A method for activating a hydrofining catalyst for hydrocarbon oils

Abstract

The application discloses a kind of hydrorefining catalyst activation methods of hydrocarbon oil.The method includes the process of reduction to hydrorefining catalyst of hydrocarbon oil, wherein, the hydrorefining catalyst includes alumina carrier, metal molybdenum, organic nickel and organic metal auxiliary agent, the metal auxiliary agent is at least one or several of zinc, copper, magnesium, gallium, with the weight of final hydrogenation catalyst as basis, the mass content of organic nickel is 0.1% to 4.0%, preferably 0.2% to 3.0%, further preferably 0.5% to 2.0%, with the metal auxiliary agent element as basis, the mass content of organic metal auxiliary agent is 0.05% to 2.5%, preferably 0.1% to 2.0%, further preferably 0.2% to 1.5%.The method has the advantages of time-saving and high efficiency, without adding sulfidation agent, and more simple and convenient to switch raw materials.

Description

Technical Field

[0001] This invention relates to an activation method for a hydrocarbon oil hydrorefining catalyst, specifically a time-saving and efficient activation method for a hydrocarbon oil hydrorefining catalyst that eliminates the need for adding sulfiding agents and simplifies feedstock switching. Background Technology

[0002] Diesel hydrorefining technology, as a core strategy for improving fuel quality and reducing environmental pollution in the modern oil refining industry, relies heavily on the effective conversion and application of catalysts for its core efficiency. Catalysts typically remain in an oxidized state at the production stage; however, for conventional diesel hydrorefining to exert its hydrorefining activity, it must undergo a critical conversion process called sulfidation start-up to transform into a sulfidized state. This maximizes its catalytic activity, promoting the effective conversion of harmful components in diesel fuel, such as unsaturated hydrocarbons, sulfur-containing and nitrogen-containing compounds, into cleaner products that are easier to process.

[0003] In the vulcanization start-up process, the introduction of vulcanizing agents constitutes an indispensable core step. Traditional vulcanizing agents such as dimethyl disulfide (DMDS) and carbon disulfide (CS2), while effectively providing the sulfur required for vulcanization, significantly increase the complexity and risk of the operation due to their hazardous chemical properties. From a logistical perspective, the transportation of these vulcanizing agents must strictly comply with national safety and environmental regulations, involving special packaging, clear labeling, and specific transportation methods, which not only increases transportation costs but also poses a potential risk of environmental pollution. During the usage phase, even more stringent requirements are placed on operator safety measures, emergency response mechanisms, and waste disposal; any negligence could trigger a safety accident or environmental crisis.

[0004] Furthermore, the sulfidation start-up process is technically demanding and time-consuming, requiring operators with advanced professional skills and extensive practical experience. Precise temperature control and a programmed heating strategy are crucial for gradually activating the catalyst's active sites, ensuring the uniformity and sufficiency of the sulfidation process. Simultaneously, real-time monitoring of H2S concentration changes in the circulating hydrogen becomes a key basis for adjusting the amount of sulfiding agent injected, placing extremely high demands on operational precision and efficiency. After catalyst sulfidation, cooling and straight-run diesel stabilization stages (1-2 days) are still required. However, prolonged unconventional operation undoubtedly weakens the company's production efficiency and economic benefits.

[0005] To address the complexity and challenges of traditional sulfidation start-up processes, researchers have innovatively developed sulfur-supported and fully sulfidated hydrotreating catalysts. These catalysts accelerate the start-up process to some extent by pre-introducing the sulfidation step during catalyst production, aiming to simplify on-site operations. However, it is worth noting that while this method shifts the sulfidation burden to the production source, it does not fundamentally eliminate economic costs and environmental pressures, as the sulfidation process itself still involves resource consumption and potential environmental risks. Furthermore, since sulfur-supported and fully sulfidated catalysts already contain sulfiding agents or possess activity at the factory, they also introduce additional safety hazards during transportation, storage, and equipment installation, increasing operational complexity.

[0006] CN103789009A discloses a wet start-up method for a hydrocracking unit. This method is characterized by blending a portion of light distillate oil with high olefin content into the start-up oil. The exothermic hydrogenation of olefins eliminates the need for a heating furnace, simplifying the start-up process. However, the overall process still requires operations such as injecting a sulfiding agent.

[0007] CN105754637A discloses a wet start-up method for a hydrocracking unit. This method is characterized by blending a portion of light distillate oil with high olefin content into the start-up oil. The exothermic hydrogenation of olefins eliminates the need for a heating furnace, simplifying the start-up process. However, the overall process still requires operations such as injecting a sulfiding agent.

[0008] CN103773436A discloses a start-up method for an externally pre-sulfurized type II active center hydrogenation catalyst. This method is characterized by adjusting the load of the circulating hydrogen compressor to 0-20% of its maximum load after the unit is sealed, releasing heat at low temperatures, and simplifying the start-up process of the pre-sulfurized hydrogenation catalyst by utilizing the catalyst's characteristics. However, essentially, the diesel hydrogenation catalyst still needs to be sulfidated to achieve its activity. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides an activation method for a hydrocarbon oil hydrorefining catalyst. This method is characterized by being time-saving, highly efficient, requiring no sulfiding agent, and offering a simpler feedstock switching process.

[0010] This invention discloses an activation method for a hydrocarbon oil hydrorefining catalyst. The method includes a reduction process of the hydrocarbon oil hydrorefining catalyst, wherein the hydrorefining catalyst comprises an alumina support, metallic molybdenum, organonickel, and an organometallic auxiliary. The auxiliary is at least one or more of zinc, copper, magnesium, and gallium. Based on the weight of the final hydrorefining catalyst, the organonickel contains 0.1%-4.0% by mass, preferably 0.2%-3.0%, more preferably 0.5%-2.0% by mass, based on elemental nickel content; the organometallic auxiliary contains 0.05%-2.5% by mass, preferably 0.1%-2.0%, more preferably 0.2%-1.5% by mass, based on elemental metal content.

[0011] In the method of the present invention, the reduction can be carried out in a hydrogen-containing atmosphere, which includes reduction in a hydrogen-containing mixture or reduction alone in a hydrogen atmosphere.

[0012] In the method of the present invention, the reduction temperature is 230~330℃, more preferably 250~280℃, the reduction time is 2~24 hours, preferably 3~8 hours, and the partial pressure of reduced hydrogen is 0.1~20.0MPa, preferably 2.0~10.0MPa.

[0013] In the method of the present invention, the hydrocarbon oil hydrorefining catalyst can be first loaded into a fixed bed reactor, and then reduced after being sealed with an inert gas, nitrogen and / or hydrogen.

[0014] In the method of the present invention, a stable oil fraction can be introduced at a temperature of 70~200℃, more preferably 120~160℃, and then the temperature is further increased to the reduction temperature.

[0015] In the method of the present invention, the stabilized oil fraction may be one or more of straight-run jet fuel, straight-run diesel, hydrotreated diesel fuel, cracked diesel fuel, and hydrotreated refined diesel fuel; the final boiling point of the stabilized oil fraction is ≤375℃, and more preferably ≤360℃.

[0016] In the method of the present invention, there are no special requirements for the heating rate, which is generally 5~30℃ / h, and preferably 3~25℃.

[0017] In the method of this invention, the hydrocarbon oil hydrorefining catalyst, after reduction, can be directly fed into the hydrocarbon oil feedstock for reaction.

[0018] In the method of this invention, the hydrocarbon feedstock can be diesel oil or wax oil, preferably diesel oil. The diesel feedstock is generally a mixture of straight-run diesel oil and secondary diesel oil, and the secondary diesel oil is one or more of coking diesel oil, catalytic diesel oil, residue hydrotreated diesel oil, fluidized bed diesel oil, and slurry bed diesel oil.

[0019] In the method of this invention, the reaction conditions for introducing hydrocarbon oil feedstock are as follows: reaction temperature 300~410℃, operating pressure 3.0~13.0MPa, hydrogen-to-oil volume ratio 100:1~1000:1, and volume hourly space velocity 0.1~10.0h⁻¹. -1 .

[0020] In the method of the present invention, based on the weight of the final hydrogenation catalyst, the mass content of the alumina support is 40%-85%, preferably 45%-80%, and more preferably 50%-75%.

[0021] In the method of the present invention, the alumina carrier is doped with a small amount of one or more of silicon, phosphorus, boron, magnesium and fluorine, and the amount of doping does not exceed 5.0% of the total mass of the carrier.

[0022] In the method of this invention, the pore volume is 0.6~1.3 cm. 3 / g, with a preferred pore volume of 0.7~1.2 cm³. 3 / g, specific surface area is 180-340m² 2 / g, preferably 210-310m 2 / g.

[0023] In the method of the present invention, metallic molybdenum exists in the form of molybdenum salt, molybdenum oxide or elemental molybdenum. Based on the weight of the final hydrogenation catalyst, the mass content of metallic molybdenum, calculated as molybdenum element, is 3.0%-25%, preferably 4.0%-20%, and more preferably 5.0%-18.0%.

[0024] In the method of the present invention, 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, tartrate, glycolate, and gluconate. The organic complexes are one or more of acetylacetone, EDTA, NTA, and ethylenediamine.

[0025] In the method of the present invention, the organic acid anions or organic complexes corresponding to the organonickel and organometallic additives may be the same or different, but it is preferred to use the same organic acid anions or organic complexes.

[0026] In the method of the present invention, based on the weight of the final hydrogenation catalyst, the mass content of organic acid anions and / or organic complexes in the catalyst is 4%-20%, preferably 6%-18%.

[0027] In the method of the present invention, the hydrorefining catalyst can be prepared by the following method: (1) Introducing metallic molybdenum onto an alumina carrier; (2) Step (1) Introduce organonickel and organometallic additives onto the inorganic refractory oxide support of molybdenum metal, and then dry them to obtain the final hydrogenation catalyst.

[0028] Furthermore, the introduction of metallic molybdenum in step (1) 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.

[0029] Furthermore, in step (2), the organonickel and organometallic additives introduced onto the alumina support containing molybdenum can be introduced 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.

[0030] Furthermore, in step (2), 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 tartaric acid, citric acid, water, ethanol, acetone, and toluene. During co-impregnation, 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.

[0031] Furthermore, in step (2), the drying temperature is 80-180℃, preferably 100-160℃, and the drying time is 1-10 hours, preferably 2-8 hours.

[0032] The sulfidation start-up of existing diesel hydrorefining units involves sulfiding the catalyst and preparing the unit for operation through a series of precisely controlled temperature ramp-up steps in a hydrogen environment. Specifically, the operation begins with the introduction of straight-run diesel as start-up fuel when the catalyst bed temperature is between 100°C and 160°C, gradually increasing the temperature (at a rate not exceeding 8°C / h) to 230°C. When the catalyst bed temperature reaches the range of 160°C to 200°C, the sulfiding agent is injected into the unit. This stage requires close monitoring, with the H2S concentration in the circulating hydrogen checked every half hour to ensure it reaches the critical threshold of 1000 mg / kg, preventing excessive reduction of the catalyst's active sites to a low valence state and thus maintaining its catalytic activity. Once the H2S concentration reaches the target, the temperature is steadily increased to 230°C and maintained for at least 8 hours to promote complete catalyst sulfidation. Subsequently, the temperature is further increased to 290°C at a rate not exceeding 6°C / h and maintained at this temperature for at least 6 hours. Subsequently, the temperature is increased to 320°C at a rate not exceeding 5°C / h and maintained at this temperature for at least 2 hours to further stabilize the catalyst's activity. After the 320°C isothermal phase, the temperature is slowly reduced to 280-300°C at a rate not exceeding 20°C / h, while gradually switching the start-up fuel oil to the straight-run diesel feedstock required for actual production. The feedstock is stabilized under straight-run diesel conditions for 24-48 hours. After stabilization with straight-run diesel, the current secondary diesel feedstock is switched to for normal production. During this switching process, a sulfiding agent needs to be continuously injected, and the H2S content in the circulating hydrogen needs to be analyzed every half hour. The injection amount of sulfiding agent is adjusted accordingly to ensure that the catalyst maintains optimal activity during the conversion process.

[0033] Compared with existing technologies, the present invention has the following advantages: 1. This patented start-up method eliminates the traditional vulcanizing agent injection step, significantly reducing operating costs for enterprises, especially the procurement cost of vulcanizing agents, and demonstrating significant advantages in environmental protection and safety. Traditional vulcanizing agents such as carbon disulfide (CS2) and dimethyl disulfide (DMDS) pose significant challenges to daily operations due to their high toxicity, strong pungent odor, and low safety. These substances not only increase the difficulty of transportation and storage but also pose a potential threat to the environment and the health and safety of operators. This method also avoids errors in the vulcanization process that could affect the catalyst's activity.

[0034] 2. In conventional start-up processes, the sulfidated catalyst needs to be stabilized with straight-run diesel for 24 to 48 hours before it can be exposed to secondary diesel. However, the active phase of the catalyst in this patent is different from the traditional sulfidated active phase, allowing it to directly process secondary diesel while maintaining stable catalytic activity after start-up.

[0035] 3. This startup method, with its high efficiency, convenience, and safety, revolutionizes the traditional sulfidation startup process. Existing methods require tedious analysis of the H2S content in the circulating hydrogen every half hour to adjust the amount of sulfiding agent injected. This process not only consumes significant manpower but also carries safety risks due to the sampling operation itself. In contrast, the startup method of this invention completely eliminates this step, eliminating the need for sampling and analysis of the H2S content in the circulating hydrogen. This greatly simplifies the operation, reduces labor costs, and improves operational safety. Furthermore, traditional startup methods require the H2S content in the circulating hydrogen to reach at least 1000 mg / kg before heating to the critical temperature of 230°C. This condition not only increases operational uncertainty but also often leads to delays in the startup process, hindering the overall progress. The startup method of this invention is not subject to this limitation, allowing for more flexible and efficient operation. Even under ideal conditions, traditional methods take at least 40 hours, while this method reduces the time to between 10 and 20 hours, achieving a time saving of over 50%. At the same time, it saves 24 to 48 hours of time switching raw materials. This significant time saving advantage not only improves the efficiency of start-up but also reduces the amount of defective products generated during the start-up process, further reducing the company's operating costs and enhancing its market competitiveness. Detailed Implementation

[0036] 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. The properties of the catalysts and feedstocks used in the following embodiments are shown in Tables 1 and 2.

[0037] Table 1. Catalyst Properties in Examples

[0038] Table 1. Main Properties of Stable Oil Fractions and Feedstock Example 1

[0039] The diesel hydrorefining catalyst is SSL-1. A stable oil fraction is introduced into the unit at 120°C, and the catalyst bed temperature is increased to 280°C at a heating rate of 25°C / h for hydrogen reduction. The hydrogen reduction time is 3 hours, and the partial pressure of reduced hydrogen is 10.0 MPa. After reduction, the feedstock is directly switched to a mixed diesel feedstock, which is a mixture of straight-run diesel and slurry-bed diesel, with the slurry-bed diesel proportion being 30% wt. The operating pressure is 10.0 MPa, the hydrogen-to-oil volume ratio is 600:1, and the volume hourly space velocity (VHSV) is 1.0 h⁻¹. -1 Adjust the temperature to normal production. Example 2

[0040] The diesel hydrorefining catalyst is SSL-2. A stable oil fraction is introduced into the unit at 150°C, and the catalyst bed temperature is increased to 250°C at a heating rate of 20°C / h for hydrogen reduction. The hydrogen reduction time is 6 hours, and the partial pressure of reduced hydrogen is 5.0 MPa. After reduction, the feedstock is directly switched to a blended diesel feedstock, which is a mixture of straight-run diesel and catalytic diesel, with the catalytic diesel proportion being 10% wt. The operating pressure is 5.0 MPa, the hydrogen-to-oil volume ratio is 1000:1, and the volume hourly space velocity (VHSV) is 0.6 h⁻¹. -1 Adjust the temperature to normal production. Example 3

[0041] The diesel hydrorefining catalyst is SSL-3. A stable oil fraction is introduced into the unit at 160°C, and the catalyst bed temperature is increased to 260°C at a heating rate of 15°C / h for hydrogen reduction. The hydrogen reduction time is 8 hours, and the partial pressure of reduced hydrogen is 8.0 MPa. After reduction, the feedstock is directly switched to a blended diesel feedstock, which is a mixture of straight-run diesel, catalytic diesel, and slurry-bed diesel, with catalytic diesel accounting for 15% wt and slurry-bed diesel accounting for 5% wt. The operating pressure is 8.0 MPa, the hydrogen-to-oil volume ratio is 800:1, and the volume hourly space velocity (VHSV) is 1.2 h⁻¹. -1 Adjust the temperature to normal production.

[0042] Comparative Example 1 The diesel hydrorefining catalyst is a conventional commercial FHUDS-6 catalyst (with the same metal content as SSL-1). A stable oil fraction is introduced into the unit at 120°C, and the catalyst bed temperature is increased to 280°C at a heating rate of 25°C / h for hydrogen reduction. The hydrogen reduction time is 3 hours, and the partial pressure of reduced hydrogen is 10.0 MPa. After reduction, the feedstock is directly switched to a mixed diesel feedstock, which is a mixture of straight-run diesel and slurry-bed diesel, with the slurry-bed diesel proportion being 30% wt. The operating pressure is 10.0 MPa, the hydrogen-to-oil volume ratio is 600:1, and the volume hourly space velocity (VHSV) is 1.0 h⁻¹. -1 Adjust the temperature to the production temperature of Example 1.

[0043] Comparative Example 2 The diesel hydrorefining catalyst is a conventional commercial FHUDS-6 catalyst (with the same metal content as SSL-1). The catalyst is sulfided using conventional wet sulfidation. After sulfidation, the feedstock is directly switched to a blended diesel mixture, which is a mixture of straight-run diesel and slurry-bed diesel, with the slurry-bed diesel comprising 30% wt. The operating pressure is 10.0 MPa, the hydrogen-to-oil volume ratio is 600:1, and the volume hourly space velocity (VHSV) is 1.0 h⁻¹. -1 Adjust the temperature to the production temperature of Example 1.

[0044] Comparative Example 3 The diesel hydrorefining catalyst is a conventional commercial FHUDS-8 catalyst (with the same metal content as SSL-2). A stable oil fraction is introduced into the unit at 150°C, and the catalyst bed temperature is increased to 250°C at a heating rate of 20°C / h for hydrogen reduction. The hydrogen reduction time is 6 hours, and the partial pressure of reduced hydrogen is 5.0 MPa. After reduction, the feedstock is directly switched to a mixed diesel feedstock, which is a mixture of straight-run diesel and catalytic diesel, with the catalytic diesel proportion being 10% wt. The operating pressure is 5.0 MPa, the hydrogen-to-oil volume ratio is 1000:1, and the volume hourly space velocity (VHSV) is 0.6 h⁻¹. -1 Adjust the temperature to the production temperature of Example 2.

[0045] Comparative Example 4 The diesel hydrorefining catalyst is a conventional commercial FHUDS-8 catalyst (with the same metal content as SSL-2). The catalyst is sulfided using a conventional dry sulfidation process. After sulfidation, the feedstock is directly switched to a blended diesel mixture, which is a mixture of straight-run diesel and catalytic diesel, with the catalytic diesel comprising 10% wt. The operating pressure is 5.0 MPa, the hydrogen-to-oil volume ratio is 1000:1, and the volume hourly space velocity (VHSV) is 0.6 h⁻¹. -1 Adjust the temperature to the production temperature of Example 2. Example 4

[0046] The diesel hydrorefining catalyst is a conventional commercial FHUDS-9 catalyst (with the same metal content as SSL-3). A stable oil fraction is introduced into the unit at 160°C, and the catalyst bed temperature is increased to 260°C at a rate of 15°C / h for hydrogen reduction. The hydrogen reduction time is 8 hours, and the partial pressure of reduced hydrogen is 8.0 MPa. After reduction, the feedstock is directly switched to a blended diesel feedstock, which is a mixture of straight-run diesel, catalytic diesel, and slurry-bed diesel, with catalytic diesel comprising 15% wt and slurry-bed diesel comprising 5% wt. The operating pressure is 8.0 MPa, the hydrogen-to-oil volume ratio is 800:1, and the volume hourly space velocity (VHSV) is 1.2 h⁻¹. -1 Adjust the temperature to the production temperature of Example 3. Example 5

[0047] The diesel hydrorefining catalyst is a conventional commercial FHUDS-9 catalyst (with the same metal content as SSL-3). The catalyst is sulfided using conventional wet sulfidation. After sulfidation, the feedstock is directly switched to a blend of straight-run diesel, catalytic diesel, and slurry-bed diesel, with catalytic diesel comprising 15% wt and slurry-bed diesel comprising 5% wt. The operating pressure is 8.0 MPa, the hydrogen-to-oil volume ratio is 800:1, and the volume hourly space velocity (VHSV) is 1.2 h⁻¹. -1 Adjust the temperature to the production temperature of Example 3.

[0048] Table 3 Results of the Examples

[0049] Table 4 Comparative Results

[0050] The results from the examples and comparative examples show that the start-up method of the diesel hydrorefining catalyst of the present invention can effectively reduce the amount of sulfiding agent used, and at the same reaction temperature, the product quality is significantly improved, bringing significant benefits to enterprises in terms of economic benefits, safe production and environmental protection.

Claims

1. A method for activating a catalyst for the hydrorefining of hydrocarbon oils, characterized in that: The method includes a process of reducing a hydrocarbon oil hydrorefining catalyst, wherein the hydrorefining catalyst comprises an alumina support, metallic molybdenum, organonickel, and an organometallic auxiliary, wherein the auxiliary is at least one or more of zinc, copper, magnesium, and gallium, and based on the weight of the final hydrorefining catalyst, the organonickel has a mass content of 0.1%-4.0% based on nickel element, preferably 0.2%-3.0%, more preferably 0.5%-2.0%; the organometallic auxiliary has a mass content of 0.05%-2.5% based on the auxiliary element, preferably 0.1%-2.0%, more preferably 0.2%-1.5%.

2. The method according to claim 1, characterized in that: The reduction is carried out in a hydrogen-containing atmosphere, which includes reduction in a hydrogen-containing gas mixture or reduction alone in a hydrogen atmosphere.

3. The method according to claim 1, characterized in that: The reduction temperature is 230~330℃, more preferably 250~280℃, the reduction time is 2~24 hours, preferably 3~8 hours, and the partial pressure of reduced hydrogen is 0.1~20.0MPa, preferably 2.0~10.0MPa.

4. The method according to claim 1, characterized in that: First, the hydrocarbon oil hydrorefining catalyst is loaded into a fixed-bed reactor, and then reduced after being sealed with an inert gas, nitrogen and / or hydrogen.

5. The method according to claim 1, characterized in that: The stable oil fraction is introduced at a temperature of 70~200℃, more preferably 120~160℃, and then the temperature is further increased to the reduction temperature.

6. The method according to claim 1, characterized in that: The stabilized oil fraction is one or more of the following: straight-run jet fuel, straight-run diesel, hydrogenated diesel fuel, cracked diesel fuel, and hydrogenated refined diesel fuel.

7. The method according to claim 1, characterized in that: After reduction by the catalyst in the hydrorefining of hydrocarbon oil, it is directly fed into the hydrocarbon oil feedstock for reaction.

8. The method according to claim 1, characterized in that: The hydrocarbon oil feedstock is diesel oil or wax oil, preferably diesel oil.

9. The method according to claim 1, characterized in that: The reaction conditions for introducing hydrocarbon oil feedstock are as follows: reaction temperature 300~410℃, operating pressure 3.0~13.0MPa, hydrogen-to-oil volume ratio 100:1~1000:1, and volume hourly space velocity 0.1~10.0h⁻¹. -1 .

10. The method according to claim 1, characterized in that: Based on the weight of the final hydrorefining catalyst, the alumina support mass content is 40%-85%, preferably 45%-80%, and even more preferably 50%-75%.

11. The method according to claim 10, characterized in that: The alumina carrier is doped with a small amount of one or more of silicon, phosphorus, boron, magnesium and fluorine, and the amount of doping does not exceed 5.0% of the total mass of the carrier.

12. The method according to claim 1, characterized in that: The pore volume of the hydrogen refining catalyst is 0.6~1.3 cm. 3 / g, with a preferred pore volume of 0.7~1.2 cm³. 3 / g, specific surface area is 180-340m² 2 / g, preferably 210-310m 2 / g.

13. The method according to claim 1, characterized in that: Molybdenum exists in the form of molybdenum salt, molybdenum oxide, or elemental molybdenum. Based on the weight of the final hydrogenation catalyst, the mass content of molybdenum, calculated as elemental molybdenum, is 3.0%-25%, preferably 4.0%-20%, and more preferably 5.0%-18.0%.

14. The method according to claim 1, characterized in that: The organic groups corresponding to 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, tartrate, glycolate, and gluconate. The organic complexes are one or more of acetylacetone, EDTA, NTA, and ethylenediamine.

15. The method according to claim 1, characterized in that: The organic acid anions or organic complexes corresponding to organonickel and organometallic additives may be the same or different, but it is preferred to use the same organic acid anion or organic complex.

16. The method according to claim 1, characterized in that: Based on the weight of the hydrorefining catalyst, the mass content of organic acid radicals and / or organic complexes in the catalyst is 4%-20%, preferably 6%-18%.

17. The method according to claim 1, characterized in that: The hydrorefining catalyst is prepared by the following method: (1) Introducing metallic molybdenum onto an alumina carrier; (2) Step (1) Introduce organonickel and organometallic additives onto the inorganic refractory oxide support of molybdenum metal, and then dry them to obtain the final hydrogenation catalyst.

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