal impregnation solution. By controlling the heating rate of the carbonization roasting process, excessive volatilization of organic matter is avoided, thereby achieving coking in the catalyst.

[0006] The above preparation methods all involve introducing carbon-containing organic matter onto a support or catalyst and then carrying out a carbonization process to cover the acid centers, but they do not achieve a reasonable distribution of carbon, active components, and acidic sites. Summary of the Invention

[0007] To overcome the shortcomings of existing technologies, this invention provides a hydrogenation catalyst, its preparation method, and its application. The hydrogenation catalyst prepared by the method of this invention exhibits significantly improved desulfurization and denitrification activities.

[0008] The first aspect of this invention provides a method for preparing a hydrogenation catalyst, comprising:

[0009] 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, drying, pre-coking, and calcination, a hydrogenation-treated catalyst is obtained.

[0010] 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%.

[0011] 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.

[0012] 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.

[0013] 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.

[0014] 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.

[0015] 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%.

[0016] 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.

[0017] 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% (calculated as oxide).

[0018] 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%.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] In the method of the present invention, the drying process is to impregnate the carrier with the impregnation liquid and then dry it under conditions not exceeding the decomposition temperature of the generated polydopamine. The drying temperature is generally 30℃~180℃, preferably 50~120℃; the drying time is 0.5h~20h, preferably 2~10h.

[0024] In the method of this invention, the pre-coking is carried out under an inert atmosphere, preferably nitrogen. The pre-coking reaction conditions are: a reaction temperature of 200–500°C, preferably 250–350°C, and a reaction time of 1–5 hours, preferably 2–4 hours. Further, the carbon content in the catalyst after pre-coking is 0.5 wt%–5 wt%, preferably 2.5 wt%–4.0 wt%.

[0025] In the method of this invention, the calcination is carried out under an oxygen-containing atmosphere. The oxygen-containing atmosphere is one of air, a mixture of oxygen and nitrogen, or a mixture of oxygen and an inert gas, wherein the volume fraction of oxygen in the mixture is 10%–50%, preferably 15%–45%. The calcination conditions are: a calcination temperature of 400–600°C and a calcination time of 0.5–6 hours, preferably 1–3 hours.

[0026] 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%.

[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 solution pH, 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, facilitating efficient dispersion and anchoring of the active component, thus 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 sites during metal "anchoring". The center also helps to prevent excessive polymerization of dopamine, ensuring the permeability of the catalyst channels. The use of inert gas pre-coating allows partial coking of polydopamine and anchoring of the hydrogenation active metal components, effectively preventing the aggregation of active components. After high-temperature calcination, the protective agent deposited at the medium-strong acid sites, the remaining polydopamine, and some of the coking are burned off. This not only effectively disperses the hydrogenation active metal but also retains the medium-strong acid on the catalyst surface, achieving an effective match between the acid centers and the hydrogenation centers, which is beneficial to improving the hydrodesulfurization and hydrodenitrification activities 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 precursor.

[0040] (3) The catalyst precursor obtained in step (2) was placed in a calcining furnace, nitrogen gas was introduced into the furnace, and the catalyst was calcined at a constant temperature of 350°C for 2 hours for pre-coking; then, an oxygen / nitrogen mixture with an oxygen content of 25% was introduced into the calcining furnace, and the catalyst was calcined at 450°C for 3 hours to obtain the catalyst C1 of the present invention. The carbon content in the pre-coked catalyst was 2.6 wt%.

[0041] Example 2

[0042] (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.

[0043] (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 precursor.

[0044] (3) The catalyst precursor obtained in step (2) is placed in a calcining furnace, nitrogen gas is introduced into the calcining furnace, and it is calcined at a constant temperature of 300°C for 3 hours for pre-coking; then, an oxygen / nitrogen mixed gas with an oxygen content of 10% is introduced into the calcining furnace, and it is calcined at 450°C for 3 hours to obtain the catalyst C2 of the present invention. The carbon content in the pre-coked catalyst is 4.5 wt%.

[0045] Example 3

[0046] (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.

[0047] (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 precursor.

[0048] (3) The catalyst precursor obtained in step (2) was placed in a calcining furnace, nitrogen gas was introduced into the furnace, and the catalyst was calcined at a constant temperature of 350°C for 4 hours for pre-coking; then, an oxygen / nitrogen mixture with an oxygen content of 25% was introduced into the calcining furnace, and the catalyst was calcined at 450°C for 3 hours to obtain the catalyst C3 of the present invention. The carbon content in the pre-coked catalyst was 3.4 wt%.

[0049] Example 4

[0050] (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.

[0051] (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 precursor.

[0052] (3) The catalyst precursor obtained in step (2) is placed in a calcining furnace, nitrogen is introduced into the furnace, and the catalyst is calcined at a constant temperature of 200°C for 3 hours for pre-coking. Then, an oxygen / nitrogen mixture with an oxygen content of 25% is introduced into the calcining furnace, and the catalyst is calcined at 450°C for 3 hours to obtain the catalyst C4 of the present invention. The carbon content in the pre-coked catalyst is 3 wt%.

[0053] Example 5

[0054] (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.

[0055] (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 precursor.

[0056] (3) The catalyst precursor obtained in step (2) was placed in a calcining furnace, nitrogen gas was introduced into the furnace, and the catalyst was calcined at a constant temperature of 300°C for 4 hours for pre-coking; then, an oxygen / nitrogen mixture with an oxygen content of 25% was introduced into the calcining furnace, and the catalyst was calcined at 450°C for 3 hours to obtain the catalyst C5 of the present invention. The carbon content in the pre-coked catalyst was 3.8 wt%.

[0057] Comparative Example 1

[0058] (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 by equal volume, dry at 120℃ for 4 hours, introduce nitrogen into the calcination furnace, and calcine at 300℃ for 4 hours. Then, introduce an oxygen / nitrogen mixture with an oxygen content of 25% into the calcination furnace and calcine at 450℃ for 3 hours to obtain the comparative catalyst DC1.

[0059] Comparative Example 2

[0060] (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.

[0061] (2) Add 100g of alumina support to the impregnation solution, ripen in a water vapor saturated atmosphere for 12h, and then vacuum dry at 40℃ for 2h to obtain the catalyst precursor.

[0062] (3) The catalyst precursor obtained in step (2) was placed in a calcining furnace, nitrogen gas was introduced into the furnace, and the catalyst was calcined at a constant temperature of 300°C for 4 hours for pre-coking. Then, an oxygen / nitrogen mixture with an oxygen content of 25% was introduced into the calcining furnace, and the catalyst was calcined at 450°C for 3 hours to obtain the control catalyst DC2. The carbon content in the pre-coked catalyst was 2.2% by mass.

[0063] Comparative Example 3

[0064] Compared to Example 5, sodium allyl sulfonate was not added to prepare the impregnation solution. The comparative catalyst DC3 was obtained.

[0065] (1) Prepare 300 mL of impregnation solution containing Mo, Ni, P and 18 g of dopamine; in the impregnation solution, based on the mass of the alumina-based carrier, the active metal component (calculated as oxide) has a Mo content of 20 wt% and a Ni content of 4 wt%.

[0066] (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 precursor.

[0067] (3) The catalyst precursor obtained in step (2) was placed in a calcining furnace, nitrogen gas was introduced into the furnace, and the catalyst was calcined at a constant temperature of 300°C for 4 hours for pre-coking; then, an oxygen / nitrogen mixture with an oxygen content of 25% was introduced into the calcining furnace and calcined at 450°C for 3 hours to obtain the control catalyst DC3. The carbon content in the pre-coked catalyst was 4.1 wt%.

[0068] Comparative Example 4

[0069] Compared to Example 5, diethanolamine was not added, and the pH value was adjusted as follows:

[0070] (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.

[0071] (2) Add 100g of alumina support to the impregnation solution, impregnate at 60℃ for 20h, and then dry at 110℃ for 6h to obtain the catalyst precursor.

[0072] (3) The catalyst precursor obtained in step (2) was placed in a calcining furnace, nitrogen gas was introduced into the furnace, and the catalyst was calcined at a constant temperature of 300°C for 4 hours for pre-coking. Then, an oxygen / nitrogen mixture with an oxygen content of 25% was introduced into the calcining furnace, and the catalyst was calcined at 450°C for 3 hours to obtain the control catalyst DC4. The carbon content in the pre-coked catalyst was 2.1% by mass.

[0073] Example 6

[0074] 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.

[0075] 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℃.

[0076] Table 1 Properties of Crude Oil

[0077] <![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

[0078] 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:

[0079]

[0080]

[0081] 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.

[0082] 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 content in the reaction feedstock used; and Ndp is the nitrogen content in the reaction product of the reference reagent, wherein the sulfur content and nitrogen content are expressed as mass fractions.

[0083] The hydrorefining evaluation results of the catalysts prepared in each example and comparative example are shown in Table 2.

[0084] Table 2 Evaluation Results

[0085]

[0086] 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 alumina-based support pores. After washing, the support is dried under conditions not exceeding the decomposition temperature of the generated polydopamine, pre-coked under an inert atmosphere, and calcined to obtain a 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 hydrogenation active metal includes Group VIII metals and Group VIB metals, wherein the Group VIII metal is Ni and / or Co, and the Group VIB metal is Mo.

7. 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%.

8. The preparation method according to claim 7, 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%.

9. 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.

10. The preparation method according to claim 9, characterized in that, In the impregnation solution, the amount of additives added accounts for 1wt% to 3wt% of the alumina-based carrier.

11. 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.

12. The preparation method according to claim 11, 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.

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

14. The preparation method according to claim 13, characterized in that, The immersion temperature is 30~60℃, and the immersion time is 5~20 h.

15. The preparation method according to claim 1 or 11, 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.

16. The preparation method according to claim 15, 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.

17. The preparation method according to claim 1, characterized in that, The drying temperature is 30℃~180℃; the drying time is 0.5h~20h. And / or, the pre-coking reaction conditions are: reaction temperature of 200~500℃, reaction time of 1~5 hours; And / or, the calcination is carried out in an oxygen-containing atmosphere, and the calcination conditions are: calcination temperature of 400~600℃ and calcination time of 0.5~6h.

18. The preparation method according to claim 17, characterized in that, The drying temperature is 50~120℃; the drying time is 2~10h.

19. The preparation method according to claim 17, characterized in that, The inert atmosphere used for the pre-coking is nitrogen.

20. The preparation method according to claim 17, characterized in that, The pre-coking reaction conditions are: reaction temperature of 250~350℃ and reaction time of 2~4 hours.

21. The preparation method according to claim 17, characterized in that, The carbon content in the pre-coated catalyst is 0.5wt%~5wt%.

22. The preparation method according to claim 21, characterized in that, The carbon content in the pre-coated catalyst is 2.5wt%~4.0wt%.

23. 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.

24. The preparation method according to claim 23, characterized in that, The hydrogenation catalyst prepared by the method has, based on the mass of the alumina-based support, a Group VIII metal content of 2 wt% to 8 wt% (calculated as oxide) and a Group VIB metal content of 15 wt% to 23 wt% (calculated as oxide).

25. The hydrogenation catalyst prepared by any one of claims 1-24.

26. The application of the hydrotreating catalyst according to claim 25 in the hydrotreating of heavy distillate oil, characterized in that, The purpose of the hydrogenation treatment is to perform hydrodesulfurization and / or hydrodenitrification.

27. The application according to claim 26, 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.

28. The application according to claim 26, 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.

29. The application according to claim 28, 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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