A slurry oil selective hydrogenation catalyst and a method for preparing the same

Abstract

This invention discloses an oil slurry selective hydrogenation catalyst and its preparation method. The oil slurry selective hydrogenation catalyst comprises active metals Mo and Co, and a support γ-Al₂O₃. Based on the total weight of the catalyst, MoO₃ accounts for 9 wt%–47 wt%, and CoO accounts for 2 wt%–11%. After sulfidation, the average lamellar length of the active phase MoS₂ is 7–12 nm, preferably 8–11 nm, and the average number of lamellar layers in a single stack is 1–5. Based on the total number of stacks, the proportion of stacks with 3–5 layers is 40%–90%, preferably 40%–70%. The preparation method of the oil slurry selective hydrogenation catalyst includes the following steps: impregnating the hydrogenation catalyst support with an impregnation solution containing Mo and Co; after impregnation, the support is cured and calcined to obtain the oil slurry selective hydrogenation catalyst. The catalyst of this invention enhances direct desulfurization activity and weakens the saturation performance of tricyclic and tetracyclic aromatic hydrocarbons, making it suitable for catalyzing oil slurry selective hydrogenation desulfurization reactions.

Description

Technical Field

[0001] This invention relates to an oil slurry hydrogenation catalyst and its preparation method, particularly an oil slurry selective hydrogenation catalyst for producing needle coke feedstock and its preparation method. Background Technology

[0002] Needle coke possesses characteristics such as high crystallinity, high strength, high graphitization, low thermal expansion, and low ablation, making it widely used as a raw material for ultra-high power graphite electrodes in the metallurgical industry. Needle coke used as a raw material for graphite electrodes must have a low sulfur content; therefore, based on the properties and formation mechanism of needle coke, raw materials with low sulfur content and high tricyclic and tetracyclic aromatic hydrocarbon content should be selected. Catalytic slurry oil has a high content of polycyclic aromatic hydrocarbons, making it suitable as a raw material for needle coke production. However, since catalytic slurry oil typically has a high sulfur content, hydrodesulfurization treatment is still required.

[0003] The production of needle coke feedstock through catalytic slurry hydrotreating requires achieving high desulfurization activity while reducing the hydrosaturation activity of tricyclic and tetracyclic aromatics. Catalytic slurry oils have large molecular weights, complex structures, and high aromatic content. Sulfur is mainly distributed in polycyclic aromatic hydrocarbons, gums, and asphaltenes. The presence of these complex compounds makes the hydrodesulfurization reaction much more difficult than that of distillate oils with relatively smaller molecular weights. The complex macromolecular structure easily forms steric hindrance, hindering the adsorption of sulfur atoms by the active sites of the catalyst. The adsorption and deposition of macromolecules on the catalyst surface also increases diffusion resistance within the reaction. The feedstock contains a large amount of coking precursors, which easily form coke deposits on the catalyst surface during the reaction, causing a decrease in catalyst activity. Furthermore, while achieving desulfurization activity, it is also necessary to maintain the lowest possible saturation of tricyclic and tetracyclic aromatics.

[0004] CN110628461A discloses a method for selective hydrodesulfurization of oil slurry while retaining aromatics. First, ultrasonic-assisted centrifugation is used to remove catalyst particles from the middle layer of the oil slurry. The mechanical action of ultrasound can effectively improve the removal effect of catalyst particles. Then, the residual catalyst particles, asphaltenes, and gums in the oil slurry are removed, while the extracted oil enriched with aromatics is retained. Then, the extracted oil is selectively hydrodesulfurized using an Fe-modified CoMo / γAl2O3 selective hydrodesulfurization catalyst.

[0005] CN113862035A discloses a method for producing high-end needle coke feedstock from catalytic cracking slurry. The catalytic cracking slurry is filtered using a cross-flow filter with a high-temperature resistant ceramic membrane filter element or a metal membrane filter element. The permeate obtained after filtration is subjected to vacuum distillation. The intermediate fraction obtained from vacuum distillation is mixed with hydrogen and then introduced into a hydrogenation reactor for hydrogenation treatment. The reaction stream first enters the desulfurization catalyst unit in the hydrogenation reactor, and then enters the hydrogenation aromatization and repair catalyst unit, which meets the requirements for producing high-end needle coke components.

[0006] The CN113862035A reaction stream first enters the desulfurization catalyst unit in the hydrogenation reactor, and then enters the hydrogenation aromatization repair catalyst unit. The hydrogenation desulfurization catalyst is a hydrogenation desulfurization catalyst with γ-Al2O3 as the support and molybdenum and nickel as the active components. Aromatics need to be restored to meet the requirements for producing high-end needle coke components. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a selective hydrodesulfurization catalyst for oil slurry and its preparation method. The catalyst of this invention enhances direct desulfurization activity and weakens the saturation properties of tricyclic and tetracyclic aromatic hydrocarbons, making it suitable for catalytic selective hydrodesulfurization reactions in oil slurry.

[0008] The selective hydrogenation catalyst for oil slurry of the present invention comprises active metals Mo and Co, and a support γ-Al₂O₃. By total weight of the catalyst, Mo, calculated as MoO₃, comprises 9 wt% to 47 wt%, preferably 15 wt% to 35 wt%, and Co, calculated as CoO, comprises 2 wt% to 11%, preferably 4 wt% to 9 wt%. The γ-Al₂O₃ has an average pore size of 8.0 to 12.0 nm, preferably 8.5 to 11.5 nm, and a specific surface area of ​​270 to 330 m². 2 ·g -1 Preferred size: 280~320m 2 ·g -1 The pore volume is 0.66~0.99cm. 3 ·g -1 The preferred diameter is 0.68~0.80cm. 3 ·g -1 The total amount of pyridine-infrared acid is 0.4~0.7 mmol·g. -1 The preferred dosage is 0.45~0.65 mmol·g. -1 The amount of Brønsted acid is 0.13~0.20 mmol·g. -1 The preferred dosage is 0.15~0.18 mmol·g. -1 The acid content of L-acid is 0.20~0.57 mmol·g. -1 The preferred dosage is 0.27~0.50 mmol·g. -1 The ratio of Brønsted acid to Lourdesic acid is 0.30 to 1.00, preferably 0.35 to 0.66.

[0009] After sulfidation, the oil slurry selective hydrogenation catalyst of the present invention has an average lamellar length of 7-12 nm, preferably 8-11 nm, for the active phase MoS2, and an average number of lamellar layers in a single stack layer of 1-5 layers. Based on the total number of stack layers, the proportion of stack layers with 3-5 layers is 40%-90%, preferably 40%-70%.

[0010] The preparation method of the oil slurry selective hydrogenation catalyst of the present invention includes the following steps: impregnating the hydrogenation catalyst support with an impregnation solution containing Mo and Co, and then curing and calcining the impregnated support to obtain the oil slurry selective hydrogenation catalyst.

[0011] In the method of this invention, the preparation of the impregnation solution is well known to those skilled in the art. Generally, a compound containing an active metal element is used as the source, and the concentration and amount of the impregnation solution are determined according to the catalyst composition. Generally, Mo is molybdenum trioxide, and Co is basic cobalt carbonate; the impregnation method generally employs a saturated spray impregnation method to load the active component.

[0012] In this invention, the conditioning method utilizes natural wind dehumidification based on ambient temperature. The ambient temperature generally does not exceed 50℃, preferably 20-40℃. Hot air recycling is not used. The dehumidification time is 10-24 hours, preferably 12-20 hours, to achieve a catalyst dry basis of 70%-90%, preferably 75%-85%. The natural wind dehumidification process is generally carried out using an exhaust gas dehumidification fan. The catalyst is placed on the conditioning belt, and natural wind is introduced through the exhaust gas dehumidification fan to remove moisture. The catalyst layer thickness is generally controlled at 2-15cm, preferably 3-8cm. The frequency of the conditioning exhaust gas dehumidification fan (to increase the airflow) is 25-50Hz, corresponding to an airflow of 3918m³ under full load. 3 / h (50Hz), the frequency is proportional to the air volume, preferably 30~40Hz.

[0013] In the method of this invention, the calcination temperature is 300~550℃ and the calcination time is 3~4 hours.

[0014] The selective hydrogenation catalyst for oil slurry of this invention employs an in-vessel or external sulfidation process for the sulfidation treatment. The amount of sulfiding agent introduced is 90% to 150% of the theoretical sulfur requirement of the catalyst. The sulfidation process uses a programmed temperature rise, maintaining a temperature of 200 to 350°C for 1 to 16 hours. The sulfiding agent is generally one or more of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide.

[0015] The application of the slurry selective hydrogenation catalyst of the present invention in the slurry selective hydrogenation process generally follows these process conditions: pressure 4.0~6.0 MPa, space velocity 0.5~1.0 h⁻¹. -1 The temperature is 300~390℃, and the hydrogen-to-oil volume ratio is 100~800, making it particularly suitable for the selective hydrogenation of oil slurry to prepare needle coke feedstock. The catalyst of this invention is also applicable to the hydrodesulfurization process of gasoline, kerosene, diesel, and wax oil fractions.

[0016] The selective hydrogenation catalyst for oil slurry of the present invention uses γ-Al₂O₃ with suitable pore size, specific surface area, pore volume, and acidity. The average pore size of γ-Al₂O₃ is 8.0~12 nm, and the specific surface area is 270~330 m². 2 .g -1 The pore volume is between 0.66 and 0.99 cm. 3 .g -1 The acid content of pyridine-infrared acid β-carboxylic acid is 0.13~0.20 mmol·g. -1 The acid content of L-acid is between 0.20 and 0.57 mmol·g. -1 The ratio of Brønsted acid to Lønsted acid is between 0.22 and 1.00. In the method of this invention, the curing process utilizes natural ventilation to remove moisture at ambient temperature. After sulfidation, the average lamellar length of the active phase (taking MoS2 as an example) of the prepared Mo-Co catalyst is 7-12 nm, and the average number of lamellar layers in a single stack is 1-5. Based on the total number of stacks, the proportion of stacks with 3-5 layers is 40%-90%. The increase in the average lamellar length of the active phase MoS2 enhances the DDS reaction of sulfides. Maintaining a stack ratio of 3-5 layers ensures that the catalyst still possesses relatively high hydrodesulfurization performance. Combined with the suitable pore size of γ-Al2O3, the selective hydrogenation of oil slurry is achieved.

[0017] The molecular diameters of 4,6-dimethyldibenzothiophene and 2,4,8-trimethyldibenzothiophene, which are difficult to remove sulfur-containing compounds, are 0.88 nm and 0.98 nm, respectively, while the macromolecular diameters of tricyclic and tetracyclic aromatic hydrocarbons are around 1.15 nm. The average pore size of γ-Al₂O₃ in this invention is close to 10 times the macromolecular diameter of the sulfur-containing compounds and tricyclic and tetracyclic aromatic hydrocarbons, placing the macromolecules in Knudsen diffusion. Since the average pore size of γ-Al₂O₃ is more than 10 times the diameter of the sulfur-containing compounds, collisions between the macromolecular sulfur-containing compounds and the catalyst pore walls are more frequent than intermolecular collisions, increasing the contact frequency between the reactant molecules and the active center, which is beneficial to the desulfurization reaction. Conversely, the average pore size of γ-Al₂O₃ is less than 1 / 10 the macromolecular diameter of tricyclic and tetracyclic aromatic hydrocarbons. The confinement effect of the pores leads to more frequent collisions between tricyclic and tetracyclic aromatic hydrocarbon molecules compared to collisions with the catalyst pore walls, hindering contact with active centers and reducing the saturation of tricyclic and tetracyclic aromatic hydrocarbons. In this invention, the traditional high-temperature drying process is eliminated, resulting in a gentler dispersion of the active metal on the support. Experiments have shown that this leads to longer active phase lamellar crystal lengths after sulfidation, while the larger specific surface area and pore volume of γ-Al₂O₃ further facilitates the dispersion of the active metal. The average number of lamellar layers in a single stack of active phase lamellar crystals after sulfidation is 1-5 layers. A higher Brønsted acid / Low acid ratio indicates a reduction in L-acid in the support, which improves the catalyst's resistance to coking, while an increase in Brønsted acid enhances the catalyst's hydrodesulfurization activity. This invention improves production efficiency and saves energy. Attached Figure Description

[0018] Figure 1 Transmission electron microscopy image of the catalyst in Example 1 of this invention.

[0019] Figure 2 Transmission electron microscopy image of catalyst in Comparative Example 1. Detailed Implementation

[0020] In this invention, the specific surface area and pore volume were determined using a low-temperature liquid nitrogen adsorption method. The lamellar length and stack-layer ratio were determined using field emission transmission electron microscopy. Specifically, more than 350 MoS2 lamellars were selected, and the average number of layers, average length, and the proportion of 3-5 layer wafers were statistically analyzed. The statistical formula is as follows:

[0021]

[0022] Among them l i N represents the chip length. i Represents the number of layers i, a i Representative chip l i The number, b i Represents the number of layers N i The number. In this invention, wt% represents the mass percentage.

[0023] Example 1

[0024] 100g of alumina support A (water absorption rate 90mL / 100g) was placed in a boiling pot. Under rotating conditions, 90mL of an impregnation solution containing 27.5g of molybdenum trioxide and 22.7g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes. Under the conditions of an ambient temperature of 30℃, a material layer thickness of 8cm, and a tail gas fan frequency of 30Hz, natural air was used for dehumidification for 8 hours. The catalyst dry basis was 76%. The catalyst was then calcined at 500℃ for 4 hours to obtain the finished catalyst A. The finished catalyst A was sulfided using an in-vessel sulfidation process. The amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, and the temperature was maintained at 320℃ for 10 hours.

[0025] Example 2

[0026] 100g of alumina support B (water absorption rate 90mL / 100g) was placed in a boiling pot. Under rotating conditions, 90mL of an impregnation solution containing 29.0g of molybdenum trioxide and 17.9g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes. Under the conditions of an ambient temperature of 29℃, a material layer thickness of 6cm, and a tail gas fan frequency of 30Hz, natural air was used for dehumidification for 10 hours. The catalyst dry basis was 78%. The catalyst was then calcined at 500℃ for 4 hours to obtain the finished catalyst B. The finished catalyst B was then subjected to an in-vessel sulfidation process. The amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, and the temperature was maintained at 320℃ for 10 hours.

[0027] Example 3

[0028] 100g of alumina support C (water absorption rate 90mL / 100g) was placed in a boiling pot. Under rotating conditions, 90mL of an impregnation solution containing 25.0g of molybdenum trioxide and 16.3g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes. Under the conditions of an ambient temperature of 31℃, a material layer thickness of 7cm, and a tail gas fan frequency of 25Hz, natural air was used for dehumidification for 10 hours, resulting in a catalyst dry basis of 77%. The catalyst was then calcined at 500℃ for 4 hours to obtain the finished catalyst C. The finished catalyst C was sulfided using an in-vessel sulfidation process, introducing dimethyl disulfide at 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, with the temperature reaching 320℃ and held at that temperature for 10 hours.

[0029] Example 4

[0030] 100g of alumina support D (water absorption rate 90mL / 100g) was placed in a boiling pot. Under rotating conditions, 90mL of an impregnation solution containing 28.6g of molybdenum trioxide and 16.8g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes. Under the conditions of an ambient temperature of 26℃, a material layer thickness of 6cm, and a tail gas fan frequency of 35Hz, natural air was used for dehumidification for 10 hours, resulting in a catalyst dry basis of 78%. The catalyst was then calcined at 500℃ for 4 hours to obtain the finished catalyst C. The finished catalyst C was sulfided using an in-vessel sulfidation process, introducing dimethyl disulfide at 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, with the temperature reaching 320℃ and held at that temperature for 10 hours.

[0031] Example 5

[0032] In a 200 mL fixed-bed small-scale hydrogenation unit, catalysts A, B, C, and D were used respectively, at a hydrogen partial pressure of 5.0 MPa and a liquid hourly space velocity of 0.7 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500 Nm. 3 / m 3 The raw materials in Table 2 were hydrogenated under an average reaction temperature of 340℃.

[0033] Comparative Example 1

[0034] 100g of alumina support E (water absorption rate 75mL / 100g) was placed in a boiling pot. Under rotating conditions, 75mL of an impregnation solution containing 27.5g of molybdenum trioxide and 22.7g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes, dried at 120℃ for 6 hours, and calcined at 500℃ for 4 hours to obtain the finished catalyst E. The finished catalyst E was sulfided using an in-vessel sulfidation process, with the amount of dimethyl disulfide introduced being 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, with the temperature reaching 320℃ and held at that temperature for 10 hours.

[0035] Comparative Example 2

[0036] 100g of alumina support E (water absorption rate 75mL / 100g) was placed in a boiling pot. Under rotating conditions, 75mL of an impregnation solution containing 29.0g of molybdenum trioxide and 19.9g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes. Under the conditions of ambient temperature 26℃, material layer thickness 8cm, and exhaust gas fan frequency 35Hz, natural air was used for dehumidification for 10 hours. The catalyst dry basis was 76%. The catalyst was then calcined at 500℃ for 4 hours to obtain the finished catalyst F. The finished catalyst F was sulfided using an in-vessel sulfidation process. The amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, and the temperature was held at 320℃ for 10 hours.

[0037] Comparative Example 3

[0038] 100g of alumina support B (water absorption rate 90mL / 100g) was placed in a boiling pot. Under rotating conditions, 90mL of an impregnation solution containing 25.0g of molybdenum trioxide and 16.3g of basic cobalt carbonate was sprayed onto the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes, dried at 120℃ for 6 hours, and calcined at 500℃ for 4 hours to obtain the finished catalyst G. The finished catalyst G was sulfided using an in-vessel sulfidation process, with the amount of dimethyl disulfide introduced being 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, with the temperature reaching 320℃ and held at that temperature for 10 hours.

[0039] Comparative Example 4

[0040] 100g of alumina support H (water absorption rate 70mL / 100g) was placed in a boiling pot. Under rotating conditions, 70mL of an impregnation solution containing 28.6g of molybdenum trioxide and 16.8g of basic cobalt carbonate was sprayed into the alumina support in the boiling pot via atomization. After the solution was sprayed, the pot was rotated for another 30 minutes. Under the conditions of an ambient temperature of 26℃, a material layer thickness of 6cm, and a tail gas fan frequency of 35Hz, natural air was used for dehumidification for 10 hours. The catalyst dry basis was 78%. The catalyst was then calcined at 500℃ for 4 hours to obtain the finished catalyst H. The finished catalyst H was sulfided using an in-vessel sulfidation process. The amount of dimethyl disulfide introduced was 120% of the theoretical sulfur requirement of the catalyst. The sulfidation process used a programmed temperature rise, and the temperature was maintained at 320℃ for 10 hours.

[0041] Comparative Example 5

[0042] Catalysts E, F, G, and H were evaluated separately, using the same evaluation method as in Example 5.

[0043] Example 6

[0044] This example compares the physicochemical properties of the catalysts prepared in the above examples with the results of operating the above examples on a small-scale hydrogenation unit for 600 hours, as shown in Tables 1 and 2.

[0045] Table 1. Main properties of the catalyst

[0046]

[0047] Table 2. Test results of the catalyst

[0048]

[0049] The results in Table 2 show that the sulfur content in the slurry after hydrorefining of the catalyst of the present invention is <0.4%, and the loss rate of (tricyclic + tetracyclic) aromatics is 2 percentage points, which meets the feed requirements of high-end graphite units.

Claims

1. A selective hydrogenation catalyst for oil slurry, characterized in that: The catalyst comprises active metals Mo and Co, and a support γ-Al₂O₃. By weight of the total catalyst, Mo accounts for 9%–47% as MoO₃, and Co accounts for 2%–11% as CoO. The γ-Al₂O₃ has an average pore size of 8.0–12.0 nm and a specific surface area of ​​270–330 m². 2 ·g -1 The pore volume is 0.66~0.99cm. 3 ·g -1 The total amount of pyridine-infrared acid is 0.4~0.7 mmol.g. -1 The amount of Brønsted acid is 0.13~0.20 mmol·g. -1 The acid content of L-acid is 0.20~0.57 mmol·g. -1 The Brønsted acid / Low acid ratio is 0.30~1.00; the preparation method of the oil slurry selective hydrogenation catalyst includes the following: impregnating the hydrogenation catalyst support with an impregnation solution containing Mo and Co, and then curing and calcining the support to obtain the oil slurry selective hydrogenation catalyst; the curing is carried out by natural ventilation at an ambient temperature not exceeding 50℃, and the dehumidification time is 10~24 hours, so as to achieve a catalyst dry basis of 70%~90%.

2. The hydrogenation catalyst according to claim 1, characterized in that: Based on the total weight of the catalyst, Mo, calculated as MoO3, comprises 15wt%~35wt%, and Co, calculated as CoO, comprises 4wt%~9wt%; the γ-Al2O3 has an average pore size of 8.5~11.5nm and a specific surface area of ​​280~320m². 2 ·g -1 The pore volume is 0.68~0.80 cm³. 3 ·g -1 The total amount of pyridine-infrared acid is 0.45~0.65 mmol.g -1 The amount of Brønsted acid is 0.15~0.18 mmol·g. -1 The acid content of L-acid is 0.27~0.50 mmol·g. -1 The ratio of Brønsted acid to Lourdesic acid is 0.35 to 0.

66.

3. The hydrogenation catalyst according to claim 1, characterized in that: After sulfidation, the average lamellar length of the active phase MoS2 in the selective hydrogenation catalyst is 7~12nm, and the average number of lamellar layers in a single stack is 1~5. Based on the total number of stacks, the proportion of stacks with 3~5 layers is 40%~90%.

4. A method for preparing the oil slurry selective hydrogenation catalyst according to any one of claims 1 to 3, characterized in that... The process includes the following: impregnating a hydrogenation catalyst support with an impregnation solution containing Mo and Co, followed by curing and calcination of the support to obtain an oil slurry selective hydrogenation catalyst; the curing process involves natural ventilation to remove moisture at an ambient temperature not exceeding 50°C for 10-24 hours, aiming to achieve a catalyst dry basis of 70%-90%.

5. The method according to claim 4, characterized in that: The impregnation process employs a saturated spray impregnation method to load the active component.

6. The method according to claim 4, characterized in that: The ambient temperature is 20~40℃, and the dehumidification time is 12~20 hours, so as to achieve a catalyst dry basis of 75%~85%.

7. The method according to claim 4, characterized in that: The process of introducing natural wind to remove moisture is carried out using an exhaust gas dehumidification fan. The catalyst is placed on the conditioning belt, and natural wind is introduced through the exhaust gas dehumidification fan to remove the moisture. The thickness of the catalyst layer is controlled between 2 and 15 cm.

8. The method according to claim 7, characterized in that: The exhaust gas dehumidification fan operates at a frequency of 25~50Hz, corresponding to an exhaust volume of 3918m³ / h at full load (50Hz). 3 / h, the frequency is directly proportional to the induced draft volume.

9. The method according to claim 4, characterized in that: The roasting temperature is 300~550℃, and the roasting time is 3~4 hours.

10. The hydrogenation catalyst according to claim 3, characterized in that: The vulcanization treatment is carried out in-vessel or external vulcanization process. The amount of vulcanizing agent introduced is 90% to 150% of the theoretical sulfur required by the catalyst. The vulcanization process adopts programmed temperature rise, and the temperature is kept constant at 200 to 350°C for 1 to 16 hours. The vulcanizing agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide and n-butyl sulfide.

11. The application of the slurry selective hydrogenation catalyst according to any one of claims 1 to 3 in a slurry selective hydrogenation process, wherein the process conditions are: pressure 4.0 to 6.0 MPa, space velocity 0.5 to 1.0 h⁻¹. -1 Temperature 300~390℃, hydrogen-to-oil volume ratio 100~800.

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