Catalytic hydrogenation method for oil slurry

Abstract

The invention relates to a catalytic hydrogenation method for oil slurry, which comprises the following steps: under a hydrodesulfurization condition, contacting an oil slurry raw material with a hydrogenation catalyst to carry out a catalytic hydrodesulfurization reaction, wherein the hydrogenation catalyst comprises a core-layer catalyst and a SiO2 layer coated on the surface of the core-layer catalyst; the core layer catalyst comprises an alumina carrier and an active component loaded on the alumina carrier; the active component comprises at least one group VIB metal; the content of the group VIB metal is 8-25wt% in terms of oxide and on the basis of the total weight of the core-layer catalyst; the SiO2 layer is of a porous structure, and the pore diameter of the SiO2 layer is 0.5-3 nm. The content of VIB group metal in the hydrogenation catalyst used in the invention is high, the SiO2 layer can realize coupling of raw material separation and hydrodesulfurization reaction, and tetracyclic and more aromatic hydrocarbons are limited from entering a nuclear layer catalyst, so that the hydrodesulfurization activity and the retention rate of tetracyclic aromatic hydrocarbons in the raw materials are improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of petrochemical industry, and particularly relates to a method for catalytic hydrogenation of oil slurry. BACKGROUND

[0002] Needle coke has a series of advantages such as low thermal expansion coefficient, low porosity, low metal content, low ash content, high electrical conductivity and easy graphitization, and is a high-quality raw material for producing high-power and super-high-power graphite electrodes, special carbon materials, carbon fibers and their composites, and other high-end carbon products, and has a wide application in the electrode, fuel cell and lithium ion battery industries.

[0003] Catalytic cracking slurry oil has the characteristics of large density, low hydrogen-carbon atomic ratio, high carbon residue value and high aromatic content, and most of the aromatics are 2-4 ring structure (300-500℃) fractions, and the catalytic slurry oil also contains a considerable amount of saturated fractions, which is an important raw material for preparing needle coke. However, the content of impurities such as sulfur in catalytic slurry oil is relatively high, therefore, the catalytic slurry oil with sulfur content less than 0.5 wt% and high content of three-ring and four-ring short side chain aromatics obtained by hydrogenation desulfurization treatment is an ideal raw material for preparing needle coke.

[0004] The sulfur-containing compounds in the oil slurry are mainly C1-C3 alkyl side chain substituted benzothiophene, diphenylthiophene and naphthalene benzothiophene. The hydrogenation desulfurization reaction of such sulfur-containing compounds requires first saturating the aromatics and then hydrogenolysis desulfurization, and the reaction pathway of the first step is similar to that of polycyclic aromatic hydrocarbon hydrogenation. However, polycyclic aromatic hydrocarbons are more easily adsorbed on the hydrogenation active sites of the catalyst than sulfur-containing molecules, and have stronger competitive adsorption, thereby more greatly inhibiting the desulfurization reaction, increasing the difficulty of desulfurization, and causing loss of ideal aromatic components, and the desulfurization selectivity cannot be effectively improved. Therefore, how to improve the desulfurization activity of the oil slurry while improving the retention rate of three-ring / tetra-ring aromatics has become a research focus for preparing high-quality needle coke.

[0005] CN114984985A discloses a preparation method of a hydrodesulfurization catalyst, which uses a wetting agent and a pore-expanding agent to modify the carrier to enhance the adsorption capacity of the carrier to the impregnation liquid; the catalyst prepared by using the carrier has a good pore structure and certain acidity, and the catalyst can effectively remove complex thiophene-containing sulfur compounds in the needle coke raw material, and retain as many three-ring and four-ring aromatics in the needle coke raw material as possible.

[0006] CN110628461A discloses a method for selectively hydrodesulfurizing and retaining aromatic hydrocarbons in oil slurry, which removes catalyst particles in the oil slurry by ultrasonic assisted centrifugal operation; removes the residual catalyst particles, asphaltene and resin in the oil slurry while retaining the extract oil rich in aromatic hydrocarbons; and removes sulfur by selectively hydrodesulfurizing the extract oil by using Fe-modified CoMo / γ-Al2O3 selective hydrodesulfurization catalyst, thereby improving the desulfurization rate, selectively hydrogenating, retaining the content of aromatic hydrocarbon components and reducing the loss of aromatic hydrocarbons.

[0007] However, the current process still has the problem of excessive loss of beneficial aromatic components while removing sulfur compounds in the oil slurry by hydrogenation saturation. SUMMARY

[0008] The purpose of the present application is to further reduce the loss of beneficial aromatic hydrocarbons in the process of catalytic hydrodesulfurization of oil slurry.

[0009] To achieve the above purpose, the first aspect of the present application provides a method for catalytic hydrogenation of oil slurry, which comprises the following steps: contacting the oil slurry raw material with a hydrogenation catalyst under hydrodesulfurization conditions to perform a catalytic hydrodesulfurization reaction; wherein the hydrogenation catalyst comprises a core layer catalyst and a SiO2 layer coated on the surface of the core layer catalyst; the core layer catalyst comprises an alumina carrier and an active component supported on the alumina carrier; the active component comprises at least one Group VIB metal; the content of the Group VIB metal is 8-25% by weight based on the total weight of the core layer catalyst in terms of oxide; the SiO2 layer has a porous structure, and the pore size of the SiO2 layer is 0.5-3 nm.

[0010] Optionally, the active component further comprises at least one Group VIII metal; the content of the Group VIB metal is 10-20% by weight, preferably 12-20% by weight, and the content of the Group VIII metal is 0.5-15% by weight, preferably 2-10% by weight, and more preferably 2-8% by weight, based on the total weight of the core layer catalyst in terms of oxide; preferably, the Group VIB metal is selected from at least one of molybdenum and tungsten, and is preferably molybdenum; the Group VIII metal is selected from at least one of cobalt and nickel, and is preferably cobalt.

[0011] Optionally, the particle size of the hydrogenation catalyst is 0.8-1.2 mm; the average pore size of the alumina carrier is 5-15 nm; the pore volume of the alumina carrier is 0.4-1.0 cm 3 / g; and the specific surface area of the alumina carrier is 200-400 m 2 / g.

[0012] Optionally, the SiO2 layer has a thickness of 1 nm-30 µm, preferably 20 nm-20 µm; and a pore size of 1-2 nm.

[0013] Optionally, the hydrodesulfurization reaction has a reaction temperature of 300-550 ℃, preferably 330-480 ℃, a hydrogen partial pressure of 4-20 MPa, preferably 4-18 MPa, a volume space velocity of 0.1-3 h -1 , preferably 0.15-2 h -1 , and a hydrogen to oil volume ratio of 200-2500, preferably 300-2000; preferably, the oil slurry feedstock is catalytic cracking oil slurry; the sulfur content in the oil slurry feedstock is 0.5-2.5 wt%; and the content of tetranuclear aromatic hydrocarbons in the oil slurry feedstock is 20-50 wt%.

[0014] Optionally, the method for preparing the hydrogenation catalyst comprises the following steps: mixing the core layer catalyst, an alcohol and water to obtain a mixed solution; the volume ratio of the alcohol to the water is 1-10:1; mixing the mixed solution and a template agent and dispersing under ultrasonic conditions to obtain a first mixture; mixing the first mixture and an alkaline reagent under stirring conditions to obtain a second mixture; adding an organosilicon source to the second mixture under stirring conditions to coat the core layer catalyst, and solid-liquid separation and removal of the template agent to obtain the hydrogenation catalyst.

[0015] Optionally, the mass ratio of the alcohol to the water is 2-9:1; preferably, the mass ratio of the core layer catalyst to the template agent is 1:0.05-1; and the template agent is selected from one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride.

[0016] Optionally, the pH value of the second mixture is 8-10; the alkaline reagent is selected from one or more of aqueous ammonia, sodium hydroxide, potassium hydroxide and triethanolamine, preferably aqueous ammonia and / or sodium hydroxide; preferably, the mass ratio of the organosilicon source to the core layer catalyst is 0.03-0.8:1, calculated based on SiO2; and preferably, the organosilicon source is selected from at least one of dimethyldiethylsiloxane, methyl orthosilicate and ethyl orthosilicate.

[0017] Optionally, the coating reaction has a reaction temperature of 20-100 ℃, preferably 20-30 ℃.

[0018] Optionally, the template agent is removed by calcination, and the calcination conditions include a temperature of 200-600 DEG C and a time of 2-10 h; preferably, the calcination includes first calcination and second calcination performed in sequence; the first calcination conditions include a temperature of 200-300 DEG C and a time of 1-3 h; and the second calcination conditions include a temperature of 400-500 DEG C and a time of 3-5 h; the heating rate is 0.5 DEG C / min-10 DEG C / min, preferably 1 DEG C / min-3 DEG C / min.

[0019] By the technical solution, the SiO2 layer is coated on the surface of the core layer catalyst, and the core layer catalyst with high content of the Group VIB metal is used, and by controlling the pore size of the SiO2 layer, the coupling of the feedstock separation and the hydrodesulfurization reaction can be realized, the tetranuclear and above aromatic hydrocarbons are limited to enter the core layer catalyst, and thus the hydrodesulfurization activity and the retention rate of the tetranuclear aromatic hydrocarbons in the feedstock are improved.

[0020] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0021] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0022] The first aspect of the present application provides a method for catalytic hydrogenation of oil slurry, which comprises the following steps: Under the hydrodesulfurization conditions, the oil slurry feedstock is contacted with a hydrogenation catalyst to perform a catalytic hydrodesulfurization reaction; wherein the hydrogenation catalyst comprises a core layer catalyst and a SiO2 layer coated on the surface of the core layer catalyst; the core layer catalyst comprises an alumina carrier and an active component loaded on the alumina carrier; the active component comprises at least one Group VIB metal; the content of the Group VIB metal is 8-25% by weight, calculated as an oxide and based on the total weight of the core layer catalyst; and the SiO2 layer has a porous structure, and the pore size of the SiO2 layer is 0.5-3 nm.

[0023] The hydrogenation catalyst used in the method for catalytic hydrogenation of oil slurry provided by the present application has a core-shell structure, by coating a SiO2 layer on the surface of the core layer catalyst, and using a core layer catalyst with high content of the Group VIB metal, the coupling of the feedstock separation and the hydrodesulfurization reaction can be realized by controlling the pore size of the SiO2 layer, the tetranuclear and above aromatic hydrocarbons are limited to enter the core layer catalyst, and thus the hydrodesulfurization activity and the retention rate of the tetranuclear aromatic hydrocarbons in the feedstock are improved.

[0024] Since polycyclic aromatic hydrocarbons have stronger competitive adsorption than sulfur-containing molecules, by calculating the size of a typical four-ring aromatic hydrocarbon pyrene molecule, using the separation and reaction coupling function of the shell material, and controlling the pore size of the porous shell material, the four-ring aromatic hydrocarbon can be limited to enter the shell layer, thereby improving the desulfurization selectivity of the catalyst to sulfur-containing molecules in the oil slurry and improving the catalytic performance of the desulfurization catalyst.

[0025] In some embodiments of the present application, the active component further comprises at least one Group VIII metal; the content of the Group VIB metal is 10-20% by weight, preferably 12-20% by weight, and the content of the Group VIII metal is 0.5-15% by weight, preferably 2-10% by weight, and more preferably 2-8% by weight, based on the total weight of the core layer catalyst.

[0026] Preferably, the Group VIB metal is selected from at least one of molybdenum and tungsten, and preferably molybdenum; and the Group VIII metal is selected from at least one of cobalt and nickel, and preferably cobalt.

[0027] In some embodiments of the present application, the particle size of the hydrogenation catalyst is 0.8-1.2 mm.

[0028] In the present application, the shape of the alumina carrier can be cylindrical, butterfly-shaped or spherical, and preferably spherical. The average pore size of the alumina carrier is 5-15 nm; the pore volume of the alumina carrier is 0.4-1.0 cm 3 / g; and the specific surface area of the alumina carrier is 200-400 m 2 / g.

[0029] In some embodiments of the present application, the thickness of the SiO2 layer is 1 nm-30 µm, and preferably 20 nm-20 µm.

[0030] The pore size of the SiO2 layer is 1-2 nm, which is conducive to the adsorption of sulfur-containing compounds on the hydrogenation active sites of the core layer catalyst, limits the entry of four-ring and above aromatic hydrocarbons into the pores of the hydrogenation catalyst, and improves the retention rate of three-ring or four-ring aromatic hydrocarbons in the raw material while improving the desulfurization activity of the catalyst.

[0031] In some embodiments of the present application, the conditions of the hydrodesulfurization reaction include a reaction temperature of 300-550°C, preferably 330-480°C, a hydrogen partial pressure of 4-20 MPa, preferably 4-18 MPa, a volume space velocity of 0.1-3 h -1 , preferably 0.15-2 h -1 , and a hydrogen to oil volume ratio of 200-2500, preferably 300-2000.

[0032] Preferably, the oil slurry raw material is catalytic cracking oil slurry; the sulfur content in the oil slurry raw material is 0.5-2.5% by weight; and the content of tetranuclear aromatic hydrocarbon in the oil slurry raw material is 20-50% by weight.

[0033] In the present application, the device suitable for the desulfurization hydrogenation of the oil slurry includes but is not limited to a fixed bed reactor, a moving bed reactor or a boiling bed reactor. According to the conventional method in the art, the hydrogenation catalyst also needs to be presulfurized before use, and the method of presulfurization is usually to place the hydrogenation catalyst in a hydrogen-containing atmosphere, and presulfurize the hydrogenation catalyst at 140-370 ℃ using sulfur, hydrogen sulfide or sulfur-containing raw materials. The presulfurization of the hydrogenation catalyst can be carried out outside the reactor, or in-situ sulfidation in the reactor to convert the carrier-loaded active metal component into a metal sulfide component.

[0034] In some embodiments of the present application, the preparation method of the hydrogenation catalyst comprises the following steps: S1, mixing the core layer catalyst, alcohol and water to obtain a mixed solution; the volume ratio of the alcohol to the water is 1-10; S2, mixing the mixed solution and a template agent and dispersing under ultrasonic conditions to obtain a first mixture; S3, mixing the first mixture and an alkaline reagent under stirring conditions to obtain a second mixture; S4, adding an organic silicon source to the second mixture under stirring conditions to coat the core layer catalyst, and then solid-liquid separation and removal of the template agent to obtain the hydrogenation catalyst.

[0035] In some preferred embodiments of the present application, the volume ratio of the alcohol to the water is 2-9.

[0036] The pore size of the SiO2 layer can be controlled by selecting a suitable template agent, wherein the template agent is a cationic surfactant, and specifically, the template agent is selected from one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride. Preferably, the concentration of the template agent in the system during the coating treatment is 1-50 mmol / L, preferably 5-30 mmol / L, so as to form a continuous and complete coating on the surface of the core layer catalyst.

[0037] Preferably, the mass ratio of the core layer catalyst to the template agent is 1:0.05-1.

[0038] In some embodiments of the present application, the pH value of the second mixture is 8-10; in particular, the basic reagent is selected from one or more of ammonia, sodium hydroxide, potassium hydroxide, triethanolamine and the like, preferably ammonia and / or sodium hydroxide. In particular, the concentration of the basic reagent is 0.05-2 mol / L, preferably 0.1-0.5 mol / L. The appropriate amount of the basic reagent is conducive to the hydrolysis and condensation of the organosilicon source to coat the surface of the core layer catalyst. Too little (too low concentration) or too much (too high concentration) of the basic reagent is not conducive to the formation of a continuous shell layer, or it may not be able to coat the surface of the core layer catalyst.

[0039] In some embodiments of the present application, the mass ratio of the organosilicon source to the core layer catalyst, calculated based on SiO2, is 0.03-0.8:1; in particular, the organosilicon source is selected from at least one of dimethyldiethylsiloxane, methyl orthosilicate and ethyl orthosilicate, preferably ethyl orthosilicate. In particular, the concentration of the organosilicon source in the system during the coating process is 1-50 mmol / L, preferably 5-30 mmol / L.

[0040] In some embodiments of the present application, the coating reaction temperature is 20-100℃, preferably 20-30℃.

[0041] In the above method, the mixture after coating is subjected to solid-liquid separation by filtration, and the obtained solid is washed with an organic solvent and / or deionized water, and the organic solvent includes but is not limited to one or more of ethanol, toluene and acetone.

[0042] In some embodiments of the present application, the template agent is removed by calcination; the calcination conditions include a temperature of 200-600℃ and a time of 2-10 h.

[0043] In particular, the calcination includes sequentially performed first calcination and second calcination; the first calcination conditions include a temperature of 200-300℃ and a time of 1-3 h; the second calcination conditions include a temperature of 400-500℃ and a time of 3-5 h. Preferably, the temperature is raised in stages, first from room temperature to 200-300℃, maintained for 1-3 h, then raised to 400-500℃, maintained for 3-5 h, and the heating rate is 0.5℃ / min-10℃ / min, preferably 1℃ / min-3℃ / min.

[0044] The method provided by the present application can convert low-value catalytic cracking slurry oil into an ideal component and important raw material for producing needle coke, promote the high-value utilization of catalytic cracking slurry oil, and has a broad application prospect.

[0045] The application will be further illustrated in detail by the following examples, but the application is not limited to the following examples.

[0046] The raw materials used in the examples can be obtained by commercial channels. Among them, dodecyl trimethyl ammonium chloride (DTAC), purity ≥ 99.0%; Tetradecyl trimethyl ammonium bromide (TTAB), purity ≥ 99.0%; Cetyl trimethyl ammonium bromide (CTAB), purity ≥ 99.0%; Anhydrous ethanol, 99.5 wt%; Ammonia water, ammonia mass fraction is 26-28 wt%; Tetraethyl orthosilicate (TEOS), purity ≥ 99.0%; Alumina carrier, specific surface area is 268 m 2 / g, average pore size is 13.52 nm, total pore volume is 0.9 cm 3 / g.

[0047] The properties of the raw oil in the examples and comparative examples of the application are shown in Table 1.

[0048] Table 1

[0049] Example 1 This example is used to illustrate the preparation method of the hydrogenation catalyst provided by the application, which comprises the following steps: S1, 100 g of an alumina carrier is weighed, and the alumina carrier is impregnated with 85 mL of an impregnating solution for 1 hour; then the impregnated solid is dried and calcined to obtain a core layer catalyst K1; wherein the impregnating solution is prepared from molybdenum trioxide, basic cobalt carbonate and phosphoric acid, the content of molybdenum compound in the impregnating solution is 304.4 g / L, the content of cobalt compound in the impregnating solution is 141.9 g / L, and the content of P2O5 is 41 g / L; the drying temperature is 120 ℃, and the drying time is 3 h; the calcination temperature is 400 ℃, and the calcination time is 3 h; S2, 10 g of the core layer catalyst K1 is weighed and dispersed in an ethanol solution to obtain a mixed solution; wherein the ethanol solution is obtained by mixing 360 mL of anhydrous ethanol and 40 mL of deionized water; S3, 1 g of the template DTAC is added to the mixed solution obtained in step S2, and ultrasonic treatment is performed for 30 min to obtain a first mixture; S4, 5 mL of ammonia water is added to the first mixture obtained in step S3 under stirring, and the reaction is carried out for 30 min to obtain a second mixture; S5, 1 mL of TEOS was added dropwise to the second mixture obtained in step S4 under stirring, and the reaction was carried out for 6 h; then the mixture after the reaction was filtered, and the solid obtained by filtration was washed with ethanol for 3 times; S6, the washed solid was dried at 120 ℃ for 4 h, and then template removal was carried out by stepwise calcination to obtain a hydrogenation catalyst, denoted as C1; the stepwise calcination included a first calcination and a second calcination, the first calcination included: increasing the temperature from room temperature to 250 ℃ at a rate of 1.5 ℃ / min, and maintaining for 2 h; the second calcination included: increasing the temperature to 400 ℃ at a rate of 1.5 ℃ / min, and maintaining for 3 h.

[0050] The properties of the hydrogenation catalyst C1 are shown in Table 2.

[0051] Example 2 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference from Example 1 is that the template added in step S3 is TTAB, and the amount added is 3 g; The volume of TEOS added in step S5 is 3 mL. The obtained hydrogenation catalyst is denoted as C2, and the properties are shown in Table 2.

[0052] Example 3 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference from Example 1 is that the template added in step S3 is CTAB, and the amount added is 5 g; The volume of ammonia added in step S4 is 10 mL; The volume of TEOS added in step S5 is 5 mL. The obtained hydrogenation catalyst is denoted as C3, and the properties are shown in Table 2.

[0053] Example 4 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference from Example 1 is that: The volume of ammonia added in step S4 is 1.5 mL. The obtained hydrogenation catalyst is denoted as C4, and the properties are shown in Table 2.

[0054] Example 5 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference from Example 1 is that: The mass ratio of anhydrous ethanol in step S2 is 280 mL, and the mass ratio of deionized water is 120 mL. The obtained hydrogenation catalyst is denoted as C5, and the properties are shown in Table 2.

[0055] Example 6 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference from Example 1 is that: The amount of anhydrous ethanol and deionized water in step S2 is 200 mL. The obtained hydrogenation catalyst is recorded as C6, and its properties are shown in Table 2.

[0056] Example 7 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference between this example and Example 1 is that: In step S1, the content of the molybdenum compound in the impregnation solution is 152.2 g / L calculated as MoO3, the content of the cobalt compound is 141.9 g / L calculated as CoO, and the content of P2O5 is 23 g / L. The obtained hydrogenation catalyst is recorded as C7, and its properties are shown in Table 2.

[0057] Comparative Example 1 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference between this example and Example 1 is that: In step S1, the impregnation solution is prepared by dissolving basic cobalt carbonate and ammonium heptamolybdate tetrahydrate in deionized water, and the content of the molybdenum compound in the impregnation solution is 128.0 g / L calculated as MoO3, and the content of the cobalt compound is 141.9 g / L calculated as CoO; In step S2, the mass ratio of anhydrous ethanol is 160 mL, and the mass ratio of deionized water is 240 mL. The obtained hydrogenation catalyst is recorded as D1, and its properties are shown in Table 2.

[0058] Comparative Example 2 The method for preparing the hydrogenation catalyst in this example refers to Example 1, and the difference between this example and Example 1 is that: The thickness of the SiO2 layer obtained by coating the surface of the core layer catalyst K1 is 10 μm, and the pore size of the SiO2 layer is 3.2 nm. The obtained hydrogenation catalyst is recorded as D3. The properties of D3 are shown in Table 2.

[0059] Table 2

[0060] Example 8 This example is used to illustrate the method for catalytically hydrogenating oil slurry provided by the application.

[0061] The hydrogenation catalyst C1 is pre-sulfided before the reaction, and the pre-sulfiding conditions include: a temperature of 360 ℃, a time of 3 hours, a hydrogen partial pressure of 4.0 MPa, a hydrogen / oil volume ratio of 600, and a liquid hourly space velocity of the sulfiding oil (5 wt% CS2+95 wt% cyclohexane) of 1.2 h -1 .

[0062] The oil slurry having the properties shown in Table 1 was used as a raw material, and was fed into a 100 mL small-sized fixed bed reactor to contact with a hydrogenation catalyst Cl (catalyst loading amount: 100 mL, particle size: 0.8-1.2 mm) packed therein to perform catalytic hydrogenation reaction. The conditions of the catalytic hydrogenation reaction included a reaction temperature of 320°C, a hydrogen partial pressure of 4 MPa, a liquid hourly space velocity of 0.5 h -1 , and a hydrogen / oil volume ratio of 600.

[0063] The sulfur content and tetra-cyclic aromatic hydrocarbon content in the produced oil were measured, and the desulfurization rate and tetra-cyclic aromatic hydrocarbon retention rate were calculated, and the results are shown in Table 3.

[0064] The calculation formulas of the desulfurization rate and aromatic hydrocarbon retention rate are as follows: ; Tetra-cyclic aromatic hydrocarbon retention rate = (tetra-cyclic aromatic hydrocarbon content in produced oil / tetra-cyclic aromatic hydrocarbon content in raw material) x 100%.

[0065] Examples 9-14 The method of catalytic hydrogenation of the oil slurry in Examples 9-14 was performed with reference to Example 8, and the difference from Example 8 was that the catalyst packed in the reactor was hydrogenation catalyst C2, hydrogenation catalyst C3, hydrogenation catalyst C4, hydrogenation catalyst C5, hydrogenation catalyst C6, and hydrogenation catalyst C7, respectively.

[0066] The sulfur content and tetra-cyclic aromatic hydrocarbon content in the produced oil were measured, and the results of the desulfurization rate and tetra-cyclic aromatic hydrocarbon retention rate are shown in Table 3.

[0067] Comparative Example 3 The method of catalytic hydrogenation of the oil slurry in this comparative example was performed with reference to Example 8, and the difference from Example 8 was that the catalyst packed in the reactor was core layer catalyst K1 prepared in Example 1. The sulfur content and tetra-cyclic aromatic hydrocarbon content in the produced oil were measured, and the results of the desulfurization rate and tetra-cyclic aromatic hydrocarbon retention rate are shown in Table 3.

[0068] Comparative Example 4 The method of catalytic hydrogenation of the oil slurry in this comparative example was performed with reference to Example 8, and the difference from Example 8 was that the catalyst packed in the reactor was hydrogenation catalyst D1 prepared in Comparative Example 1. The sulfur content and tetra-cyclic aromatic hydrocarbon content in the produced oil were measured, and the results of the desulfurization rate and tetra-cyclic aromatic hydrocarbon retention rate are shown in Table 3.

[0069] Comparative Example 5 The method of catalytic hydrogenation of the oil slurry in this comparative example was performed with reference to Example 8, and the difference from Example 8 was that the catalyst packed in the reactor was hydrogenation catalyst D2 prepared in Comparative Example 2. The sulfur content and tetra-cyclic aromatic hydrocarbon content in the produced oil were measured, and the results of the desulfurization rate and tetra-cyclic aromatic hydrocarbon retention rate are shown in Table 3.

[0070] Table 3

[0071] From the data in the above table, it can be seen that the oil slurry catalytic hydrogenation method provided by the application can not only ensure the oil slurry desulfurization rate, but also can significantly improve the retention rate of tetranuclear aromatic hydrocarbons in the raw material.

[0072] The preferred embodiments of the application are described in detail above, but the application is not limited to the specific details in the above-described embodiments, and various simple modifications can be made to the technical solutions of the application within the technical concept of the application, and these simple modifications all belong to the protection scope of the application.

[0073] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again by the application.

[0074] In addition, various different embodiments of the application can also be combined in any manner, as long as it does not deviate from the idea of the application, and it should also be considered as disclosed by the application.

Claims

1. A process for catalytic hydroprocessing of oil slurry, characterized by, The method comprises the following steps: under the hydrogen desulfurization condition, the oil slurry raw material is contacted with a hydrogenation catalyst to perform a catalytic hydrodesulfurization reaction; The hydrogenation catalyst comprises a core layer catalyst and a SiO2 layer coated on the surface of the core layer catalyst; the core layer catalyst comprises an alumina carrier and an active component loaded on the alumina carrier; the active component comprises at least one Group VIB metal; the content of the Group VIB metal is 8-25% by weight based on the total weight of the core layer catalyst; the SiO2 layer has a porous structure, and the pore size of the SiO2 layer is 0.5-3 nm.

2. The method of claim 1, wherein, The active component further comprises at least one Group VIII metal; The content of the Group VIB metal is 10-20% by weight, preferably 12-20% by weight, and the content of the Group VIII metal is 0.5-15% by weight, preferably 2-10% by weight, and more preferably 2-8% by weight, based on the total weight of the core layer catalyst; Preferably, the Group VIB metal is selected from at least one of molybdenum and tungsten, and preferably molybdenum; and the Group VIII metal is selected from at least one of cobalt and nickel, and preferably cobalt.

3. The method of claim 1, wherein, The particle size of the hydrogenation catalyst is 0.8-1.2 mm; The average pore diameter of the alumina support is 5-15 nm; the pore volume of the alumina support is 0.4-1.0 cm 3 / g; the specific surface area of the alumina support is 200-400 m 2 / g.

4. The method of claim 1, wherein, The thickness of the SiO2 layer is 1 nm-30 µm, and preferably 20 nm-20 µm; The pore size of the SiO2 layer is 1-2 nm.

5. The method of claim 1, wherein, The conditions of the hydrodesulfurization reaction include a reaction temperature of 300-550°C, preferably 330-480°C, a hydrogen partial pressure of 4-20 MPa, preferably 4-18 MPa, a volume space velocity of 0.1-3 h -1 , preferably 0.15-2 h -1 , a hydrogen to oil volume ratio of 200-2500, preferably 300-2000; Preferably, the oil slurry raw material is catalytic cracking oil slurry; the sulfur content in the oil slurry raw material is 0.5-2.5% by weight; and the content of tetranuclear aromatic hydrocarbon in the oil slurry raw material is 20-50% by weight.

6. The method of claim 1, wherein, The preparation method of the hydrogenation catalyst comprises the following steps: The core layer catalyst, alcohol and water are mixed to obtain a mixed solution; the volume ratio of the alcohol to the water is 1-10; The mixed solution and a template agent are mixed and dispersed under ultrasonic conditions to obtain a first mixed material; The first mixed material and an alkaline reagent are mixed under stirring to obtain a second mixed material; The second mixed material is added with an organic silicon source under stirring to coat the core layer catalyst, and the template agent is removed through solid-liquid separation to obtain the hydrogenation catalyst.

7. The method of claim 6, wherein, The volume ratio of the alcohol to the water is 2-9; Preferably, the mass ratio of the core layer catalyst to the template agent is 1:0.05-1; and the template agent is selected from one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride.

8. The method of claim 6, wherein, The pH value of the second mixed material is 8-10; The alkaline reagent is selected from one or more of aqueous ammonia, sodium hydroxide, potassium hydroxide and triethanolamine, and preferably aqueous ammonia and / or sodium hydroxide; Preferably, the mass ratio of the organic silicon source to the core layer catalyst is 0.03-0.8:1, based on SiO2; Preferably, the organic silicon source is selected from at least one of dimethyldiethylsiloxane, methyl orthosilicate and ethyl orthosilicate.

9. The method of claim 6, wherein, The time is 10-60 min; The coating reaction temperature is 20-100 ℃, preferably 20-30 ℃.

10. The method of claim 6, wherein, The template is removed by calcination, and the calcination conditions include a temperature of 200-600 ℃ and a time of 2-10 h. Preferably, the calcination includes first calcination and second calcination performed in sequence; the first calcination conditions include a temperature of 200-300 ℃ and a time of 1-3 h; and the second calcination conditions include a temperature of 400-500 ℃, a time of 3-5 h, and a temperature increase rate of 0.5 ℃ / min-10 ℃ / min, preferably 1 ℃ / min-3 ℃ / min.

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