A hydroprocessing catalyst, its preparation method and use

Abstract

The application discloses a high-activity hydrogenation catalyst and a preparation method and application thereof. The hydrogenation treatment catalyst contains at least molybdenum, nickel active metal, metal additive, carbon and inorganic refractory oxide carrier; the metal additive is at least one or more of zinc, copper, magnesium and gallium, and the hydrogen temperature programmed reduction (H2-TPR) of the catalyst should have the following properties: the peak area integral value of the reduction peak in the temperature range of 350-450 DEG C accounts for more than 50%, preferably more than 60%, further preferably more than 70%, more further preferably 65%-85%, and best preferably 70%-80% of the total peak area integral value in the temperature range of 150-650 DEG C. The hydrogenation catalyst not only has strong hydrogenation activity without sulfuration, but also has good stability compared with conventional noble metal and nickel catalysts when treating low-sulfur raw materials.

Description

Technical Field

[0001] This invention relates to a hydrotreating catalyst, its preparation method, and its application; more specifically, it relates to a hydrotreating catalyst that does not require sulfidation, its preparation method, and its application. Background Technology

[0002] Currently, distillate oil hydrotreating catalysts mainly use sulfide-formed Group VIB and VIII metals as the active phase. Although sulfide-formed active phases have high hydrotreating capacity, their use has certain limitations: First, to maintain the stability of catalytic activity, a certain concentration of hydrogen sulfide is required in the feedstock and reaction atmosphere to maintain the structural stability of the active phase. Therefore, when processing increasingly more sulfur-free or low-sulfur feedstocks, sulfide-formed catalysts need to have some sulfur added or blended, limiting their application range. Second, sulfide-formed catalysts require sulfidation during start-up and regeneration after use, which is not only cumbersome but also causes significant environmental pollution. To solve these problems, researchers have attempted to prepare sulfur-free active phases for hydrotreating oil products.

[0003] CN112742478A discloses a method for preparing a hydrogenation catalyst. This catalyst contains an organomolybdenum compound and an organoferric salt arranged in a specific chemical formula as the active phase. This catalyst exhibits good hydrogenation performance, ring-opening activity, and denitrification effect while possessing high metal content and low cost. However, this catalyst has poor stability and deactivates rapidly under high-temperature conditions.

[0004] CN1146164A discloses a catalyst with nickel and zirconium as active components and silicon-aluminum as a support, used in the preparation of medical white oil, high-purity medical paraffin, and mixtures of hydrocarbons with low boiling points and low or no aromatic content. However, this catalyst is less effective when processing petroleum fractions with high aromatic content.

[0005] CN103071509A discloses a hydrogenation catalyst. It uses nickel and zinc as active components, manganese oxide and molybdenum oxide as promoters, and potassium oxide, magnesium oxide, and calcium oxide as auxiliary agents. This catalyst has the advantages of low hydrogen consumption and ease of start-up. However, its stability is relatively poor, making it unsuitable for long-term, high-temperature operation.

[0006] CN101157056A discloses a hydrogenation catalyst, wherein the support material is Al2O3, SiO2, TiO2, or a composite oxide of two thereof prepared by a sol-gel method. A nickel- and cobalt-containing salt solution is introduced during the sol-gel preparation of the support material. The catalyst of this invention exhibits excellent hydrodesulfurization and hydrodenitrogenation activity. However, when processing high-aromatic feedstocks, the catalyst's hydrogenation activity is slightly insufficient.

[0007] In existing technologies, the active component of hydrogenation catalysts is generally a metal sulfide, which usually needs to be pre-sulfurized, especially when processing low-sulfur feedstock oil. In order to maintain hydrogenation activity, sulfur replenishment is required. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a highly active hydrogenation catalyst, its preparation method, and its applications. The hydrogenation catalyst exhibits strong hydrogenation activity without the need for sulfidation, and also demonstrates superior stability compared to conventional noble metal and nickel-based catalysts when processing low-sulfur feedstocks.

[0009] The first aspect of this invention provides a hydrogenation treatment catalyst, wherein the hydrogenation treatment catalyst contains at least molybdenum and nickel active metals, a metal additive, carbon, and an inorganic refractory oxide support; the metal additive is at least one or more of zinc, copper, magnesium, and gallium, and the H2-TPR of the catalyst should have the following properties: the peak area integral value of the reduction peak in the temperature range of 350-450℃ accounts for more than 50% of the total peak area integral value in the temperature range of 150-650℃, preferably more than 60%, further preferably more than 70%, even more preferably 65%-85%, and most preferably 70%-80%.

[0010] In the hydrogenation catalyst of this invention, based on the weight of the final hydrogenated catalyst, the mass content of molybdenum (calculated as oxide) is 5.0%-35%, preferably 10%-30%, more preferably 12-28%; the mass content of carbon is 0.5%-6.0%, preferably 1.0-5.5%, more preferably 1.5%-5.0%; the mass content of nickel (calculated as elemental) is 1.0%-6.0%, preferably 1.5%-5.5%, more preferably 2.0%-5.0%; and the mass content of metal additives (calculated as elemental) is 0.2%-4.0%, preferably 0.3%-3.5%, more preferably 0.5%-3.0%.

[0011] In the hydrogenation catalyst of this invention, the inorganic refractory oxide support can be one or more of alumina, amorphous silica-alumina, macroporous silica, and titanium-silicon composite materials, preferably γ-alumina. Based on the weight of the final hydrogenation catalyst, the support mass content is 50%-90%, preferably 55%-85%, and more preferably 60%-80%.

[0012] In the hydrogenation catalyst of this invention, the support may be doped with a small amount of one or more heteroatoms such as silicon, phosphorus, boron, magnesium, and fluorine to improve the support performance. The amount of heteroatoms incorporated shall not exceed 5.0% of the total mass of the support, preferably 0-4.0%. The heteroatoms may be incorporated in a manner that is already known, either during the preparation of the support or after the support is prepared.

[0013] In the hydrogenation catalyst of this invention, the support should have the following properties: a pore volume of 0.6~1.4 cm³. 3 / g, with a preferred pore volume of 0.7~1.3 cm³. 3 / g, specific surface area is 190-340m² 2 / g, preferably 220-320m 2 / g.

[0014] A second aspect of the present invention provides a method for preparing a hydrotreating catalyst, the method comprising the following steps: (4) Select or prepare a hydrogenation catalyst support. (5) Introducing metallic molybdenum onto the carrier in step (1); (6) In step (2), an organonickel and organometallic additives are introduced onto an inorganic refractory oxide support for molybdenum metal, and the final hydrogenation catalyst is obtained after calcination under an inert atmosphere.

[0015] Furthermore, the carrier in step (1) can be a commercially available product or prepared according to existing technology.

[0016] Furthermore, the introduction of metallic molybdenum in step (2) can be achieved through conventional impregnation. After introduction, it can be dried at a temperature of 100-180°C, preferably 120-160°C, for a time of 2-20 hours, preferably 4-16 hours. After drying, it can be calcined at a temperature of 380-600°C, preferably 400-550°C, for a time of 2-12 hours, preferably 3-10 hours.

[0017] After calcination, reduction can be performed. Taking hydrogen reduction as an example, the hydrogen reduction temperature is 150-500℃, preferably 250-400℃, the hydrogen reduction pressure is 1.0-12.0MPa, preferably 2.0-10.0MPa, and the hydrogen flow rate is 1.0-30 Nml / min·g. 催化剂 The preferred concentration is 3.0-20 Nml / min·g. 催化剂 The hydrogen treatment time is 2-30 hours, preferably 4-28 hours.

[0018] Furthermore, after introducing metallic molybdenum in step (2), the form of metallic molybdenum on the carrier can be molybdenum salt, molybdenum oxide, or elemental molybdenum.

[0019] Further, in step (3), the organic groups corresponding to the organonickel and organometallic additives are organic acid radicals or organic complexes. The organic acid radicals are one or more of malonate, citrate, oxalate, ethylenediaminetetramethylenephosphonate, salicylate, benzoate, and tartrate. The organic complexes are one or more of acetylacetone, EDTA, and NTA. The organic acid radicals or organic complexes corresponding to the organonickel and organometallic additives can be the same or different; preferably, the same organic acid radical or organic complex is used.

[0020] Furthermore, in step (3), organonickel and organometallic additives can be introduced separately or simultaneously onto the carrier on which metallic molybdenum is introduced, preferably simultaneously; more preferably, when they are introduced simultaneously, the organonickel and organometallic additives correspond to the same organic acid anion or organic complex.

[0021] Furthermore, in step (3), an organic carbon deposition aid can be further introduced onto the inorganic refractory oxide carrier of metallic molybdenum introduced in step (2). The organic carbon deposition aid is a substance containing double bonds, preferably one or more of acrylic acid, acrylamide, butenoic acid, butenoamide, 2-pentenoic acid, and 3-hexenoic acid. The introduction method can be by introducing it alone or by introducing it alone together with organonitrile and organometallic aids.

[0022] Furthermore, in step (3), the organic carbon deposition aid introduced on the inorganic refractory oxide carrier of metallic molybdenum in step (2) can be introduced simultaneously or sequentially with the introduced organonickel and organometallic aids.

[0023] Furthermore, in step (3), the organonickel and organometallic additives are introduced using an impregnation method, which can be either stepwise impregnation or co-impregnation, with co-impregnation being preferred. The solvent used can be one or more of water, ethanol, acetone, and toluene. During the co-impregnation process, the molar concentration of the organonickel, calculated as nickel, is 0.1-2.0 mol / L, preferably 0.2-1.5 mol / L, and the molar concentration of the organometallic additive, calculated as a metal additive, is 0.05-1.0 mol / L, preferably 0.1-0.5 mol / L. The impregnation can be performed multiple times as needed.

[0024] Furthermore, before the heat treatment in step (3), the total mass content of organic acid radicals and / or organic additives is 3.0%-25.0%, preferably 4.0%-22.0%, and more preferably 5.0%-18.0%, based on the weight of the final hydrogenation catalyst.

[0025] Furthermore, in step (3), the heat treatment needs to be divided into two steps. First, drying in air at a temperature of 80-180℃, preferably 100-160℃, for a drying time of 1-10 hours, preferably 2-8 hours. Then, calcination is carried out under an inert gas such as nitrogen or argon at a temperature of 280-550℃, preferably 300-500℃, for a calcination time of 1.0-8.0 hours, preferably 2.0-6.0 hours.

[0026] The third aspect of the present invention provides a method for hydrogenating low-sulfur feedstock oil, wherein the above-mentioned hydrogenation catalyst is used to introduce low-sulfur oil with a high degree of unsaturation into the reduced hydrogenation catalyst to carry out the hydrogenation reaction.

[0027] Furthermore, the low-sulfur, high-unsaturation feedstock oil refers to oil with a sulfur content between 0-200 ppm and a bromine index between 1000-100000 mgBr·100g. -1 Raw materials, such as Fischer-Tropsch synthetic oil and coal-based feedstock oil.

[0028] Furthermore, the hydrogenation reaction conditions are as follows: reaction temperature 150-380℃, preferably 180-350℃; hydrogen pressure 2.0-18.0 MPa, preferably 4.0-16.0 MPa; and liquid hourly space velocity 0.2-3.0 h⁻¹. -1 Preferably 0.3-2.0 h -1 The hydrogen-to-oil ratio is 200:1-1500:1, preferably 400:1-1200:1.

[0029] Furthermore, the reduction is performed by hydrogen activation treatment, specifically at a treatment temperature of 150-280℃, preferably 180-240℃, a hydrogen pressure of 2.0-18.0 MPa, preferably 3.0-14.0 MPa, and a treatment time of 2.0-12.0 hours, preferably 3.0-8.0 hours.

[0030] Compared with existing technologies, the catalyst provided by this invention has the following advantages: 1. The catalyst can stably process non-traditional petroleum-based feedstocks with low sulfur content and high unsaturation. During the processing, no additional sulfur species are required to maintain the hydrogen sulfide partial pressure of the reaction system, effectively expanding the application range of hydrogenation catalysts.

[0031] 2. The catalyst does not require sulfidation treatment before use. Activation of the catalyst can be achieved during the gas-tight process of the reactor, effectively simplifying the catalyst start-up process. Detailed Implementation

[0032] The present invention will be further described below with reference to the embodiments, but the following embodiments do not constitute a limitation of the present invention. Unless otherwise specified, the percentage content of the materials mentioned herein is a mass percentage content.

[0033] Weigh 6000.0 g of alumina dry adhesive powder, add 100.0 g of acetic acid, 200.0 g of citric acid, 200.0 g of polyethylene glycol, 100.0 g of urea, 200.0 g of guar gum powder, and 100.0 g of cellulose. Mix thoroughly, then add 4000.0 g of an aqueous solution containing 2.0% nitric acid. Compress for 10.0 min, then extrude using a 2.0 mm diameter four-leaf clover-shaped perforated plate. Dry at 120℃ for 6.0 h, then calcine at 650℃ for 4.0 h. The resulting carrier is denoted as S-0.

[0034] The pore properties of the S-0 carrier were determined as follows: specific surface area of ​​251 m². 2 / g, pore volume 1.07 cm³ 3 / g.

[0035] In the method of this invention, TPR is determined by the following method: This experiment determined the reduction temperature of the active metal on the catalyst surface using H2-TPR. The instrument used was an AutoChem-2950 chemisorption analyzer from Micron Technology, USA. The heating rate was 10℃ / min, the initial temperature was 100℃, and the final temperature was 1000℃.

[0036] Example 1 Weigh 15.0 g of ammonium heptamolybdate tetrahydrate, dissolve it in 120 ml of deionized water, and prepare a solution labeled MQ-1.

[0037] 100.0 g of carrier S-0 was weighed, impregnated with MQ-1, dried at 120°C for 6.0 hours, calcined at 450°C for 4.0 hours, and then subjected to hydrogen gas at a pressure of 6.0 MPa, a temperature of 300°C, and a hydrogen flow rate of 6.0 Nml / min·g. 催化剂 The reaction was carried out for 6.0 hours, and the intermediate obtained was denoted as M-1.

[0038] Weigh 8.0g nickel tartrate, 2.0g copper tartrate, 2.0g tartaric acid, and 5.0g butenoic acid, dissolve them in deionized water, and bring the volume to 110ml. The resulting impregnation solution is labeled NQ-1.

[0039] M-1 was impregnated with NQ-1 and dried at 120°C for 6.0 hours to obtain the catalyst intermediate, denoted as TM-1.

[0040] The catalyst obtained by calcining TM-1 at 350°C for 4.0 hours under a nitrogen pressure of 0.2 MPa was designated as Cat-1.

[0041] Example 2 Weigh 20.0g of ammonium heptamolybdate tetrahydrate, dissolve it in 120 ml of deionized water, and prepare a solution labeled MQ-2.

[0042] 100.0 g of carrier S-0 was weighed, impregnated with MQ-2, dried at 120°C for 6.0 hours, calcined at 450°C for 4.0 hours, and then subjected to hydrogen gas at a pressure of 6.0 MPa, a temperature of 300°C, and a hydrogen flow rate of 6.0 Nml / min·g. 催化剂 The reaction was carried out for 6.0 hours, and the intermediate obtained was denoted as M-2.

[0043] Weigh 10.0 g nickel acetylacetone, 4.0 g copper acetylacetone, and 5.0 g butenamide, dissolve them in a 1:1 mixture of deionized water and ethanol, and bring the volume to 110 ml. The resulting impregnation solution is labeled NQ-2.

[0044] M-2 was impregnated with NQ-2 and dried at 120°C for 6.0 hours to obtain the catalyst intermediate, denoted as TM-2.

[0045] The catalyst obtained by calcining TM-2 at 350°C for 4.0 hours under nitrogen pressure of 0.2 MPa was designated as Cat-2.

[0046] Example 3 Weigh 25.0g of ammonium heptamolybdate tetrahydrate, dissolve it in 120ml of deionized water, and prepare a solution labeled MQ-3.

[0047] 100.0 g of carrier S-0 was weighed, impregnated with MQ-3, dried at 120°C for 6.0 h, calcined at 450°C for 4.0 h, and then subjected to hydrogen gas at a pressure of 6.0 MPa, a temperature of 300°C, and a hydrogen flow rate of 6.0 Nml / min·g. 催化剂 The reaction was carried out for 6.0 hours, and the intermediate obtained was designated as M-3.

[0048] Weigh out 10.0g of nickel citrate, 4.0g of zinc citrate, 5.0g of citric acid, and 5.0g of 2-pentenoic acid, dissolve them in deionized water, and bring the volume to 110ml. The resulting impregnation solution is labeled NQ-3.

[0049] M-3 was impregnated with NQ-3 and dried at 120°C for 6.0 hours to obtain the catalyst intermediate, denoted as TM-3.

[0050] The catalyst obtained by calcining TM-3 at 350°C for 4.0 hours under nitrogen pressure of 0.2 MPa was designated as Cat-3.

[0051] Example 4 Weigh 30.0g of ammonium heptamolybdate tetrahydrate and 20.0g of ammonia solution with a mass fraction of 20%, dissolve them in 120ml of deionized water, and prepare a solution labeled MQ-4.

[0052] 100.0 g of carrier S-0 was weighed, impregnated with MQ-4, dried at 120°C for 6.0 hours, calcined at 450°C for 4.0 hours, and then subjected to hydrogen gas at a pressure of 6.0 MPa, a temperature of 300°C, and a hydrogen flow rate of 6.0 Nml / min·g. 催化剂 The reaction was carried out for 6.0 hours, and the intermediate obtained was designated as M-4.

[0053] Weigh out 12.0 g of nickel glycolate, 10.0 g of zinc gluconate, and 5.0 g of 3-hexenoic acid, dissolve them in deionized water, and bring the volume to 110 ml. The resulting impregnation solution is labeled NQ-4.

[0054] M-4 was impregnated with NQ-4 and dried at 120°C for 6.0 hours to obtain the catalyst intermediate, denoted as TM-4.

[0055] The catalyst obtained by calcining TM-4 at 350°C for 4.0 hours under a nitrogen pressure of 0.2 MPa was designated as Cat-4.

[0056] Comparative Example 1 The preparation of impregnation solution MQ-3 and intermediate M-3 is the same as in Example 3.

[0057] Weigh 15.0g of nickel nitrate hexahydrate and 10.0g of citric acid, dissolve them in deionized water, and bring the volume to 110ml. The resulting impregnation solution is labeled DQ-1.

[0058] The catalyst obtained by impregnating M-3 with DQ-1 and drying it at 120°C for 6.0 hours is designated as DTM-1.

[0059] The catalyst obtained by calcining DTM-1 at 350°C for 4.0 hours under a nitrogen pressure of 0.2 MPa is designated as DCT-1.

[0060] Comparative Example 2 The preparation of intermediate M-3 is the same as in Example 3.

[0061] Weigh out 15.0g of nickel nitrate hexahydrate, 10.0g of citric acid, 6.0g of zinc nitrate hydrate, and 5.0g of 2-pentenoic acid, dissolve them in deionized water, and bring the volume to 110ml. The resulting impregnation solution is labeled DQ-2.

[0062] The catalyst obtained by impregnating M-3 with DQ-2 and drying it at 120°C for 6.0 hours is designated as DTM-2.

[0063] The catalyst obtained by calcining DTM-2 at 350°C for 4.0 hours under a nitrogen pressure of 0.2 MPa was designated as DCT-2.

[0064] Comparative Example 3 The preparation of intermediate M-3 is the same as in Example 3.

[0065] Weigh 15.0g of nickel nitrate hexahydrate, 4.0g of zinc citrate, 5.0g of citric acid, and 5.0g of 2-pentenoic acid, dissolve them in deionized water, and bring the volume to 110ml. The resulting impregnation solution is labeled DQ-3.

[0066] The catalyst obtained by impregnating M-3 with DQ-3 and drying it at 120°C for 6.0 hours is designated as DTM-3.

[0067] The catalyst obtained by calcining DTM-3 at 350°C for 4.0 hours under a nitrogen pressure of 0.2 MPa was designated as DCT-3.

[0068] Comparative Example 4 TM-3 from Example 3 was used as catalyst DCT-4.

[0069] The composition of the catalyst is shown in Table 1.

[0070] Table H2-TPR analysis was performed on catalysts Cat-1, Cat-2, Cat-3, Cat-4, DCT-1, DCT-2, DCT-3, and DCT-4. After baseline subtraction, the ratio of peak areas in each temperature range of 150-650℃ in the spectra is shown in Table 2.

[0071] Table 2. Area statistics for each temperature range of H2-TPR

[0072] Examples 5-8 Cat-1, Cat-2, Cat-3, and Cat-4 were placed in a reaction tube and the reaction was carried out at 210°C, 6.0 MPa, and a hydrogen flow rate of 6.0 ml / min·g. 催化剂 The catalyst was activated under the following conditions. Then, Fischer-Tropsch synthesis oil (properties of the feedstock are shown in Table 3) was introduced into the reaction tube. The reaction pressure was set to 6.0 MPa, the reaction temperature was controlled at 260℃, and the liquid hourly space velocity was 1.0 h⁻¹. -1 The hydrogen-to-oil ratio was 500:1. After 1000 hours of reaction, the composition and properties of the sample were analyzed, and the results are shown in Table 4.

[0073] Comparative Examples 5-8 DCT-1, DCT-2, DCT-3, and DCT-4 were placed in a reaction tube and the reaction was carried out at 210°C, 6.0 MPa, and a hydrogen flow rate of 6.0 ml / min·g. 催化剂 The catalyst was activated under the following conditions: Fischer-Tropsch synthesis oil (properties of the feedstock are shown in Table 3) was then introduced into the reaction tube, the reaction pressure was set to 6.0 MPa, the reaction temperature was controlled at 260 °C, and the liquid hourly space velocity was 1.0 h⁻¹. -1 The hydrogen-to-oil ratio was 500:1. After 1000 hours of reaction, the composition and properties of the sample were analyzed, and the results are shown in Table 4.

[0074] Table 3 Properties of Fischer-Tropsch Synthetic Oils

[0075] Table 4 Reaction Evaluation Results

[0076] As can be seen from the hydrogenation products of Fischer-Tropsch synthesis oil by various catalysts, the present invention provides a catalyst with excellent hydrogenation effect on this low-sulfur and highly unsaturated feedstock.

Claims

1. A hydrogenation catalyst, characterized in that: The hydrogenation catalyst contains at least molybdenum and nickel active metals, metal additives, carbon, and an inorganic refractory oxide support; the metal additives are at least one or more of zinc, copper, magnesium, and gallium, and the H2-TPR of the catalyst should have the following properties: the peak area integral value of the reduction peak in the temperature range of 350-450℃ accounts for more than 50% of the total peak area integral value in the temperature range of 150-650℃, preferably more than 60%, and more preferably 65%-85%.

2. The catalyst according to claim 1, characterized in that: Based on the weight of the final hydrogenation catalyst, the molybdenum content (calculated as oxide) is 5.0%-35%, preferably 10%-30%, more preferably 12%-28%; the carbon content is 0.5%-6.0%, preferably 1.0%-5.5%, more preferably 1.5%-5.0%; the nickel content (calculated as elemental) is 1.0%-6.0%, preferably 1.5%-5.5%, more preferably 2.0%-5.0%; and the metal additive content (calculated as elemental) is 0.2%-4.0%, preferably 0.3%-3.5%, more preferably 0.5%-3.0%.

3. The catalyst according to claim 1, characterized in that: The inorganic refractory oxide support is one or more of alumina, amorphous silica-alumina, macroporous silica, and titanium-silicon composite materials, preferably γ-alumina; based on the weight of the final hydrogenation catalyst, the support mass content is 50%-90%, preferably 55%-85%, and more preferably 60%-80%.

4. A method for preparing a hydrogenation catalyst, characterized in that: The method includes the following: (1) Select or prepare a hydrogenation catalyst support, (2) Introducing metallic molybdenum onto the carrier in step (1); (3) In step (2), an organonickel and organometallic additives are introduced onto an inorganic refractory oxide support for molybdenum, and the final hydrogenation catalyst is obtained after calcination under an inert atmosphere.

5. The method according to claim 4, characterized in that: The carrier in step (1) can be a commercially available product or prepared according to existing technology.

6. The method according to claim 4, characterized in that: In step (2), after introducing metallic molybdenum, it is dried at a temperature of 100-180℃, preferably 120-160℃, for a time of 2-20 hours, preferably 4-16 hours.

7. The method according to claim 6, characterized in that: After drying, the product is calcined at a temperature of 380-600℃, preferably 400-550℃, for a time of 2-12 hours, preferably 3-10 hours.

8. The method according to claim 7, characterized in that: After calcination, reduction is carried out at a hydrogen reduction temperature of 150-500℃, preferably 250-400℃, and a hydrogen reduction pressure of 1.0-12.0MPa, preferably 2.0-10.0MPa.

9. The method according to claim 4, characterized in that: In step (3), the organic groups corresponding to the organonitrile and organometallic additives are organic acid radicals or organic complexes. The organic acid radicals are one or more of malonate, citrate, oxalate, ethylenediaminetetramethylenephosphonate, salicylate, benzoate, and tartrate. The organic complexes are one or more of acetylacetone, EDTA, and NTA.

10. The method according to claim 9, characterized in that: The organic acid radicals or organic complexes corresponding to organonickel and organometallic additives may be the same or different, and it is preferred to use the same organic acid radicals or organic complexes.

11. The method according to claim 4, characterized in that: In step (3), organonickel and organometallic additives are introduced onto the carrier of molybdenum, either separately or simultaneously, preferably simultaneously; more preferably, when introduced simultaneously, the organonickel and organometallic additives correspond to the same organic acid anion or organic complex.

12. The method according to claim 4, characterized in that: In step (3), an organic carbon deposition aid is introduced onto the inorganic refractory oxide carrier of metallic molybdenum introduced in step (2). The organic carbon deposition aid is a substance containing double bonds, preferably one or more of acrylic acid, acrylamide, butenoic acid, butenoamide, 2-pentenoic acid, and 3-hexenoic acid.

13. The method according to claim 4, characterized in that: In step (3), an organic carbon deposition aid is introduced onto the inorganic refractory oxide carrier of metallic molybdenum introduced in step (2), either simultaneously or sequentially with the introduced organic nickel and organic metal aids.

14. The method according to claim 4, characterized in that: In step (3), the heat treatment is divided into two steps. First, the air is dried at a temperature of 80-180℃, preferably 100-160℃, for a drying time of 1-10 hours, preferably 2-8 hours. Then, the air is calcined under nitrogen or inert gas at a temperature of 280-550℃, preferably 300-500℃, for a calcination time of 1.0-8.0 hours, preferably 2.0-6.0 hours.

15. A method for hydrogenating low-sulfur feedstock oil, characterized in that: Using any one of the hydrogenation catalysts of claims 1-3, low-sulfur oil is introduced into the reduced hydrogenation catalyst to carry out the hydrogenation reaction.

16. The method according to claim 15, characterized in that: The low-sulfur oil has a sulfur content between 0 and 200 ppm and a bromine index between 1000 and 100000 mg Br·100g. -1 between.

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