Preparation method of oil slurry hydrogenation catalyst

Abstract

This invention discloses a method for preparing a slurry hydrodesulfurization catalyst, comprising the following steps: impregnating a hydrodesulfurization catalyst support with an impregnation solution containing Mo and Co; loading the impregnated support into a fixed-bed reactor and performing dry sulfidation to obtain the finished sulfidated catalyst; wherein the dry sulfidation process is as follows: after the hydrogen gas is gastight and a hydrogen circulation is established, the temperature is raised from room temperature to 350-550℃ and held at that temperature for 2-6 hours, wherein a certain H2S concentration is maintained in the circulating hydrogen after 230℃. The catalyst prepared by this method has high direct desulfurization activity, weakens the saturation performance of tricyclic and tetracyclic aromatic hydrocarbons, and is suitable for catalytic selective hydrodesulfurization reactions of slurry oil.

Description

Technical Field

[0001] This invention belongs to the field of petroleum refining, and specifically relates to a method for preparing a catalyst for the selective hydrogenation of oil slurry, particularly a method for preparing a catalyst for the selective hydrogenation of oil slurry. 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 aforementioned patents mainly focus on process improvements. CN110628461A mentions an Fe-modified CoMo / γ-Al2O3 selective hydrodesulfurization catalyst, but its function is not described in detail. CN113862035A states that the reaction stream first enters the desulfurization catalyst unit in the hydrotreating reactor, and then enters the hydroaromatics repair catalyst unit. The hydrodesulfurization catalyst is a hydrodesulfurization catalyst with γ-Al2O3 as the support and molybdenum and nickel as 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 method for preparing a slurry hydrodesulfurization catalyst. The catalyst prepared by this method exhibits high direct desulfurization activity, weakens the saturation properties of tricyclic and tetracyclic aromatic hydrocarbons, and is suitable for catalytic selective hydrodesulfurization reactions in slurry oil.

[0008] The preparation method of the slurry 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 loading the impregnated support into a fixed-bed reactor for dry sulfidation to obtain the finished sulfidated catalyst; wherein the dry sulfidation process is as follows: after the hydrogen gas is qualified and hydrogen circulation is established, the temperature is raised from room temperature to 350~550℃ and held at a constant temperature for 2~10 hours, wherein a certain H2S concentration in the circulating hydrogen is maintained after 230℃.

[0009] In the method of the present invention, the hydrogenation catalyst support is alumina, modified alumina, or a composite oxide containing alumina, such as silicon oxide-alumina, magnesium oxide-alumina, zinc oxide-alumina, etc., preferably alumina.

[0010] 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 a metal element is used as the source, and the concentration and amount of the impregnation solution are determined according to the catalyst composition. For example, if the active metal of Group VIB is Mo, molybdenum trioxide is generally used; if the active metal of Group VIII is Co, basic cobalt carbonate is generally used.

[0011] In the method of this invention, the reactor inlet pressure is 2.0~6.0MPa, and the dry vulcanization process adopts programmed temperature rise with a temperature rise rate of 3~30℃ / h.

[0012] In the method of this invention, fresh hydrogen is injected during the dry vulcanization process to maintain a constant system pressure, and the hydrogen circulation volume is approximately 2000~20000 m³. 3 If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen.

[0013] In the method of the present invention, the temperature is above 220°C, preferably above 230°C, during the sulfidation process, and the H2S concentration in the circulating hydrogen is maintained at 200~20000ppm. The H2S concentration before 220°C is adjusted according to actual needs.

[0014] In the method of this invention, H2S in the circulating hydrogen can be directly mixed in with H2S gas, or it can be controlled by controlling the injection of sulfide dosage. The sulfide agent is generally one or more of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide.

[0015] In the method of the present invention, the preferred dry vulcanization process is: (1) heating at room temperature to 230°C and holding at that temperature for 2 to 12 hours; (2) heating at 230°C to 350 to 550°C and holding at that temperature for 2 to 6 hours.

[0016] In the method of the present invention, the dry vulcanization process is further preferably: (1) the room temperature is programmed to 230°C and kept at a constant temperature for 2 to 12 hours; (2) the temperature is programmed to 320°C and kept at a constant temperature for 2 to 12 hours; (3) the temperature is programmed to 350 to 550°C and kept at a constant temperature for 2 to 6 hours.

[0017] In the method of the present invention, the dry vulcanization operation process is more preferably as follows: (1) heating from room temperature to 60°C at a rate of 5-25°C / h, holding the temperature for 3-5 hours, then heating at a rate of 5-25°C / h to 150°C, holding the temperature for 1-3 hours; (2) heating at a rate of 5-25°C / h to 230°C, holding the temperature for 4-10 hours, maintaining the H2S concentration in the circulating hydrogen at 200-5000ppm; (3) heating at a rate of 5-15°C / h to 320°C, holding the temperature for 4-10 hours, maintaining the H2S concentration in the circulating hydrogen at 5000-10000ppm; (4) heating at a rate of 5-15°C / h to 350-550°C, maintaining the H2S concentration in the circulating hydrogen at >10000ppm.

[0018] In the method of this invention, after dry vulcanization, feedstock oil (slurry oil) can be directly introduced for hydrogenation reaction. Typical process conditions are: 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 selective hydrotreating processes in oil slurry. This catalyst is also applicable to hydrodesulfurization processes for gasoline, kerosene, diesel, and wax oil fractions.

[0019] The slurry hydrogenation catalyst prepared by the method of the present invention comprises a Group VIB active metal, a Group VIII active metal, and γ-Al₂O₃; the Group VIB active metal is Mo; the Group VIII active metal is Co; based on the total weight of the catalyst, MoS₂ is 10wt%~52wt%, preferably 16wt%~39wt%, and Co₉S₈ is 2%~8%, preferably 3wt%~7wt%; the γ-Al₂O₃ has an average pore size of 8.0~12.0 nm, preferably 8.5~11.5 nm, and a specific surface area of ​​270~330 m². 2 .g -1 Preferred 280~320 m 2 .g -1 The pore volume is between 0.66 and 0.99 cm. 3 ·g -1 The preferred diameter is 0.68~0.80cm. 3 .g -1 The total amount of pyridine-infrared acid is between 0.4 and 0.7 mmol / g. -1 The preferred dosage is 0.45~0.65 mmol·g. -1 The amount of Brønsted acid is between 0.13 and 0.20 mmol / g. -1 The preferred dosage is 0.15~0.18 mmol·g. -1 The acid content of L-acid is between 0.20 and 0.57 mmol·g. -1 The preferred dosage is 0.27~0.50 mmol·g. -1 The ratio of Brønsted acid to Lønsted acid is 0.22 to 1.00, preferably 0.30 to 0.66. In the oil slurry selective hydrogenation catalyst of the present invention, the average lamellar length of the active phase (taking MoS2 as an example) is 7 to 12 nm, preferably 8 to 11 nm, and the average number of lamellar layers in a single stack is 1 to 5. Based on the total number of stacks, the proportion of stacks with 3 to 5 layers is 40% to 90%, preferably 40% to 70%.

[0020] 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. -1The ratio of Brønsted acid to Leached acid is between 0.22 and 1.00. In the method of this invention, the impregnated support is directly loaded into a fixed-bed reactor for dry sulfidation to obtain the finished sulfided catalyst. The average lamellar length of the active phase (taking MoS2 as an example) 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 increases the DDS reaction of sulfides. Maintaining a stack ratio of 3-5 layers allows the catalyst to still have relatively high hydrodesulfurization performance. Combined with the suitable pore size of γ-Al2O3, the selective hydrogenation of oil slurry is achieved.

[0021] 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 the 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 reactant molecules and active centers, which is beneficial for the desulfurization reaction. Conversely, since the average pore size of γ-Al₂O₃ is less than 10 times the macromolecular diameter of tricyclic and tetracyclic aromatic hydrocarbons, the confinement effect of the pores further restricts the flow of the tricyclic and tetracyclic aromatic hydrocarbons. Collisions between aromatic hydrocarbon molecules are more frequent than collisions with the catalyst pore walls, which is detrimental to contact with active centers and reduces the saturation of tricyclic and tetracyclic aromatic hydrocarbons. In this invention, the traditional drying, calcination, and sulfidation process is eliminated; the drying and calcination of the catalyst are completed directly during the dry sulfidation process, shortening the preparation process of the sulfided catalyst. Experimental verification shows that this increases the length of the active phase lamellar crystals after sulfidation of the active metal, while the large specific surface area and pore volume of γ-Al₂O₃ are beneficial for 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 means a reduction in L acid in the support, which is beneficial for improving the catalyst's resistance to coking, while an increase in Brønsted acid is beneficial for improving the catalyst's hydrodesulfurization activity. This invention improves production efficiency and saves energy. Attached Figure Description

[0022] Figure 1 Transmission electron microscopy image of the catalyst in Example 1 of this invention.

[0023] Figure 2 Transmission electron microscopy image of catalyst in Comparative Example 1. Detailed Implementation

[0024] 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:

[0025]

[0026] 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.

[0027] Example 1

[0028] 100g of alumina carrier A (water absorption rate 90mL / 100g) was placed in a rotating pot. While rotating, 90mL of an impregnation solution containing 27.5g of molybdenum trioxide and 22.7g of basic cobalt carbonate was sprayed into the alumina carrier in a mist manner. After spraying, the pot was rotated for another 30 minutes. The solution was then directly loaded into a fixed-bed reactor. After the hydrogen gas tightness was verified and circulation was established, the reactor inlet pressure was 4.0MPa, and the hydrogen circulation rate was approximately 7000m³. 3 If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen, raise the temperature to 60°C at a rate of 20°C / h, hold for 3 hours, then raise the temperature to 150°C at a rate of 20°C / h, hold for 2 hours, raise the temperature to 230°C at a rate of 10°C / h, hold for 6 hours to maintain the H2S concentration in the circulating hydrogen at 3000ppm, raise the temperature to 320°C at a rate of 10°C / h, hold for 6 hours to maintain the H2S concentration in the circulating hydrogen at 8000ppm, then raise the temperature to 450°C at a rate of 15°C / h, hold for 3 hours to achieve the H2S concentration in the circulating hydrogen at 11000ppm, thus obtaining the finished catalyst A.

[0029] Example 2

[0030] 100g of alumina carrier B (water absorption rate 90mL / 100g) was placed in a rotating pot. While rotating, 90mL of an impregnation solution containing 29.0g of molybdenum trioxide and 17.9g of basic cobalt carbonate was sprayed into the alumina carrier in a mist manner. After the solution was sprayed, the pot was rotated for another 30 minutes. The solution was then directly loaded into a fixed-bed reactor. After the hydrogen gas tightness was verified and circulation was established, the reactor inlet pressure was 5.0MPa, and the hydrogen circulation rate was approximately 8000m³. 3If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen, raise the temperature to 60°C at a rate of 25°C / h, hold for 4 hours, then raise the temperature to 150°C at a rate of 25°C / h, hold for 2 hours, raise the temperature to 230°C at a rate of 15°C / h, hold for 8 hours to maintain an H2S concentration of 4000ppm in the circulating hydrogen, raise the temperature to 320°C at a rate of 15°C / h, hold for 8 hours to maintain an H2S concentration of 7000ppm in the circulating hydrogen, and raise the temperature to 500°C at a rate of 15°C / h, hold for 3 hours to achieve an H2S concentration of 12000ppm in the circulating hydrogen, thus obtaining the finished catalyst B.

[0031] Example 3

[0032] 100g of alumina carrier C (water absorption rate 90mL / 100g) was placed in a rotating pot. While rotating, 90mL of an impregnation solution containing 25.0g of molybdenum trioxide and 16.3g of basic cobalt carbonate was sprayed into the alumina carrier in a mist manner. After spraying, the pot was rotated for another 30 minutes. The solution was then directly loaded into a fixed-bed reactor. After the hydrogen gas tightness was verified and circulation was established, the reactor inlet pressure was 4.0MPa, and the hydrogen circulation rate was approximately 7000m³. 3 If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen, raise the temperature to 230°C at a rate of 15°C / h, hold for 4 hours to maintain the H2S concentration in the circulating hydrogen at 4000ppm, raise the temperature to 400°C at a rate of 10°C / h, hold for 2 hours to achieve an H2S concentration of 10000ppm in the circulating hydrogen, and obtain the finished catalyst C.

[0033] Example 4

[0034] 100g of alumina carrier D (water absorption rate 90mL / 100g) was placed in a rotating pot. While rotating, 90mL of an impregnation solution containing 28.6g of molybdenum trioxide and 16.8g of basic cobalt carbonate was sprayed into the alumina carrier in a mist manner. After spraying, the pot was rotated for another 30 minutes. The solution was then directly loaded into a fixed-bed reactor. After the hydrogen gas tightness was verified and circulation was established, the reactor inlet pressure was 6.0MPa, and the hydrogen circulation rate was approximately 8000m³. 3 If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen, raise the temperature to 230°C at a rate of 20°C / h, hold for 4 hours to maintain an H2S concentration of 3000ppm in the circulating hydrogen, raise the temperature to 320°C at a rate of 10°C / h, hold for 6 hours to maintain an H2S concentration of 6000ppm in the circulating hydrogen, raise the temperature to 450°C at a rate of 15°C / h, hold for 3 hours to achieve an H2S concentration of 11000ppm in the circulating hydrogen, and obtain the finished catalyst D.

[0035] Example 5

[0036] 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℃.

[0037] Comparative Example 1

[0038] 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.

[0039] Comparative Example 2

[0040] 100g of alumina carrier E (water absorption rate 75mL / 100g) was placed in a rotating pot. While rotating, 75mL of an impregnation solution containing 29.0g of molybdenum trioxide and 19.9g of basic cobalt carbonate was sprayed into the alumina carrier in a mist manner. After the solution was sprayed, the pot was rotated for another 30 minutes. The mixture was then directly loaded into a fixed-bed reactor. After the hydrogen gas tightness was verified and circulation was established, the reactor inlet pressure was 4.0MPa, and the hydrogen circulation rate was approximately 7000m³. 3 If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen, raise the temperature to 60°C at a rate of 20°C / h, hold for 3 hours, then raise the temperature to 150°C at a rate of 20°C / h, hold for 2 hours, raise the temperature to 230°C at a rate of 10°C / h, hold for 6 hours to maintain the H2S concentration in the circulating hydrogen at 0.3%, raise the temperature to 320°C at a rate of 10°C / h, hold for 6 hours to maintain the H2S concentration in the circulating hydrogen at 0.8%, and raise the temperature to 450°C at a rate of 15°C / h, hold for 3 hours to achieve the H2S concentration in the circulating hydrogen at 1.1%, thus obtaining the finished catalyst F.

[0041] Comparative Example 3

[0042] 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.

[0043] Comparative Example 4

[0044] 100g of alumina carrier D (water absorption rate 90mL / 100g) was placed in a rotating pot. While rotating, 90mL of an impregnation solution containing 28.6g of molybdenum trioxide and 16.8g of basic cobalt carbonate was sprayed into the alumina carrier in a mist manner. After the solution was sprayed, the pot was rotated for another 30 minutes. The mixture was then directly loaded into a fixed-bed reactor. After the hydrogen gas tightness was verified and circulation was established, the reactor inlet pressure was 4.0MPa, and the hydrogen circulation rate was approximately 7000m³. 3 If the pressure is too high, open the bypass valve to release pressure to the flare. If the pressure is too low, add fresh hydrogen, raise the temperature to 150°C at a rate of 20°C / h, hold for 2 hours, raise the temperature to 250°C at a rate of 10°C / h, hold for 6 hours to maintain the H2S concentration in the circulating hydrogen at 3000ppm, raise the temperature to 320°C at a rate of 10°C / h, hold for 6 hours to maintain the H2S concentration in the circulating hydrogen at 8000ppm, raise the temperature to 450°C at a rate of 15°C / h, hold for 3 hours to achieve the H2S concentration in the circulating hydrogen at 11000ppm, and obtain the finished catalyst H.

[0045] Comparative Example 5

[0046] Catalysts E, F, G, and H were evaluated separately, using the same evaluation method as in Example 5.

[0047] Example 6

[0048] 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.

[0049] Table 1. Main properties of the catalyst

[0050]

[0051] Table 2. Test results of the catalyst

[0052]

[0053] 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 slurry hydrogenation catalyst, characterized in that, The catalyst comprises active metals Mo and Co, and γ-Al₂O₃; by total weight of the catalyst, MoS₂ accounts for 10wt%~52wt%, and Co₉S₈ accounts for 2wt%~8wt%; 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 ratio of Brønsted acid to Lourdesic acid is 0.30~1.00; In the catalyst, the average lamellar length of the active phase MoS2 is 7~12nm, the average number of lamellar layers in a single stack is 1~5, and based on the total number of stacks, the proportion of stacks with 3~5 layers is 40%~90%.

2. The slurry hydrogenation catalyst according to claim 1, characterized in that, Based on the total weight of the catalyst, MoS2 accounts for 16wt%~39wt%, and Co9S8 accounts for 3wt%~7wt%; the specific surface area of ​​the γ-Al2O3 is 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 L-carnitine is 0.30 to 0.

66.

3. The slurry hydrogenation catalyst according to claim 1, characterized in that, The average lamellar length of the active phase MoS2 is 8~11 nm. Based on the total number of stack layers, the proportion of stack layers with 3~5 layers is 40%~70%.

4. The method for preparing the slurry hydrogenation catalyst according to any one of claims 1-3, characterized in that, The process includes the following: impregnating γ-Al2O3 with an impregnation solution containing Mo and Co, then loading it into a fixed-bed reactor for dry sulfidation to obtain the finished sulfidated oil slurry hydrogenation catalyst; wherein the dry sulfidation process is as follows: after the hydrogen gas is qualified and hydrogen circulation is established, the temperature is raised from room temperature to 350~550℃ and held at a constant temperature for 2~10 hours, wherein a certain H2S concentration in the circulating hydrogen is maintained above 220℃.

5. The method according to claim 4, characterized in that: The fixed-bed reactor has an inlet pressure of 2.0~6.0MPa, and the dry vulcanization process uses programmed temperature rise at a rate of 3~30℃ / h.

6. The method according to claim 4, characterized in that: During the dry sulfidation process, the temperature is above 220°C, and the H2S concentration in the circulating hydrogen is maintained at 200~20000ppm.

7. The method according to claim 4, characterized in that: H2S in the circulating hydrogen is introduced by directly mixing in H2S gas or by injecting a sulfiding agent; the sulfiding agent is one or more of carbon disulfide, dimethyl disulfide, methyl sulfide, and n-butyl sulfide.

8. The method according to claim 4, characterized in that: The dry vulcanization process is as follows: (1) The temperature is increased to 230°C at room temperature and kept constant for 2 to 12 hours; (2) The temperature is increased to 350 to 550°C at 230°C and kept constant for 2 to 6 hours.

9. The method according to claim 4, characterized in that: The dry vulcanization process is as follows: (1) the temperature is increased to 230°C at room temperature and kept constant for 2 to 12 hours; (2) the temperature is increased to 320°C and kept constant for 2 to 12 hours; (3) the temperature is increased to 350 to 550°C and kept constant for 2 to 6 hours.

10. The method according to claim 4, characterized in that: The dry vulcanization process is as follows: (1) Heat the temperature to 60°C at room temperature at a rate of 5-25°C / h, hold the temperature for 3-5 hours, then heat the temperature to 150°C at a rate of 5-25°C / h, and hold the temperature for 1-3 hours; (2) Heat the temperature to 230°C at a rate of 5-25°C / h, hold the temperature for 4-10 hours, and maintain the H2S concentration in the circulating hydrogen at 200-5000ppm; (3) Heat the temperature to 320°C at a rate of 5-15°C / h, hold the temperature for 4-10 hours, and maintain the H2S concentration in the circulating hydrogen at 5000-10000ppm; (4) Heat the temperature to 350-550°C at a rate of 5-15°C / h, and maintain the H2S concentration in the circulating hydrogen at >10000ppm.

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