A method for preparing a hydrogenation catalyst

Abstract

This invention discloses a method for preparing a hydrotreating catalyst, the method comprising the following steps: (1) preparing or selecting a sulfidation catalyst; (2) introducing an organic complex formed by an amino group and a nickel ion into the sulfidation catalyst prepared in step (1); (3) activating the final hydrotreating catalyst by introducing a sulfidating agent into the material obtained in step (2) under a hydrogen atmosphere. The catalyst prepared by this method exhibits significantly improved long-term operational stability.

Description

Technical Field

[0001] This invention relates to a method for preparing a hydrogenation catalyst, and more specifically to a method for preparing a highly stable hydrogenation catalyst. Background Technology

[0002] Currently, industrially used hydrogenation catalysts are mainly sulfide-based catalysts with Group VIB and Group VIII metals as the active phase. During use, the reactivity of these catalysts gradually decreases over time, requiring increasingly stringent operating conditions to maintain initial reaction activity. This not only increases operating costs but also significantly shortens the catalyst's expected lifespan, especially with low-quality oils or older equipment. Therefore, improving the stability of catalysts during use is of paramount importance.

[0003] CN107457006A discloses a method for improving the stability of a hydrogenation catalyst by impregnating it with an impregnation solution containing olefins and / or aromatics. This technique of pretreating the active phase after sulfidation with aromatics essentially passivates the high-activity sites of the catalyst, resulting in a waste of highly active catalytic sites. When processing heavier oil products, the effect will be affected.

[0004] CN112844417A discloses a post-treatment method for a sulfurized hydrotreating catalyst, which involves mixing industrial white oil with automotive diesel oil and then impregnating the sulfurized hydrotreating catalyst. This method forms a coating layer on the inner and outer surfaces of the sulfurized hydrotreating catalyst, improving its stability in the initial stages of use. While this method pre-covers the highly active sites and allows them to act slowly during use, thus improving catalyst stability, it does not fundamentally extend the lifespan of these highly active sites throughout the entire catalytic cycle. The improved stability comes at the cost of reduced catalyst activity.

[0005] CN102311765A discloses a start-up sulfidation method for a type II active site hydrogenation catalyst in a trickle bed: sulfided oil is introduced at the bottom of the reactor to wet the type II active site hydrogenation catalyst; then a sulfiding agent is gradually injected into the sulfided oil, and the temperature is continued to rise to complete the sulfidation. This method is beneficial for increasing the number of type II active sites, thereby improving the catalyst activity. However, the active sites produced by this method are highly active metastable active sites, with high initial activity but poor stability, which will affect the long-term use of the catalyst. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a method for preparing a hydrogenation catalyst, which significantly improves the long-term operational stability of the catalyst prepared by the method.

[0007] A method for preparing a hydrotreating catalyst, the method comprising the following steps:

[0008] (1) Prepare or select a sulfidation catalyst;

[0009] (2) An organic complex formed by amino-containing anions and nickel ions is introduced into the sulfidation catalyst prepared in step (1).

[0010] (3) The final hydrogenation catalyst is obtained by passing a sulfurizing agent into the material obtained in step (2) under a hydrogen atmosphere for activation.

[0011] In step (1) of the method of the present invention, the sulfidation catalyst can be a commercially available product or prepared according to existing technology. The preparation method is to prepare or select an oxidized catalyst and then sulfidate it.

[0012] Furthermore, the aforementioned oxidized catalyst contains Group VIB metals in a +6 oxidation state accounting for 10%-30% of the total catalyst mass, preferably 14%-28%; Group VIII metals in a +2 oxidation state accounting for 2%-6% of the total catalyst mass, preferably 3%-5%; and the support portion accounting for 65%-85% of the total catalyst mass, preferably 67%-83%. The support can be alumina, amorphous silica-alumina, titanium dioxide-alumina materials, etc., and may further contain modifying elements such as silicon, phosphorus, fluorine, and boron.

[0013] Furthermore, vulcanization can be carried out using wet or dry methods, with wet vulcanization being preferred. The vulcanizing agent used is a mixed solution of a sulfur-containing substance and a solvent. The sulfur-containing substance is one or more of carbon disulfide, dimethyl disulfide, dimethyl sulfoxide, and diethylene sulfoxide, while the solvent is cyclohexane, toluene, petroleum ether, n-heptane, xylene, refined kerosene, refined diesel oil, etc. The sulfur-containing substance in the vulcanizing agent has a mass fraction of 0.5%-5.0%, preferably 1%-3%, with the remainder being solvent. During the vulcanization process, the flow rate of the vulcanizing agent is 0.2-4.0 ml / h·g. -1 The catalyst is preferably 0.5-2.0 ml / h·g. -1 catalyst.

[0014] Furthermore, the hydrogen pressure during sulfidation is 1.0-10.0 MPa, preferably 2.0-6.0 MPa, and the hydrogen flow rate is 5.0-40.0 ml / min·g. -1 The catalyst is preferably 10.0-30.0 ml / min·g. -1 catalyst.

[0015] Furthermore, a programmed temperature rise is adopted, with an initial temperature of 0-80℃, preferably 20-60℃, a heating rate of 0.1-3.0℃ / min, preferably 0.2-2.0℃ / min, a target temperature of 200-320℃, preferably 220-280℃, and a duration of 1.0-8.0 hours, preferably 2.0-4.0 hours.

[0016] In step (2) of the method of the present invention, a nickel-ammonia-acid complex solution is introduced into the sulfide catalyst obtained in step 1 under a certain temperature and inert gas atmosphere. For example, this can be carried out under an inert gas such as nitrogen or argon. The pressure of the inert gas is 0.1-1.0 MPa, preferably 0.2-0.8 MPa, and the flow rate of the inert gas is 2.0-50.0 ml / min·g. -1 The catalyst is preferably 5.0-40.0 ml / min·g. -1 catalyst.

[0017] In step (2) of the method of the present invention, the organic complex formed by the amino acid anion and nickel ion includes one or more of EDTA nickel, nickel aminetrimethylenephosphonate, nickel ethylenediaminetetramethylenephosphate, nickel aminetriacetate, nickel aminetrimethylenephosphonate, and nickel hexamethylenediaminetetramethylenephosphonate. The organic complex formed by the amino acid anion and nickel ion is dispersed in a solvent, which is one or more of acetone, ethanol, toluene, cyclohexane, petroleum ether, xylene, and n-heptane. The mass fraction of the nickel-amine-acid complex is 0.2%-5.0%, preferably 0.5%-3.0%, with the remainder being solvent. The amount of solution used is 0.5-10.0 ml / h·g. -1 The catalyst is preferably 2.0-6.0 ml / h·g. -1 catalyst.

[0018] Furthermore, under a certain temperature and an inert gas atmosphere, the reaction temperature for introducing a nickel-ammonia-acid complex solution into the sulfidated catalyst obtained in step 1 is 10-60°C, preferably 20-50°C, and the reaction time is 1.0-10.0 hours, preferably 2.0-6.0 hours.

[0019] In step (3) of the method of the present invention, the material obtained in step (2) is activated under hydrogen pressure and the action of a sulfiding agent (low-sulfur solution). The hydrogen pressure is 0.5-10.0 MPa, preferably 1.0-8.0 MPa, and the hydrogen flow rate is 2.0-10.0 ml / min·g. -1 The preferred concentration is 3.0-8.0 ml / min·g. -1The reaction temperature is 160°C. The low-sulfur solution is a mixed solution of a sulfur-containing substance and a solvent. The sulfur-containing substance is one or more of carbon disulfide, dimethyl disulfide, dimethyl sulfoxide, and diethylene sulfoxide. The solvent is cyclohexane, toluene, petroleum ether, n-heptane, refined kerosene, refined diesel oil, etc. In the vulcanizing agent, the mass fraction of the sulfur-containing substance is 0.1%-1.0%, preferably 0.2%-0.5%, with the remainder being solvent. During the vulcanization process, the flow rate of the vulcanizing agent is 0.1-2.0 ml / h·g. -1 The catalyst is preferably 0.3-1.0 ml / h·g. -1 Catalyst. 150-300℃, preferably 180-280℃. Reaction time is 1.0-8.0 hours, preferably 2.0-6.0 hours.

[0020] Through in-depth research, the inventors discovered that the initial activity and long-term stability of catalysts are often compromised during the design and development of catalysts. In sulfide-state hydrogenation catalysts, the most active sites are located at the edges of the active phase where they contact the acidic centers of the support. These sites exhibit both strong hydrogenation activity and strong acidity. Their tendency to deactivate during reaction is often due to the acidity being stronger than the hydrogenation activity, leading to carbon deposition. Introducing hydrogenation-active metals directionally near these acidic centers to enhance hydrogenation activity can not only improve the catalytic performance at these sites and appropriately modify the acidity, but also prevent carbon deposition at these highly active catalytic sites during use, achieving the dual goal of improving both catalyst activity and selectivity. Following this approach, this invention provides a method for stabilizing and improving the high-energy active centers of hydrogenation catalysts. First, the oxidized catalyst undergoes pre-sulfidation treatment, which generates many strongly acidic, highly active, metastable active centers. Second, these active centers are treated with a nickel complex containing amino groups. The amino groups in the complex guide the adsorption of the complex onto these strongly acidic, highly active centers. The third step involves hydrogen reduction of the complex, which reduces metallic nickel to the vicinity of these strong acid-highly active sites, thereby modifying the acidity of the active sites and improving their stability. To prevent the already produced active phase from being reduced, a low-sulfur solution is also introduced during this process to protect the active phase. Implementation

[0021] The effects and functions of the present invention are further illustrated below with reference to embodiments and comparative examples, but the following embodiments do not constitute a limitation on the method of the present invention.

[0022] In the embodiments and comparative examples of this invention, the preparation method of the oxidized catalyst is as follows: 2000.0 g of alumina dry gel powder was weighed, and 60.0 g of citric acid, 50.0 g of ammonium dihydrogen phosphate, 50.0 g of guar gum powder, and 60.0 g of silica sol were added. After mixing evenly, 1800.0 g of an aqueous solution containing 2.0% nitric acid by mass was added. After rolling for 15.0 min, the mixture was extruded using a cloverleaf perforated plate with a diameter of 1.8 mm. After drying at 120℃ for 6.0 h, the mixture was calcined at 600℃ for 4.0 h. The resulting support is denoted as S-0.

[0023] Take 300.0 g of ammonium heptamolybdate and 200.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 1000 ml solution. The prepared solution is denoted as Q-0.

[0024] Take 1000.0 g of S-0, impregnate it with Q-0, then dry it at 120℃ for 4 hours, and calcine it at 420℃ for 4 hours. The resulting catalyst is denoted as C-0.

[0025] Analysis revealed that the mass fraction of MoO3 in catalyst C-0 was 18.53%, and the mass fraction of nickel oxide was 3.87%.

[0026] Example 1:

[0027] Take 400.0 g of cyclohexane and 8.0 g of carbon disulfide, and prepare a sulfidation liquid, denoted as SL-1.

[0028] Take 400.0 g of cyclohexane and 4.0 g of nickel trimethylphosphonate to prepare a complex solution, which is denoted as NL-1.

[0029] Take 400.0 g of cyclohexane and 1.2 g of carbon disulfide to prepare a protective solution, which is denoted as PL-1.

[0030] 20.0 g of C-0 was placed into a reaction tube for initial vulcanization. During the vulcanization process, the flow rate of the vulcanizing liquid SL-1 was 20 ml / h, the hydrogen pressure was 4.0 MPa, and the hydrogen flow rate was 300 ml / h. The initial temperature was 40℃, the heating rate was 1.5℃ / min, the temperature was increased to 250℃, and then stabilized for 3.0 hours.

[0031] The temperature of the reaction tube was lowered to 40°C, and nitrogen gas was introduced into the reaction tube at a pressure of 0.5 MPa and a flow rate of 200.0 ml / min. At the same time, NL-1 was introduced into the reaction tube at a flow rate of 50.0 ml / h for 5.0 hours.

[0032] Hydrogen gas was introduced into the reaction tube, and the reaction pressure was controlled at 4.0 MPa, with a hydrogen flow rate of 60.0 ml / min. Simultaneously, PL-1 was introduced into the reaction tube at a flow rate of 10.0 ml / h, and the temperature of the reaction tube was raised to 240℃ and maintained for 4.0 hours. The resulting catalyst was designated Cat-1.

[0033] Example 2:

[0034] Take 400.0 g of n-heptane and 10.0 g of dimethyl disulfide, and prepare a sulfidation solution, denoted as SL-2.

[0035] Take 400.0 g of n-heptane and 5.0 g of ethylenediaminetetramethylene nickel phosphate to prepare a complex solution, which is denoted as NL-2.

[0036] Take 400.0 g of n-heptane and 1.6 g of dimethyl disulfide to prepare a protective solution, which is denoted as PL-2.

[0037] 20.0 g of C-0 was placed into a reaction tube for initial vulcanization. During the vulcanization process, the flow rate of the vulcanizing liquid SL-2 was 30 ml / h, the hydrogen pressure was 5.0 MPa, and the hydrogen flow rate was 350 ml / h. The initial temperature was 40℃, the heating rate was 1.0℃ / min, the temperature was increased to 240℃, and then stabilized for 4.0 hours.

[0038] The temperature of the reaction tube was raised to 50°C, and nitrogen gas was introduced into the reaction tube at a controlled pressure of 0.6 MPa and a flow rate of 180.0 ml / min. At the same time, NL-2 was introduced into the reaction tube at a flow rate of 60.0 ml / h for 4.5 hours.

[0039] Hydrogen gas was introduced into the reaction tube, and the reaction pressure was controlled at 5.0 MPa, with a hydrogen flow rate of 80.0 ml / min. Simultaneously, PL-2 was introduced into the reaction tube at a flow rate of 10.0 ml / h, and the temperature of the reaction tube was raised to 230℃ and maintained for 4.0 hours. The resulting catalyst was designated Cat-2.

[0040] Example 3:

[0041] Take 400.0 g of toluene and 15.0 g of dimethyl sulfoxide, and prepare a sulfidation solution, denoted as SL-3.

[0042] Take 400.0 g of toluene and 6.0 g of nickel hexamethylenediaminetetramethylenephosphonate to prepare a complex solution, which is denoted as NL-3.

[0043] Take 400.0 g of n-heptane and 2.0 g of dimethyl sulfoxide to prepare a protective solution, which is denoted as PL-3.

[0044] 20.0 g of C-0 was placed into a reaction tube for initial vulcanization. During the vulcanization process, the flow rate of the vulcanizing liquid SL-3 was 40 ml / h, the hydrogen pressure was 4.0 MPa, and the hydrogen flow rate was 320 ml / h. The initial temperature was 30℃, the heating rate was 1.5℃ / min, the temperature was increased to 250℃, and then stabilized for 3.0 hours.

[0045] The temperature of the reaction tube was raised to 40°C, and nitrogen gas was introduced into the reaction tube at a controlled pressure of 0.8 MPa and a flow rate of 150.0 ml / min. At the same time, NL-3 was introduced into the reaction tube at a flow rate of 50.0 ml / h for 6.0 hours.

[0046] Hydrogen gas was introduced into the reaction tube, and the reaction pressure was controlled at 4.0 MPa, with a hydrogen flow rate of 100.0 ml / min. Simultaneously, PL-3 was introduced into the reaction tube at a flow rate of 12.0 ml / h, and the temperature of the reaction tube was raised to 260℃ and maintained for 5.0 hours. The resulting catalyst was designated Cat-3.

[0047] Example 4:

[0048] Take 400.0 g of petroleum ether and 12.0 g of diethyl sulfoxide, and prepare a sulfidation solution, denoted as SL-4.

[0049] Take 400.0 g of petroleum ether and 6.0 g of nickel triacetate to prepare a complex solution, which is denoted as NL-4.

[0050] Take 400.0 g of petroleum ether and 1.6 g of diethyl sulfoxide to prepare a protective solution, which is denoted as PL-4.

[0051] 20.0 g of C-0 was placed into a reaction tube for initial vulcanization. During the vulcanization process, the flow rate of the vulcanizing liquid SL-4 was 50 ml / h, the hydrogen pressure was 5.0 MPa, and the hydrogen flow rate was 270 ml / h. The initial temperature was 50℃, the heating rate was 1.0℃ / min, the temperature was increased to 240℃, and then stabilized for 4.0 hours.

[0052] Maintain the reaction tube temperature at 50℃, introduce nitrogen gas into the reaction tube, control the pressure at 0.6 MPa, and the nitrogen flow rate at 120.0 ml / min. At the same time, introduce NL-4 into the reaction tube at a flow rate of 60.0 ml / h for 4.0 hours.

[0053] Hydrogen gas was introduced into the reaction tube, and the reaction pressure was controlled at 6.0 MPa, with a hydrogen flow rate of 80.0 ml / min. Simultaneously, PL-4 was introduced into the reaction tube at a flow rate of 16.0 ml / h, and the temperature of the reaction tube was raised to 250°C and maintained for 6.0 hours. The resulting catalyst was designated Cat-4.

[0054] Comparative Example 1:

[0055] 20.0 g of C-0 was loaded into a reaction tube for sulfidation. During sulfidation, the flow rate of the sulfidation liquid was 50 ml / h, the hydrogen pressure was 5.0 MPa, and the hydrogen flow rate was 280 ml / h. The initial temperature was 50℃, the heating rate was 3.0℃ / min, the temperature was increased to 340℃, and then stabilized for 80 hours. The prepared catalyst is designated as DCT-1.

[0056] Comparative Example 2:

[0057] Take 400.0 g of cyclohexane and 10.0 g of carbon disulfide to prepare a sulfidation liquid, denoted as DSL-2.

[0058] Take 400.0 g of cyclohexane and 5.0 g of nickel citrate to prepare a complex solution, which is denoted as DNL-2.

[0059] Take 400.0 g of cyclohexane and 2.0 g of carbon disulfide to prepare a protective solution, which is denoted as DPL-2.

[0060] 20.0 g of C-0 was placed into a reaction tube for initial vulcanization. During the vulcanization process, the flow rate of the vulcanizing liquid DSL-2 was 20 ml / h, the hydrogen pressure was 4.0 MPa, and the hydrogen flow rate was 300 ml / h. The initial temperature was 40℃, the heating rate was 1.5℃ / min, the temperature was increased to 250℃, and then stabilized for 3.0 hours.

[0061] The temperature of the reaction tube was lowered to 40°C, and nitrogen gas was introduced into the reaction tube at a pressure of 0.5 MPa and a flow rate of 200.0 ml / min. At the same time, DNL-2 was introduced into the reaction tube at a flow rate of 50.0 ml / h for 5.0 hours.

[0062] Hydrogen gas was introduced into the reaction tube, and the reaction pressure was controlled at 4.0 MPa, with a hydrogen flow rate of 60.0 ml / min. Simultaneously, DPL-2 was introduced into the reaction tube at a flow rate of 10.0 ml / h, and the temperature of the reaction tube was raised to 240℃ and maintained for 4.0 hours. The resulting catalyst was designated DCT-2.

[0063] Comparative Example 3:

[0064] Take 400.0 g of cyclohexane and 20.0 g of dimethyl disulfide, and prepare a sulfidation solution, denoted as DSL-3.

[0065] Take 400.0 g of cyclohexane and 10.0 g of nickel trimethylphosphonate to prepare a complex solution, which is denoted as DNL-3.

[0066] Take 20.0 g of C-0 and put it into a reaction tube. Control the temperature at 40°C and introduce nitrogen gas into the reaction tube. Control the pressure at 0.5 MPa and the nitrogen flow rate at 200.0 ml / min. At the same time, introduce DNL-3 into the reaction tube at a flow rate of 50.0 ml / h for 5.0 hours.

[0067] The reaction pressure was controlled at 4.0 MPa, and the hydrogen flow rate was 200.0 ml / min. Simultaneously, DPL-3 was introduced into the reaction tube at a flow rate of 30.0 ml / h, and the temperature of the reaction tube was raised to 340℃ and maintained for 5.0 hours. The resulting catalyst was designated DCT-3.

[0068] The catalyst metal composition analysis of catalysts Cat-1, Cat-2, Cat-3 and Cat-4, DCT-1, DCT-2 and DCT-3 was performed, and the results are shown in Table 1.

[0069] Table 1. Catalyst Metal Composition Analysis

[0070]

[0071] Acidic NH3-TPD analysis was performed on catalysts Cat-1, Cat-2, Cat-3 and Cat-4, DCT-1, DCT-2 and DCT-3, and the results are shown in Table 2.

[0072] Table 2

[0073]

[0074] The catalyst was evaluated and characterized using raw materials shown in Table 3.

[0075] Table 3

[0076]

[0077] The catalyst evaluation conditions were: reaction temperature 370℃, reaction pressure 14.0 MPa, and liquid hourly space velocity 1.0 h⁻¹. -1 With a hydrogen-to-oil ratio of 1000:1, samples were taken and analyzed after 50 hours and 1000 hours of evaluation, and the results are shown in Table 4.

[0078] Table 4

[0079]

[0080] The evaluation results show that the catalyst modified with complexed nickel exhibits catalytic activity that is very close to that after 1000 hours of evaluation compared to after 50 hours, indicating that the catalyst has good activity stability.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that: The method includes the following steps: (1) Prepare or select a sulfidation catalyst; (2) Introduce an organic complex formed by an amino group and a nickel group into the sulfidation catalyst of step (1). (3) The final hydrogenation catalyst is obtained by passing a sulfurizing agent into the material obtained in step (2) under a hydrogen atmosphere for activation.

2. The method according to claim 1, characterized in that: The sulfidation catalyst mentioned in step (1) is prepared using commercially available products or according to existing technology. The preparation method is to first prepare or select an oxidized catalyst, and then obtain it through sulfidation.

3. The method according to claim 2, characterized in that: The oxidized catalyst contains Group VIB metals in the +6 oxidation state, accounting for 10%-30% of the total catalyst mass; Group VIII metals in the +2 oxidation state, accounting for 2%-6% of the total catalyst mass; and the support portion accounts for 65%-85% of the total catalyst mass.

4. The method according to claim 3, characterized in that: The oxidized catalyst contains Group VIB metals in the +6 oxidation state, accounting for 14%-28% of the total catalyst mass; Group VIII metals in the +2 oxidation state, accounting for 3%-5% of the total catalyst mass; and the support portion accounts for 67%-83% of the total catalyst mass.

5. The method according to claim 3, characterized in that: The carrier is aluminum oxide, amorphous silicon aluminum or titanium oxide-alumina material.

6. The method according to claim 5, characterized in that: The carrier further contains silicon, phosphorus, fluorine, or boron.

7. The method according to claim 2, characterized in that: In step (1), the vulcanization is carried out by wet vulcanization or dry vulcanization; the vulcanizing agent used is a mixed solution of sulfur-containing substances and solvents, wherein the sulfur-containing substances are one or more of carbon disulfide, dimethyl disulfide, dimethyl sulfoxide, and diethyl sulfoxide, and the solvents are one or more of cyclohexane, toluene, petroleum ether, n-heptane, xylene, refined kerosene, and refined diesel.

8. The method according to claim 7, characterized in that: In step (1), wet vulcanization is used.

9. The method according to claim 7, characterized in that: In step (1), the sulfur-containing substance has a mass fraction of 0.5%-5.0%, and the remainder is solvent.

10. The method according to claim 9, characterized in that: In step (1), the sulfur-containing substance in the vulcanizing agent has a mass fraction of 1%-3%, and the remainder is a solvent.

11. The method according to claim 7, characterized in that: The flow rate of the vulcanizing agent in the vulcanization process in Step (1) is 0.2-4.0 ml / h·g -1 Catalyst; the pressure of hydrogen is 1.0-10.0 MPa, and the flow rate of hydrogen is 5.0-40.0 ml / min·g -1 Catalyst.

12. The method according to claim 11, characterized in that: In step (1), the flow rate of the vulcanizing agent during the vulcanization process is 0.5-2.0 ml / h·g. -1 Catalyst; hydrogen pressure 2.0-6.0 MPa, hydrogen flow rate 10.0-30.0 ml / min·g -1 catalyst.

13. The method according to claim 7, characterized in that: In step (1), the vulcanization process adopts programmed temperature rise, with an initial temperature of 0-80℃, a heating rate of 0.1-3.0℃ / min, a target temperature of 200-320℃, and a duration of 1.0-8.0 hours.

14. The method according to claim 13, characterized in that: In step (1), the vulcanization process adopts a programmed temperature rise, with an initial temperature of 20-60℃, a heating rate of 0.2-2.0℃ / min, a target temperature of 220-280℃, and a duration of 2.0-4.0 hours.

15. The method according to claim 1, characterized in that: In step (2), under a certain temperature and an inert gas atmosphere, an organic complex formed by amino acid radical ions and nickel ions is introduced into the sulfidation catalyst obtained in step (1).

16. The method according to claim 15, characterized in that: The experiment is conducted under an inert gas such as nitrogen or argon, with a pressure of 0.1–1.0 MPa and a flow rate of 2.0–50.0 ml / min·g. -1 catalyst.

17. The method according to claim 16, characterized in that: The experiment is conducted under an inert gas such as nitrogen or argon, with a pressure of 0.2–0.8 MPa and a flow rate of 5.0–40.0 ml / min·g. -1 catalyst.

18. The method according to claim 1, characterized in that: In step (2), the organic complex formed by the amino acid anion and the nickel ion is selected from one or more of EDTA nickel, nickel aminetrimethylenephosphonate, nickel ethylenediaminetetramethylenephosphate, nickel aminetriacetate, nickel aminetrimethylenephosphonate, and nickel hexamethylenediaminetetramethylenephosphonate.

19. The method according to claim 18, characterized in that: An organic complex formed by an amino-containing acid radical ion and a nickel ion is dispersed in a solvent, wherein the solvent is one or more selected from acetone, ethanol, toluene, cyclohexane, petroleum ether, xylene, and n-heptane. The mass fraction of the organic complex formed by the amino-containing acid radical ion and the nickel ion is 0.2%-5.0%, with the remainder being the solvent. The volume of solution used is 0.5-10.0 ml / h·g. -1 catalyst.

20. The method according to claim 19, characterized in that: in, The mass fraction of the organic complex formed by the amino-containing anion and nickel ion is 0.5%-3.0%, with the remainder being solvent. The solution usage is 2.0-6.0 ml / h·g. -1 catalyst.

21. The method according to claim 1, characterized in that: Under a certain temperature and an inert gas atmosphere, an organic complex formed by amino acid radical ions and nickel ions is introduced into the sulfidation catalyst obtained in step (1). The reaction temperature is 10-60℃ and the reaction time is 1.0-10.0 hours.

22. The method according to claim 21, characterized in that: Under a certain temperature and inert gas atmosphere, an organic complex formed by amino-containing acid radical ions and nickel ions is introduced into the sulfidation catalyst obtained in step (1). The reaction temperature is 20-50℃ and the reaction time is 2.0-6.0 hours.

23. The method according to claim 1, characterized in that: Step (3) involves activating the material obtained in step (2) under hydrogen pressure and the action of a sulfiding agent.

24. The method according to claim 23, characterized in that: In step (3), the hydrogen pressure is 0.5-10.0 MPa and the hydrogen flow rate is 2.0-10.0 ml / min·g. -1 The reaction temperature is 120-180℃, and the vulcanizing agent is a mixed solution of sulfur-containing substances and solvents. The sulfur-containing substances are one or more of carbon disulfide, dimethyl disulfide, dimethyl sulfoxide, and diethyl sulfoxide, and the solvents are one or more of cyclohexane, toluene, petroleum ether, n-heptane, refined kerosene, and refined diesel oil.

25. The method according to claim 24, characterized in that: In step (3), the hydrogen pressure is 1.0-8.0 MPa and the hydrogen flow rate is 3.0-8.0 ml / min·g. -1 .

26. The method according to claim 24, characterized in that: In step (3), the sulfur-containing substance in the vulcanizing agent has a mass fraction of 0.1%-1.0%, with the remainder being solvent; during the vulcanization process, the flow rate of the vulcanizing agent is 0.1-2.0 ml / h·g. -1 The catalyst is used, the reaction temperature is 150-300℃, and the reaction time is 1.0-8.0 hours.

27. The method according to claim 26, characterized in that: In step (3), the sulfur-containing substance in the vulcanizing agent has a mass fraction of 0.2%-0.5%, with the remainder being solvent; during the vulcanization process, the flow rate of the vulcanizing agent is 0.3-1.0 ml / h·g. -1 The catalyst is used, the reaction temperature is 180-280℃, and the reaction time is 2.0-6.0 hours.

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