A hydroprocessing catalyst, its preparation method and use

Abstract

The application discloses a hydroprocessing catalyst and a preparation method and application thereof. The hydroprocessing catalyst contains fluorophosphoric acid and a complexing agent, the mass content of the fluorophosphoric acid is 1-12% and preferably 2-10% based on the weight of the catalyst, and the mass content of the complexing agent is 2-15% and preferably 3-12%. The preparation method of the catalyst comprises the following steps: (1) preparing an active metal impregnation solution containing fluorophosphoric acid and a complex; (2) impregnating the impregnation solution of step (1) on a carrier; and (3) obtaining the hydroprocessing catalyst after drying the material of step (2). The hydroprocessing catalyst has high matching between acid sites and hydrogenation centers, and the activity stability of the catalyst is significantly improved.

Description

Technical Field

[0001] This invention relates to a hydrogenation catalyst, its preparation method, and its application; more specifically, it relates to a highly active hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Hydrorefining catalysts, especially those for hydrodenitrogenation, require a high spatial proximity between the acidic and hydrogenation sites to maximize synergistic effects. Using fluorinated additives is an effective method for enhancing catalyst acidity, and this has been reported in numerous publications.

[0003] CN114950459A discloses a hydrogenation catalyst support and its preparation method, as well as a hydrogenation catalyst and its preparation method. This method uses organic fluorides such as 3,5-difluorobenzoylhydrazine, 4-amino-2-fluoropyridine, heptafluorobutyric anhydride, 4-vinylphenylboronic acid, diphenylboronic acid-2-aminoethyl ester, and 4-carboxyphenylboronic acid as modifiers to improve the acidity of the catalyst and enhance its hydrogenation activity on distillate oils.

[0004] CN102861601A discloses a fluorine-containing hydrogenation catalyst and its preparation method. Fluorine is introduced from a support, and then an active metal is introduced to prepare the hydrogenation catalyst. The hydrogenation catalyst composition has excellent performance in the hydrorefining of hydrocarbon oils.

[0005] CN107597152A discloses a hydrogenation catalyst and its preparation method, using an F-containing compound that is at least one of the group consisting of tetrabutylammonium fluoride, trifluoroacetic acid, hexafluoroacetone, and hexafluoroisopropanol. This catalyst can be used for the hydrorefining of light distillate oils such as gasoline, kerosene, and diesel fractions, exhibiting high hydrodesulfurization activity and aromatic saturation capacity.

[0006] The aforementioned modification methods, whether modifying the support or the impregnation solution, introduce fluorine, which increases the acidity of the catalyst. Acidic sites readily adsorb highly polar macromolecules. If the hydrogenation activity around these acidic sites is mismatched, the diffusion capacity of these polar macromolecules is weakened. Furthermore, the adsorbed polar molecules further narrow the pores, hindering material diffusion and increasing the risk of pore narrowing and carbon buildup. Therefore, enhancing the spatial matching between the acidic and hydrogenation centers in the hydrogenation catalyst is an effective method to improve its acidity and stability. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a hydrotreating catalyst, its preparation method, and its application. The hydrotreating catalyst exhibits high matching between its acidic sites and hydrogenation centers, significantly improving the catalyst's activity and stability.

[0008] The first aspect of the present invention is to provide a hydrotreating catalyst, wherein the hydrotreating catalyst contains fluorophosphoric acid and a complexing agent, wherein, based on the weight of the catalyst, the fluorophosphoric acid content is 1%-12%, preferably 2%-10%; and the complexing agent content is 2%-15%, preferably 3%-12%.

[0009] In the catalyst of this invention, the fluorophosphoric acid is a polyfluorophosphoric acid, preferably containing a +5 valent phosphorus atom in its structure, with at least two fluorine atoms directly bonded to the phosphorus atom, including: difluorodioxarate phosphoric acid, sodium difluorodioxarate phosphate, ammonium difluorodioxarate phosphate, tetrafluorooxarate phosphoric acid, sodium tetrafluorooxarate phosphate, lithium tetrafluorooxarate phosphate, ammonium difluorodioxarate phosphate, hexafluorophosphate, sodium hexafluorophosphate, ammonium hexafluorophosphate, etc. Our research has found that the F atom directly bonded to the +5 valent phosphorus atom can form a stable complex structure with nickel ions.

[0010] In the catalyst of this invention, the complexing agent is citric acid, ethylenediaminetetraacetic acid, aminotriacetic acid, tartaric acid, glycine, gluconic acid, etc.

[0011] The catalyst of the present invention contains active metals of Group VIB and / or Group VIII elements, wherein Group VIB elements include molybdenum and tungsten, and Group VIII elements include nickel and cobalt. Based on the weight of the catalyst, the mass content of Group VIB elements as +6 oxides is 12%-30%, preferably 15%-25%; and the mass content of Group VIII elements as +2 oxides is 1%-8%, preferably 2%-5%.

[0012] In the catalyst of this invention, the support is at least one selected from alumina, silicon oxide, and amorphous silica-alumina, with alumina being preferred. Based on the weight of the hydrogenated catalyst, the support content is 45%-80%, preferably 55%-75%. The support may be doped with one or more modifying elements such as phosphorus, silicon, boron, sodium, and magnesium, wherein the content of the modifying element is less than 3% of the support mass, preferably 0-2.0% of the support mass.

[0013] A second aspect of the present invention provides a method for preparing the above-mentioned hydrogenation catalyst, the method comprising:

[0014] (1) Prepare an active metal impregnation solution containing fluorophosphoric acid and its complex;

[0015] (2) Impregnate the carrier with the impregnation solution from step (1);

[0016] (3) The material in step (2) is dried to obtain the hydrogenation catalyst.

[0017] Further, in step (1), the concentration of the active metal group VIB in the impregnation solution is 0.5-4.0 mol / L, preferably 1.0-3.0 mol / L. The concentration of the active metal group VIII is 0.2-2.0 mol / L, preferably 0.3-1.5 mol / L. The concentration of fluorophosphoric acid is 0.05-1.0 mol / L, preferably 0.1-0.8 mol / L. The concentration of the complex is 0.1-1.5 mol / L, preferably 0.2-1.2 mol / L.

[0018] Furthermore, in step (2), the impregnation method can be equal volume impregnation, supersaturated impregnation, or other methods.

[0019] Furthermore, in step (3), the drying method is vacuum drying, the drying temperature is 40-120℃, preferably 50-90℃, the drying time is 2.0-10.0 hours, preferably 4.0-8.0 hours, and the vacuum degree is 0.1-2.0 torr, preferably 0.2-1.0 torr.

[0020] A third aspect of the present invention provides a method for using the above-mentioned hydrotreating catalyst, the method comprising: firstly introducing an alkaline substance into the hydrotreating catalyst, and then performing a sulfidation treatment.

[0021] Furthermore, the specific process for introducing alkaline substances is as follows: The hydrogenation catalyst prepared above is loaded into a fixed-bed reactor, and an alkaline gas or liquid is slowly introduced at 0-50℃, preferably 10-30℃. Alkaline gases include ammonia, and alkaline liquids include monoethanolamine, ethylenediamine, aniline, quinoline, etc. When ammonia is introduced, the pressure is 0.1-0.5 MPa, the temperature is controlled at 20-50℃, and the flow rate is 1.0-5.0 mL·min. -1 ·g -1 The catalyst is used, and the treatment time is 2.0–8.0 hours. When introducing liquid, nitrogen or hydrogen is required as a protective gas, with a gas flow rate of 5.0–30.0 mL / min. -1 ·g -1 The catalyst pressure was controlled at 0.1-0.5 MPa, the temperature at 30-80 ℃, and the flow rate at 0.1-0.5 mL·h. -1 ·g -1 The catalyst was used for a treatment time of 1.0-6.0 hours.

[0022] Furthermore, the sulfidation process is as follows: Hydrogenation catalyst with an alkaline substance is introduced, and wet sulfidation is used. The gas is hydrogen, the pressure is 4.0-10.0 MPa, and the hydrogen flow rate is 5.0-50.0 mL·min. -1 ·g -1The vulcanizing solution is an organic solvent containing a vulcanizing agent, such as carbon disulfide, dimethyl disulfide, dibenzyl sulfide, or benzyl disulfide, accounting for 1%-10% of the total mass fraction of the vulcanizing solution, preferably 2%-8%. The organic solvent is cyclohexane, n-heptane, petroleum ether (90-120℃), or refined kerosene. The volume of the vulcanizing solution used is 0.1-2.5 mL / h. -1 ·g -1 Catalyst, preferably 0.2-2.0 mL·h -1 ·g -1 catalyst.

[0023] Furthermore, the vulcanization treatment can be divided into two stages according to temperature. In the first stage, the reaction temperature is controlled at 120-230℃, preferably 140-200℃, and the vulcanization time is 2.0-15.0 hours, preferably 3.0-12.0 hours. In the second stage, the reaction temperature is controlled at 230-370℃, preferably 240-340℃, and the vulcanization time is 2.0-15.0 hours, preferably 3.0-12.0 hours.

[0024] To address the challenge of effectively matching the active metal sites for hydrogenation with the acid sites provided by fluorine, this invention employs a series of fluorophosphate complexing agents. These agents bind the fluorine providing the acid sites to the nickel sites for hydrogenation, while simultaneously delaying sulfidation through complexation. This improves both the catalyst's acidity and hydrogenation performance, optimizes the spatial matching between the acid and hydrogenation sites, and significantly enhances the catalyst's hydrogenolysis activity.

[0025] The adsorption of alkaline substances onto the catalyst before sulfidation is primarily due to the interaction between the alkaline nitrides and the fluorine-containing strong acid centers. This provides temporary protection to these acid centers, preventing the active molybdenum from migrating to them during sulfidation and thus covering them, which would reduce the modification effect. Simultaneously, the further electron-donating effect of these alkaline nitrides enhances the complexation ability of nickel with fluorophosphoric acid, further manifesting the delayed sulfidation effect of nickel. Implementation

[0026] The present invention will be further described below with reference to embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments. In the present invention, unless otherwise expressly stated, percentages and contents are all expressed by mass.

[0027] The oxidized hydrogenation catalysts used in the following embodiments and comparative examples of this invention were all prepared by the following methods:

[0028] Weigh out 5000.0 g of alumina dry adhesive powder and 50.0 g of silica sol, add 150.0 g of citric acid and 100.0 g of guar gum powder, mix well, then add 5000.0 g of an aqueous solution containing 1.0% nitric acid and 2.0% acetic acid. After rolling for 10.0 min, extrude the mixture using a 1.5 mm diameter four-leaf perforated plate. Dry at 120℃ for 8.0 h, then calcine at 550℃ for 4.0 h. The calcined carrier is designated S-0 (the specific surface area of ​​the carrier is 315 m²). 2 / g, pore volume 0.71 cm³ 3 / g).

[0029] Example 1

[0030] Weigh out 30.0 g of ammonium molybdate, 20.0 g of nickel nitrate hexahydrate, 10.0 g of lithium difluorodioxarate phosphate, and 20.0 g of citric acid, dissolve them in 100.0 g of water, and the resulting solution is denoted as FQ-1.

[0031] Weigh 500 g of cyclohexane solution and 20.0 g of carbon disulfide to prepare a sulfidation solution, which is denoted as SQ-1.

[0032] Weigh 100.0 g of S-0, impregnate S-0 with FQ-1, let stand for 6.0 hours, and then dry the catalyst using a vacuum drying method under the following conditions: temperature 60℃, vacuum degree 0.5 torr, and drying time 5.0 hours. The resulting catalyst is designated as MC-1.

[0033] Take 20.0 g of MC-1 and load it into a fixed-bed reaction tube. Under a pressure of 0.3 MPa and a temperature of 30 °C, ammonia gas is introduced into the reaction tube at a rate of 60 mL / min for 4.0 hours. The resulting catalyst is designated as BC-1.

[0034] BC-1 was then vulcanized. The pressure in the reaction tube was controlled at 5.0 MPa, the hydrogen flow rate was 200 mL / min, and SQ-1 was introduced into the reaction tube at a flow rate of 20 mL / h. The reaction temperature was raised to 160℃ and maintained for 5.0 hours. Then the reaction temperature was maintained at 290℃ for 6.0 hours.

[0035] The resulting catalyst is designated Cat-1.

[0036] Example 2

[0037] Weigh out 30.0 g of ammonium molybdate, 20.0 g of nickel nitrate hexahydrate, 8.0 g of lithium tetrafluorooxalate phosphate, and 25.0 g of ethylenediaminetetraacetic acid, dissolve them in 100.0 g of water, and the resulting solution is designated as FQ-2.

[0038] Weigh 500 g of n-heptane solution and 20.0 g of dimethyl disulfide to prepare a sulfidation solution, which is denoted as SQ-2.

[0039] Weigh 100.0 g of S-0, impregnate S-0 with FQ-2, let stand for 6.0 hours, and then dry the catalyst using a vacuum drying method under the following conditions: temperature 70℃, vacuum degree 0.4 torr, and drying time 4.0 hours. The resulting catalyst is designated as MC-2.

[0040] Take 20.0 g of MC-2 and load it into a fixed-bed reaction tube. Under nitrogen pressure of 0.5 MPa and temperature of 50 °C, introduce monoethanolamine into the reaction tube at a rate of 6.0 mL / h for 3.0 hours. The resulting catalyst is designated as BC-2.

[0041] BC-2 was then vulcanized. The pressure in the reaction tube was controlled at 6.0 MPa, the hydrogen flow rate was 300 mL / min, and SQ-2 was introduced into the reaction tube at a flow rate of 25 mL / h. The reaction temperature was raised to 150℃ and maintained for 5.0 hours. Then the reaction temperature was maintained at 300℃ for 6.0 hours.

[0042] The resulting catalyst is designated Cat-2.

[0043] Example 3

[0044] Weigh out 30.0 g of ammonium molybdate, 20.0 g of nickel nitrate hexahydrate, 5.0 g of hexafluorophosphate, and 20.0 g of tartaric acid, dissolve them in 100.0 g of water, and the resulting solution is designated as FQ-3.

[0045] Weigh 500 g of petroleum ether and 20.0 g of benzene disulfide, and the resulting sulfidation solution is designated as SQ-3.

[0046] Weigh 100.0 g of S-0, impregnate S-0 with FQ-3, let stand for 5.0 hours, and then dry the catalyst using a vacuum drying method under the following conditions: temperature 80℃, vacuum degree 0.3 torr, drying time 6.0 hours. The resulting catalyst is designated as MC-3.

[0047] Take 20.0 g of MC-3 and load it into a fixed-bed reaction tube. Under nitrogen pressure of 0.6 MPa and temperature of 60 °C, ethylenediamine is introduced into the reaction tube at a rate of 8.0 mL / h for 3.0 hours. The resulting catalyst is designated as BC-3.

[0048] BC-3 was then vulcanized. The pressure in the reaction tube was controlled at 4.0 MPa, the hydrogen flow rate was 320 mL / min, and SQ-3 was introduced into the reaction tube at a flow rate of 30 mL / h. The reaction temperature was raised to 160℃ and maintained for 6.0 hours. Then the reaction temperature was maintained at 320℃ for 6.0 hours.

[0049] The resulting catalyst is designated Cat-3.

[0050] Example 4

[0051] Weigh out 30.0 g of ammonium molybdate, 20.0 g of nickel nitrate hexahydrate, 6.0 g of sodium hexafluorophosphate, and 15.0 g of glycine, dissolve them in 100.0 g of water, and the resulting solution is designated as FQ-4.

[0052] Weigh 500 g of petroleum ether and 25.0 g of dibenzyl sulfide, and the resulting sulfidation solution is denoted as SQ-4.

[0053] Weigh 100.0 g of S-0, impregnate S-0 with FQ-4, let stand for 6.0 hours, and then dry the catalyst using a vacuum drying method under the following conditions: temperature 70℃, vacuum degree 0.2 torr, drying time 6.0 hours. The resulting catalyst is designated as MC-4.

[0054] Take 20.0 g of MC-4 and load it into a fixed-bed reaction tube. Under nitrogen pressure of 0.5 MPa and temperature of 50 °C, quinoline is introduced into the reaction tube at a rate of 7.0 mL / h for 3.0 hours. The resulting catalyst is designated as BC-4.

[0055] BC-4 was then vulcanized, with the reaction tube pressure controlled at 5.0 MPa and the hydrogen flow rate at 280 mL / min. SQ-4 was introduced into the reaction tube at a flow rate of 40 mL / h, and the reaction temperature was raised to 180℃ and maintained for 6.0 hours. Then the reaction temperature was maintained at 300℃ for 4.0 hours.

[0056] The resulting catalyst is designated Cat-4.

[0057] Comparative Example 1

[0058] Weigh out 30.0 g of ammonium molybdate and 20.0 g of nickel nitrate hexahydrate, dissolve them in 100.0 g of water, and the resulting solution is denoted as DQ-1.

[0059] Weigh 500 g of petroleum ether and 25.0 g of carbon disulfide, and the resulting sulfidation solution is denoted as DQ-1.

[0060] Weigh 100.0 g of S-0, impregnate S-0 with DQ-1, let stand for 6.0 hours, and then dry the catalyst using a vacuum drying method under the following conditions: temperature 70℃, vacuum degree 0.2 torr, drying time 6.0 hours. The resulting catalyst is designated as DMC-1.

[0061] Take 20.0 g of DMC-1 and load it into a fixed-bed reaction tube. Under nitrogen pressure of 0.5 MPa and temperature of 50 °C, introduce monoethanolamine into the reaction tube at a rate of 7.0 mL / h for 5.0 hours. The resulting catalyst is designated as DBC-1.

[0062] Next, DBC-1 was vulcanized. The pressure in the reaction tube was controlled at 5.0 MPa, the hydrogen flow rate was 280 mL / min, DSQ-1 was introduced into the reaction tube at a flow rate of 50 mL / h, and the reaction temperature was raised to 350℃ and maintained for 6.0 hours.

[0063] The resulting catalyst was designated DCT-1.

[0064] Comparative Example 2

[0065] Weigh out 30.0 g of ammonium molybdate, 20.0 g of nickel nitrate hexahydrate, 5.0 g of ammonium fluoride, and 20.0 g of citric acid, dissolve them in 100.0 g of water, and the resulting solution is denoted as DFQ-2.

[0066] Weigh 500 g of petroleum ether and 25.0 g of dimethyl disulfide, and the resulting sulfidation solution is designated as DSQ-2.

[0067] Weigh 100.0 g of S-0, impregnate S-0 with DQ-2, let stand for 6.0 hours, and then dry the catalyst using a vacuum drying method under the following conditions: temperature 60℃, vacuum degree 0.2 torr, drying time 6.0 hours. The resulting catalyst is designated as DMC-2.

[0068] Take 20.0 g of DMC-2 and load it into a fixed-bed reaction tube. Under nitrogen pressure of 0.5 MPa and temperature of 50 °C, introduce diethanolamine into the reaction tube at a rate of 8.0 mL / h for 5.0 hours. The resulting catalyst is designated as DBC-2.

[0069] DBC-2 was then sulfided. The reaction tube pressure was controlled at 5.0 MPa, the hydrogen flow rate at 280 mL / min, and DSQ-2 was introduced into the reaction tube at a flow rate of 50 mL / h. The reaction temperature was raised to 350℃ and maintained for 6.0 hours. The resulting catalyst was designated DCT-2.

[0070] Comparative Example 3

[0071] Weigh out 30.0 g of ammonium molybdate, 20.0 g of nickel nitrate hexahydrate, 10.0 g of lithium difluorodioxarate phosphate, and 15.0 g of citric acid, dissolve them in 100.0 g of water, and the resulting solution is designated as DFQ-3.

[0072] Weigh 500 g of petroleum ether and 30.0 g of dimethyl disulfide, and the resulting sulfidation solution is designated as DSQ-3.

[0073] Weigh 100.0 g of S-0, impregnate S-0 with DSQ-2, let stand for 6.0 hours, and then dry the catalyst using vacuum drying at 60℃, 0.2 torr, and for 6.0 hours. The resulting catalyst is designated DMC-3.

[0074] DMC-3 was vulcanized with the reaction tube pressure controlled at 4.0 MPa and the hydrogen flow rate at 320 mL / min. DSQ-3 was introduced into the reaction tube at a flow rate of 30 mL / h. The reaction temperature was raised to 160℃ and maintained for 6.0 hours. Then the reaction temperature was maintained at 320℃ for 6.0 hours.

[0075] The elemental composition of catalysts MC-1, MC-2, MC-3, MC-4 and DMC-1, DMC-2 and DMC-3 was analyzed, and the results are shown in Table 1.

[0076] Table 1. Elemental composition of catalysts

[0077]

[0078] The catalyst was evaluated using feedstock oils shown in Table 2.

[0079] Table 2

[0080]

[0081] Fixed-bed hydrogenation experiments were conducted on catalysts Cat-1, Cat-2, Cat-3, Cat-4, DCT-1, DCT-2, and DCT-3. The evaluation conditions were: reaction temperature 380℃, reaction pressure 16.0 MPa, hydrogen-to-oil ratio 1000:1, and liquid hourly space velocity 1.0 h⁻¹. -1 After 500 hours of reaction, the samples were analyzed, and the results are shown in Table 3:

[0082] Table 3

[0083]

[0084] The evaluation results show that the catalyst modified with fluorophosphoric acid and treated accordingly has significantly improved its hydrodesulfurization, denitrification and dearomatics capabilities, especially the hydrodenitrification capability.

Claims

1. A hydrogenation catalyst product, characterized in that: First, an alkaline substance is introduced into the hydrotreating catalyst, followed by sulfidation treatment to obtain the hydrotreating catalyst product. The alkaline substance is an alkaline nitride. The hydrotreating catalyst contains fluorophosphoric acid and a complexing agent. Based on the weight of the catalyst, the fluorophosphoric acid content is 1%-12% by mass, and the complexing agent content is 2%-15% by mass. The fluorophosphoric acid includes one or more of the following: difluorodioxazophosphate, sodium difluorodioxazophosphate, ammonium difluorodioxazophosphate, tetrafluorooxazophosphate, sodium tetrafluorooxazophosphate, lithium tetrafluorooxazophosphate, ammonium difluorodioxazophosphate, hexafluorophosphate, sodium hexafluorophosphate, and ammonium hexafluorophosphate.

2. The catalyst product according to claim 1, characterized in that: Based on the weight of the catalyst, the mass content of fluorophosphoric acid is 2%-10%; the mass content of the complexing agent is 3%-12%.

3. The catalyst product according to claim 1, characterized in that: The complexing agent is one or more of citric acid, ethylenediaminetetraacetic acid, aminotriacetic acid, tartaric acid, glycine, and gluconic acid.

4. The catalyst product according to claim 1, characterized in that: The catalyst contains active metals of Group VIB and / or Group VIII, including molybdenum and tungsten of Group VIB and nickel and cobalt of Group VIII. Based on the weight of the catalyst, the mass content of Group VIB elements as +6 oxides is 12%-30% and the mass content of Group VIII elements as +2 oxides is 1%-8%.

5. The catalyst product according to claim 4, characterized in that: Based on the weight of the catalyst, the mass content of Group VIB elements, calculated as +6 oxides, is 15%-25%; and the mass content of Group VIII elements, calculated as +2 oxides, is 2%-5%.

6. The catalyst product according to claim 1, characterized in that: The support is at least one of alumina, silica, and amorphous silica-alumina; the support content is 45%-80% based on the weight of the hydrotreating catalyst.

7. The catalyst product according to claim 6, characterized in that: The support is alumina; based on the weight of the hydrotreating catalyst, the support content is 55%-75%.

8. The catalyst product according to claim 6, characterized in that: The carrier is doped with one or more of the following modifying elements: phosphorus, silicon, boron, sodium, and magnesium, wherein the content of the modifying element is less than 3% of the carrier mass when measured as an element.

9. The catalyst product according to claim 8, characterized in that: The content of the modified element is 0-3.0% of the carrier mass, calculated as an element.

10. A method for preparing any one of the hydrogenation catalyst products according to claims 1-9, characterized in that: The method includes: (1) Prepare an active metal impregnation solution containing fluorophosphoric acid and its complex; (2) Impregnate the carrier with the impregnation solution from step (1); (3) The material in step (2) is dried to obtain the hydrogenation catalyst.

11. The method according to claim 10, characterized in that: In the impregnation solution described in step (1), the concentration of the group VIB active metal is 0.5-4.0 mol / L; the concentration of the group VIII active metal is 0.2-2.0 mol / L; the concentration of fluorophosphoric acid is 0.05-1.0 mol / L; and the concentration of the complex is 0.1-1.5 mol / L.

12. The method according to claim 11, characterized in that: In the impregnation solution described in step (1), the concentration of the group VIB active metal is 1.0-3.0 mol / L; the concentration of the group VIII active metal is 0.3-1.5 mol / L; the concentration of fluorophosphoric acid is 0.1-0.8 mol / L; and the concentration of the complex is 0.2-1.2 mol / L.

13. The method according to claim 10, characterized in that: In step (2), the impregnation method is either equal volume impregnation or supersaturated impregnation.

14. The method according to claim 10, characterized in that: In step (3), the drying is vacuum drying, the drying temperature is 40-120℃, the drying time is 2.0-10.0 hours, and the vacuum degree is 0.1-2.0 torr.

15. The method according to claim 14, characterized in that: In step (3), the drying temperature is 50-90℃; the drying time is 4.0-8.0 hours; and the vacuum degree is 0.2-1.0 torr.

16. The method of using the hydrotreating catalyst product according to any one of claims 1-9, characterized in that: The specific process for introducing alkaline substances is as follows: The hydrogenation catalyst is loaded into a fixed-bed reactor, and an alkaline gas or liquid is slowly introduced at 0-50℃. The alkaline gas is ammonia, and the liquid is at least one of monoethanolamine, ethylenediamine, aniline, and quinoline. When ammonia is introduced, the pressure is 0.1-0.5 MPa, the temperature is controlled at 20-50℃, and the flow rate is 1.0-5.0 ml·min. -1 ·g -1 The catalyst, with a treatment time of 2.0–8.0 hours, requires nitrogen or hydrogen as a protective gas when introducing liquid, with a gas flow rate of 5.0–30.0 ml·min. -1 ·g -1 The catalyst was used at a pressure controlled at 0.1-0.5 MPa, a temperature controlled at 30-80 ℃, and a flow rate of 0.1-0.5 ml·h. -1 ·g -1 The catalyst was used for a treatment time of 1.0-6.0 hours.

17. The method of use according to claim 16, characterized in that: Slowly introduce alkaline gas or liquid at 10-30℃.

18. The method of use according to claim 16, characterized in that: The sulfidation process is as follows: Hydrogenation catalyst with alkaline substances is introduced, and wet sulfidation is used. The gas is hydrogen, the pressure is 4.0-10.0 MPa, and the hydrogen flow rate is 5.0-50.0 ml·min. -1 ·g -1 The sulfiding solution is an organic solvent containing a sulfiding agent, wherein the sulfiding agent is at least one selected from carbon disulfide, dimethyl disulfide, dibenzyl sulfide, and benzene disulfide, accounting for 1%-10% of the total mass fraction of the sulfiding solution. The organic solvent is at least one selected from cyclohexane, n-heptane, petroleum ether (90-120℃), and refined kerosene. The volume of the sulfiding solution used is 0.1-2.5 ml·h. -1 ·g -1 catalyst.

19. The method of use according to claim 18, characterized in that: The vulcanizing agent accounts for 2%-8% of the total mass fraction of the vulcanizing liquid; the volume of the vulcanizing liquid used is 0.2-2.0 ml / h. -1 ·g -1 catalyst.

20. The method of use according to claim 18, characterized in that: The vulcanization process is divided into two stages according to temperature. The first stage controls the reaction temperature at 120-230℃ and the vulcanization time at 2.0-15.0 hours. The second stage controls the reaction temperature at 230-370℃ and the vulcanization time at 2.0-15.0 hours.

21. The method of use according to claim 20, characterized in that: The vulcanization process is divided into two stages according to temperature. The first stage controls the reaction temperature at 140-200℃ and the vulcanization time at 3.0-12.0 hours. The second stage controls the reaction temperature at 240-340℃ and the vulcanization time at 3.0-12.0 hours.

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