Coal-based cracking C9 < + > component hydrogenation catalyst as well as preparation method and application thereof
By preparing a composite support and improving the physicochemical properties of pseudoboehmite, the problem of strong interaction between the alumina support and the active metal was solved, which improved the hydrodesulfurization activity and anti-carbon deposition performance of the catalyst, and realized the efficient use of the catalyst.
Patent Information
- Application Number
- CN202510952190.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-10
- Publication Date
- 2025-11-25
AI Technical Summary
In the prior art, the strong interaction between the alumina support and the active metal leads to incomplete sulfidation of the catalyst, resulting in low hydrodesulfurization activity, and the catalyst has poor resistance to carbon deposition when applied to the hydrogenation of coal-based C9+ components.
By preparing a composite support and utilizing fluorine modification and rotary spray impregnation technology, the physicochemical properties of boehmite were improved, thereby enhancing the catalyst's activity and resistance to carbon deposition. Specific steps included co-precipitation, aging, kneading, rotary spray impregnation, and calcination, combined with the use of mesoporous carbon and kaolin to improve the support structure.
It improves the hydrogenation performance and anti-carbon deposition ability of the catalyst, enhances the dispersibility and utilization rate of active metals, extends the service life of the catalyst, and meets the process production requirements of hydrogenation of coal-based C9+ components.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of hydrogenation catalysts, in particular to a coal-based cracking C9+ component hydrogenation catalyst, a preparation method and application thereof. BACKGROUND
[0002] Cracking C9+ component is a byproduct of steam cracking ethylene production device, at present, most of the domestic ethylene devices sell C9+ component as a relatively cheap primary raw material, only a small part of the device is worked as gasoline blending component or solvent oil. By comparison, it is found that the physicochemical properties of C9+ component and coal-based diesel component oil are close, and after hydro-upgrading, it can be used as aromatic solvent oil and diesel component oil blending component, and the cracking C9+ component hydrogenation technology plays an important role in the comprehensive utilization of C9+ component, and the product after hydrogenation has high added value and broad application prospect. The composition, preparation method and characteristics of C9+ component hydrogenation catalyst are still the technical secrets of each research and development unit, the special carrier with composite pore structure or the preparation method, especially the composite carrier of alumina and silica, is the research and development direction of C9+ component hydrogenation catalyst, and the sulfur resistance and gum resistance of the catalyst are the design key points of C9+ component hydrogenation catalyst.
[0003] In the hydrogenation catalyst, the active metal is supported on the carrier, the most commonly used carrier material is γ-Al2O3, because it has good structure, mechanical properties and relatively low cost, can provide high specific surface area, and can also play an important role in improving the performance of the catalyst through interaction with the active metal. Although γ-Al2O3 has good characteristics in mechanical strength, but due to the strong interaction between it and the active metal, it leads to incomplete sulfidation of the catalyst and lower hydrodesulfurization activity. SUMMARY
[0004] The present application aims to overcome the strong interaction between the alumina carrier and the active metal in the prior art, which leads to incomplete sulfidation of the catalyst during sulfidation, resulting in low hydrodesulfurization activity and poor carbon deposition resistance of the catalyst when applied to coal-based C9+ component hydrogenation, and provides a coal-based cracked C9+ component hydrogenation catalyst, a preparation method and application thereof. The technical scheme improves the physical and chemical properties of pseudo-boehmite by preparing a composite carrier, thereby improving the catalytic performance and carbon deposition resistance; during preparation of the impregnation solution, fluorine is used for modification, which not only promotes sulfidation of the catalyst and improves the activity of the catalyst, but also improves the proportion distribution of the active phase structure in the catalyst and reduces the interaction between the active component and the carrier; the impregnation process adopts rotary spray impregnation to ensure sufficient contact between the impregnation solution and the carrier and improve metal dispersion; and gas is introduced into the reaction container to accelerate evaporation of the excess impregnation solution on the surface of the carrier and prevent uneven distribution of the active metal. The present application aims to overcome the strong interaction between the alumina carrier and the active metal and improve the carbon deposition resistance of the catalyst.
[0005] To achieve the above-mentioned purpose, the first aspect of the present application provides a preparation method of a coal-based cracked C9+ component hydrogenation catalyst, which comprises the following steps: (1) co-precipitating pseudo-boehmite, mesoporous carbon and a precipitant in parallel flow to obtain a precipitate slurry; then sequentially aging the obtained precipitate slurry and separating the solid phase to obtain modified pseudo-boehmite; (2) mixing and kneading the modified pseudo-boehmite obtained in step (1), kaolin, a binder and a extrusion aid, and then shaping, first drying and first calcining to obtain a composite carrier; (3) preparing an impregnation solution containing a fluorinated salt, a first active metal salt and a second active metal salt, impregnating the composite carrier in the impregnation solution by rotary spray impregnation, introducing gas into the impregnation reactor after completing the impregnation, and then second drying and second calcining.
[0006] Preferably, in step (1), the specific process of co-precipitating pseudo-boehmite, mesoporous carbon and a precipitant in parallel flow comprises the following steps: S1, preparing a dispersion liquid containing pseudo-boehmite and mesoporous carbon; S2, co-precipitating the precipitant and the dispersion liquid obtained in step S1.
[0007] Preferably, the mass ratio of the amount of the pseudo-boehmite to the amount of the mesoporous carbon is 1:(0.02-0.2).
[0008] Preferably, the precipitant is at least one of a potassium hydroxide aqueous solution, a potassium carbonate aqueous solution and a potassium bicarbonate aqueous solution.
[0009] Preferably, the conditions of the co-current coprecipitation comprise: temperature of 60-80℃, and dropping speed of the precipitant of 20-100mL / min.
[0010] Preferably, the pH value of the precipitated slurry is 8-10.
[0011] Preferably, in step (1), the conditions of the aging comprise: temperature of 150-180℃, and time of 12-24h.
[0012] Preferably, in step (2), the mass ratio of the modified pseudoboehmite to the kaolin is 1:(0.1-0.2).
[0013] Preferably, in step (2), the binder is an acidic solution.
[0014] Preferably, the binder is aqueous citric acid solution and / or nitric acid.
[0015] Preferably, the mass ratio of the modified pseudoboehmite to the binder is 1:(0.5-0.8).
[0016] Preferably, in step (2), the extrusion aid is amaranth powder and / or methyl cellulose.
[0017] Preferably, the mass ratio of the modified pseudoboehmite to the extrusion aid is 1:(0.02-0.06).
[0018] Preferably, in step (2), the first drying process specifically comprises: drying at 20-35℃ for 12-24h, and then drying at 120-150℃ for 2-6h.
[0019] Preferably, in step (2), the conditions of the first calcination comprise: temperature of 550-700℃, and time of 4-6h.
[0020] Preferably, in step (3), the fluorinated salt is ammonium fluoride and / or ammonium bifluoride.
[0021] Preferably, in the impregnation solution, the content of the fluorinated salt in terms of fluoride ion is 0.5wt%-2wt%.
[0022] Preferably, in step (3), the first active metal salt is a molybdenum salt, preferably ammonium heptamolybdate and / or molybdenum trioxide.
[0023] Preferably, in the impregnation solution, the content of the first active metal salt in terms of oxide is 15wt%-30wt%.
[0024] Preferably, in step (3), the second active metal salt is at least one of a nickel salt, a tungsten salt and a cobalt salt.
[0025] Preferably, the nickel salt is nickel nitrate and / or nickel acetate.
[0026] Preferably, the tungsten salt is ammonium metatungstate.
[0027] Preferably, the cobalt salt is at least one of cobalt nitrate, cobalt sulfate and cobalt carbonate.
[0028] Preferably, in the impregnation solution, the content of the second active metal salt is 3wt%-7wt% in terms of oxide.
[0029] Preferably, in step (3), the second drying condition comprises: temperature is 100-120℃, time is 2-12h.
[0030] Preferably, in step (3), the second calcination condition comprises: temperature is 500-700℃, time is 2-6h.
[0031] The second aspect of the present application provides a coal-based cracked C9+ component hydrogenation catalyst prepared by the above method.
[0032] The third aspect of the present application provides a coal-based C9+ component oil hydrocracking method, comprising hydroprocessing coal-based C9+ component oil in the presence of the above coal-based cracked C9+ component hydrogenation catalyst.
[0033] Compared with the prior art, the present application has the following technical effects: (1) The mesoporous carbon is selected as an additive in the present application, which has high specific surface area, large pore volume, adjustable pore structure, can significantly improve the structure and performance of the catalyst, is beneficial to improve the dispersion of active metals, has excellent hydrogen storage capacity, can improve the hydrogenation depth and enhance the hydrogenation performance of the catalyst, has excellent electron transfer capacity to adjust the electron density of the metal active center and inhibit the generation of coke, the interface formed by in-situ compounding of the mesoporous carbon and pseudo-boehmite is more closely combined, which can improve the mechanical stability of the material, at the same time, can promote the uniform distribution of the mesoporous carbon and avoid the problem of agglomeration, and the molecular confinement effect of the mesoporous carbon is beneficial to improve the selectivity of the target product; (2) The present application introduces the additive SiO2 through kaolin, which can replace part of the Al-OH groups on the surface of Al2O3 with difficult-to-move Si-OH groups, and form Si-O-Si or Si-O-Al bonds to fill the anion vacancies on the surface of Al2O3 during the dehydroxylation process, so that the skeleton structure of Al2O3 is more stable; SiO2 is added in the form of kaolin, which is not only simple to operate, but also saves production cost, and kaolin has a unique pore structure, large specific surface area, strong adsorption capacity and good thermal stability; (3) The application utilizes fluorinated salt to modify the catalyst carrier, increases the specific surface area of the catalyst carrier, increases the active sites, simultaneously weakens the interaction between the active metal component and the catalyst carrier, forms more hydrogenation centers on the catalyst carrier, improves the effective utilization rate of the active metal component, and further improves the activity of the catalyst.
[0034] (4) The application adopts rotary spraying impregnation, and after impregnation, gas is introduced to accelerate the evaporation of the excess impregnation liquid on the surface of the carrier, prevents uneven distribution of the active metal, is beneficial to improving the dispersity of the active metal, further improves the catalytic performance, and prolongs the service life of the catalyst.
[0035] (5) The preparation method of the application has a simple process, the raw materials are easy to obtain, the cost is low, the obtained catalyst has a large specific surface area, good metal dispersity, a large pore volume, and strong anti-coking performance, can meet the quality requirements of subsequent process production, and prolongs the operation cycle of the device. DETAILED DESCRIPTION
[0036] The specific embodiments of the application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the application, and are not used to limit the application.
[0037] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and the values are approximate values and should be understood to include values approximately near these ranges and values within these ranges. For ranges of values, the endpoints of the ranges are combined with the individual points to form new ranges that are within the scope of the present application.
[0038] The preparation method of the coal-based cracking C9+ component hydrogenation catalyst comprises the following steps: (1) parallel flow co-precipitation is performed on pseudo-boehmite, mesoporous carbon and a precipitant to obtain a precipitate slurry; then the obtained precipitate slurry is sequentially subjected to aging and separation of a solid phase to obtain modified pseudo-boehmite; (2) the modified pseudo-boehmite obtained in step (1), kaolin, a binder and a extrusion aid are mixed and formed, then first drying and first calcination are performed to obtain a composite carrier; (3) an impregnation liquid containing fluorinated salt, a first active metal salt and a second active metal salt is prepared, the composite carrier is impregnated in the impregnation liquid by rotary spraying impregnation, gas is introduced into the impregnation reactor after the impregnation is completed, then second drying and second calcination are performed.
[0039] According to the method, the physicochemical properties of pseudo-boehmite are improved by preparing a composite carrier, so as to improve the catalytic performance and carbon deposition resistance of the catalyst; when the impregnation solution is prepared, fluorine is used for modification, so as to promote sulfuration of the catalyst, improve the activity of the catalyst, improve the proportion distribution of the active phase structure of the catalyst, and reduce the interaction between the active component and the carrier; the impregnation process adopts rotary spray impregnation, so as to make the impregnation solution fully contact with the composite carrier, improve the dispersity of the active metal, and simultaneously introduce gas into the reaction container, accelerate evaporation of the excessive impregnation solution on the surface of the carrier, and prevent uneven distribution of the active metal.
[0040] In the method, in step (1), the specific process of parallel flow co-precipitation of the pseudo-boehmite, the mesoporous carbon and the precipitator can include the following steps. S1, preparing a dispersion liquid containing pseudo-boehmite and mesoporous carbon; S2, performing parallel flow co-precipitation of the precipitator and the dispersion liquid obtained in step S1.
[0041] In the method, in order to solve the problem of strong interaction force between the alumina carrier and the active metal, and improve the catalytic performance and carbon deposition resistance of the hydrogenation catalyst, the mass ratio of the amount of the pseudo-boehmite to the amount of the mesoporous carbon is preferably 1:(0.02-0.2), and more preferably 1:(0.1-0.2).
[0042] In the method, the specific process of step S1 can include mixing the pseudo-boehmite, the mesoporous carbon and water to obtain a dispersion liquid. In the dispersion liquid, the content of the pseudo-boehmite can be 40-50wt%, and preferably 45-50wt%.
[0043] In the method, the precipitator can be at least one of a potassium hydroxide aqueous solution, a potassium carbonate aqueous solution and a potassium bicarbonate aqueous solution, and is preferably a potassium hydroxide aqueous solution. The concentration of the precipitator can be 0.5-3mol / L, and preferably 1-2mol / L.
[0044] In the method, the parallel flow co-precipitation is a commonly used chemical synthesis method, and belongs to a specific operation form of co-precipitation method. The core principle is to slowly drop the dispersion liquid and the precipitator into a reaction container at a certain ratio and flow rate at the same time, so that the metal ions simultaneously undergo a precipitation reaction in the same system, and finally form a precipitate with uniform composition. The conditions of the parallel flow co-precipitation include that the temperature can be 60-80℃, and preferably 65-75℃; the dropping speed of the precipitator can be 20-100mL / min, and preferably 20-50mL / min. The pH value of the precipitate slurry can be 8-10, and preferably 8.5-9.5.
[0045] In the method of the present application, in step (1), the method can further comprise stirring the obtained precipitate slurry after the end of the co-precipitation. The stirring conditions include that the temperature can be 60-80°C, preferably 65-75°C, the time can be 20-45 min, preferably 30-40 min, and the stirring rate can be 30-60 rpm, preferably 40-50 rpm.
[0046] In the method of the present application, in step (1), the aging conditions include that the temperature can be 150-180°C, preferably 150-165°C, and the time can be 12-24 h, preferably 12-18 h.
[0047] In the method of the present application, in step (1), the method can further comprise cooling the obtained material to 25-30°C after the aging. The solid phase is separated from the material obtained after the aging by filtration. The method can further comprise washing and drying the obtained solid phase. The drying conditions include that the temperature can be 80-120°C, preferably 100-120°C, and the time can be 120-360 min, preferably 240-300 min. The modified pseudoboehmite is a pseudoboehmite in situ compounded with a mesoporous carbon material.
[0048] In the method of the present application, in order to improve the catalytic performance of the hydrogenation catalyst, in step (2), the mass ratio of the modified pseudoboehmite to the kaolin is preferably 1:(0.1-0.2), more preferably 1:(0.15-0.2). The kaolin can be a silicon-containing kaolin. The silicon-containing kaolin has a large specific surface area, strong adsorption capacity, and good thermal stability, and can improve the physicochemical properties of the alumina carrier.
[0049] In the method of the present application, in step (2), the binder can be an acidic solution. In a more preferred embodiment, the binder is a citric acid aqueous solution and / or nitric acid. The concentration of the citric acid aqueous solution can be 5-10 wt%, preferably 6-8 wt%. The concentration of the nitric acid can be 0.5-2 wt%, preferably 1-1.5 wt%. The nitric acid can be prepared by diluting concentrated nitric acid with a concentration of 60-75 wt% with water. The mass ratio of the modified pseudoboehmite to the binder can be 1:(0.5-0.8), preferably 1:(0.55-0.77).
[0050] In the method of the present application, in step (2), the extrusion aid can be pearl millet powder and / or methyl cellulose, preferably pearl millet powder and methyl cellulose. In some embodiments, the extrusion aid is pearl millet powder and methyl cellulose, and the mass ratio of the amount of the pearl millet powder to the amount of the methyl cellulose is 1:(0.5-0.6). The viscosity of the pearl millet powder can be 1800-2200 centipoise, preferably 2000-2200 centipoise. The mass ratio of the amount of the modified pseudoboehmite to the amount of the extrusion aid can be 1:(0.02-0.06), preferably 1:(0.02-0.04).
[0051] In the method of the present application, in step (2), the specific process of kneading and shaping the modified pseudoboehmite, kaolin, binder and extrusion aid obtained in step (1) can include the following steps: The modified pseudoboehmite, kaolin and extrusion aid obtained in step (1) are mixed, kneaded for 5-15 min, then rolled for 25-40 min after adding the binder, and then extruded into strips using a three-leaf clover hole plate. The diameter of the three-leaf clover hole plate can be 1.5-3 mm.
[0052] In the method of the present application, in step (2), the first drying process can specifically include: first drying at 20-35℃ for 12-24h, and then drying at 120-150℃ for 2-6h.
[0053] In the method of the present application, in step (2), the first calcination conditions include: the temperature can be 550-700℃, preferably 600-650℃; and the time can be 4-6h, preferably 4-5h.
[0054] In the method of the present application, in step (3), the fluorinated salt can be ammonium fluoride and / or ammonium bifluoride, preferably ammonium fluoride. In the impregnation solution, the content of the ammonium fluoride in terms of fluoride ions can be 0.5wt%-2wt%, preferably 1wt%-1.5wt%.
[0055] In the method of the present application, in step (3), the first active metal salt can be a molybdenum salt, preferably ammonium heptamolybdate and / or molybdenum trioxide. In the impregnation solution, the content of the first active metal salt in terms of oxides can be 15wt%-30wt%, preferably 20wt%-25wt%.
[0056] In the method of the present application, in step (3), the second active metal salt can be at least one of a nickel salt, a tungsten salt and a cobalt salt, preferably a nickel salt. The nickel salt can be nickel nitrate and / or nickel acetate, preferably nickel nitrate. The tungsten salt can be ammonium metatungstate. The cobalt salt can be at least one of cobalt nitrate, cobalt sulfate and cobalt carbonate, preferably cobalt nitrate. In the impregnation solution, the content of the second active metal salt, calculated as an oxide, can be 3wt%-7wt%, preferably 4wt%-6wt%.
[0057] In a preferred embodiment, the fluorinated salt is ammonium fluoride and / or ammonium bifluoride, the first active metal salt is a molybdenum salt, and the second active metal salt is at least one of a nickel salt, a tungsten salt and a cobalt salt. Since ammonium fluoride or ammonium bifluoride is acidic, it can corrode the carrier, increase the specific surface area of the carrier, and increase the active sites; at the same time, it can weaken the interaction between the Mo, Ni active metal components and the carrier, so that more hydrogenation centers are formed on the carrier, the effective utilization rate of the Mo, Ni active metal components is improved, and the activity of the catalyst is improved.
[0058] In the method of the present application, the rotary spray impregnation is a dynamic impregnation method, specifically an impregnation process combining rotary and spray methods. The principle is that the treated object or container is rotated by the equipment rotation, and at the same time, the impregnation liquid is uniformly sprayed on the surface of the object and in the container by the spray system, so that the impregnation liquid can be fully penetrated and attached, and the impregnation effect is achieved. The conditions of the rotary spray impregnation can include a rotation speed of 50-60rpm, a temperature of 60-80℃, and a time of 30-60min. In step (3), the gas can be air. The ratio of the amount of the composite carrier to the amount of the impregnation liquid can be 100g:(80-110)mL, preferably 100g:(90-100)mL.
[0059] In the method of the present application, in step (3), the conditions of the second drying can include a temperature of 100-120℃, preferably 110-120℃, and a time of 2-12h, preferably 8-12h.
[0060] In the method of the present application, in step (3), the conditions of the second calcination can include a temperature of 500-700℃, preferably 500-600℃, and a time of 2-6h, preferably 2-4h.
[0061] In some embodiments, the method for preparing the coal-based cracked C9+ component hydrogenation catalyst of the present application comprises the following steps: (1) mixing pseudo-boehmite, mesoporous carbon and water to obtain a dispersion liquid; co-precipitating a precipitant with a concentration of 0.5-3 mol / L and the obtained dispersion liquid at 60-80℃ at a dropping speed of the precipitant of 20-100 mL / min, until the pH value of the obtained precipitate slurry is 8-10; then stirring the obtained precipitate slurry at 60-80℃ at a stirring speed of 30-60 rpm for 20-45 min; then aging the obtained material at 150-180℃ for 12-24 h, cooling the obtained material to 25-30℃, separating the solid phase from the aged material by filtration, washing the obtained solid phase and drying it at 80-120℃ for 120-360 min to obtain modified pseudo-boehmite; the mass ratio of the amount of the pseudo-boehmite to the amount of the mesoporous carbon is 1:(0.02-0.2); the content of the pseudo-boehmite in the dispersion liquid is 40-50 wt%; (2) mixing the modified pseudo-boehmite obtained in step (1), kaolin and a extrusion aid, kneading for 5-15 min, then rolling for 25-40 min after adding a binder, and then extruding into strips using a three-leaf clover hole plate with a diameter of 1.5-3 mm, then drying at 20-35℃ for 12-24 h, drying at 120-150℃ for 2-6 h, and then calcining at 550-700℃ for 4-6 h to obtain a composite carrier; the mass ratio of the amount of the modified pseudo-boehmite to the amount of the kaolin is 1:(0.1-0.2); the binder can be an acidic solution; the mass ratio of the amount of the modified pseudo-boehmite to the amount of the binder is 1:(0.5-0.8); the extrusion aid is amaranth powder and / or methyl cellulose; the mass ratio of the amount of the modified pseudo-boehmite to the amount of the extrusion aid is 1:(0.02-0.06); (3) preparing an impregnation liquid containing a fluorinated salt, a first active metal salt and a second active metal salt, impregnating the composite carrier in the impregnation liquid by using a rotary spray impregnation method, introducing air into the impregnation reactor after the impregnation is completed, then drying at 100-120℃ for 2-12 h and calcining at 500-700℃ for 2-6 h to obtain a catalyst; the fluorinated salt is ammonium fluoride and / or ammonium bifluoride; the first active metal salt is a molybdenum salt; the second active metal salt is at least one of a nickel salt, a tungsten salt and a cobalt salt; in the impregnation liquid, the content of the ammonium fluoride in terms of fluoride ions is 0.5 wt%-2 wt%, the content of the first active metal salt in terms of oxides is 15 wt%-30 wt%, and the content of the second active metal salt in terms of oxides is 3 wt%-7 wt%; the ratio of the amount of the composite carrier to the amount of the impregnation liquid is 100 g:(80-110) mL.
[0062] In some other embodiments, the preparation method of the coal-based cracked C9+ component hydrogenation catalyst according to the present application comprises the following steps: (1) mixing pseudo-boehmite, mesoporous carbon and water to obtain a dispersion liquid; carrying out co-precipitation of the obtained dispersion liquid and a 0.5-3 mol / L potassium hydroxide aqueous solution at 60-80°C at a dropping speed of the potassium hydroxide aqueous solution of 20-100 mL / min, until the pH value of the obtained precipitate slurry is 8-10; then stirring the obtained precipitate slurry at 60-80°C at a stirring speed of 30-60 rpm for 20-45 min; then aging the obtained material at 150-180°C for 12-24 h, cooling the obtained material to 25-30°C, separating the solid phase from the aged material by filtration, washing the obtained solid phase and drying it at 80-120°C for 120-360 min to obtain modified pseudo-boehmite; the mass ratio of the amount of the pseudo-boehmite to the amount of the mesoporous carbon is 1:(0.02-0.2); the content of the pseudo-boehmite in the dispersion liquid is 40-50 wt%; (2) mixing the modified pseudo-boehmite obtained in step (1), kaolin and a extrusion aid, kneading for 5-15 min, then rolling after adding a binder for 25-40 min, then extruding into strips using a three-leaf clover hole plate with a diameter of 1.5-3 mm, then drying at 20-35°C for 12-24 h, then drying at 120-150°C for 2-6 h, then calcining at 550-700°C for 4-6 h to obtain a composite carrier; the mass ratio of the amount of the modified pseudo-boehmite to the amount of the kaolin is 1:(0.1-0.2); the binder can be a citric acid aqueous solution and / or nitric acid; the mass ratio of the amount of the modified pseudo-boehmite to the amount of the binder is 1:(0.5-0.8); the extrusion aid is amaranth powder and methyl cellulose, and the mass ratio of the amount of the amaranth powder to the amount of the methyl cellulose is 1:(0.5-0.6); the mass ratio of the amount of the modified pseudo-boehmite to the amount of the extrusion aid is 1:(0.02-0.06); (3) preparing an impregnation liquid containing a fluorinated salt, a first active metal salt and a second active metal salt, impregnating the composite carrier in the impregnation liquid by using a rotary spray impregnation method, after the impregnation is completed, introducing air into the impregnation reactor, then drying at 100-120°C for 2-12 h and calcining at 500-700°C for 2-6 h to obtain a catalyst; the fluorinated salt is ammonium fluoride; the first active metal salt is ammonium heptamolybdate and / or molybdenum trioxide; the second active metal salt is nickel nitrate and / or nickel acetate; in the impregnation liquid, the content of the ammonium fluoride calculated as fluoride ions is 0.5 wt%-2 wt%, the content of the first active metal salt calculated as oxide is 15 wt%-30 wt%, and the content of the second active metal salt calculated as oxide is 3 wt%-7 wt%; the ratio of the amount of the composite carrier to the amount of the impregnation liquid is 100 g:(80-110) mL.
[0063] The second aspect of the present application provides a coal-based cracked C9+ component hydrogenation catalyst prepared by the method described above. According to the catalyst described in the present application, the proportion distribution of the active phase structure in the catalyst is improved, the interaction between the active component and the carrier is reduced, the catalytic performance and the carbon deposition resistance of the hydrogenation catalyst are improved, and the metal dispersion is improved.
[0064] The third aspect of the present application provides a coal-based C9+ component oil hydrocracking method, which comprises hydroprocessing the coal-based C9+ component oil in the presence of the coal-based cracked C9+ component hydrogenation catalyst described above. According to the method described in the present application, the hydrogenation catalyst has high catalytic performance and carbon deposition resistance.
[0065] In the method described in the present application, the activity test is carried out on a 100 mL fixed-bed hydrogenation device (JQ-7 type, Haian County Petroleum Scientific Research Instrument Co., Ltd.). Before the activity test, the catalyst is pre-sulfided. The pre-sulfiding conditions can include: liquid hourly space velocity 0.5-1 h -1 -1, hydrogen / oil volume ratio (200-600): 1, and total pressure 2.8-3.2 MPa. The activity test conditions include: total pressure 2.8-3.2 MPa, liquid hourly space velocity 0.5-1 h -1 -1, hydrogen / oil volume ratio (200-600): 1, and reaction temperature 300-320℃.
[0066] In the method described in the present application, the specific steps of the pre-sulfiding are: (1) the reactor is raised from room temperature to 120-180℃ at a rate of 5-15℃ / h, and after constant temperature for 3-5 hours, the sulfidation oil is fed; (2) the temperature is raised to 300-400℃ at a rate of 10-20℃ / h, and after constant temperature for 3-5 hours, the H2S concentration in the tail gas is detected by a colorimetric tube at the beginning and end of the constant temperature; (3) after the constant temperature at 300-400℃ is ended, the temperature is lowered at a rate of 10-20℃ / h, and the sulfidation oil is continuously fed during the temperature lowering process. In this context, the total pressure is the gauge pressure.
[0067] The coal-based cracked C9+ component hydrogenation catalyst, the preparation method and the application thereof described in the present application are further illustrated by the following examples. The examples are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following examples.
[0068] The experimental methods in the following examples are all conventional methods in the art unless otherwise specified. The experimental materials used in the following examples are all commercially available unless otherwise specified. The pseudoboehmite used in the following examples is purchased from Shandong Branch of China Aluminum Co., Ltd., with the trade name of P-DF-03LS; the mesoporous carbon is purchased from Jiangsu Xianfeng Nanometer Technology Co., Ltd., with the trade name of XFF-03; the kaolin is purchased from Tianjin Kemio Chemical Reagent Co., Ltd.; the sesbania powder is purchased from Henan Lankao Plant Gum Co., Ltd.; the methyl cellulose is purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd., with the trade name of M450.
[0069] Example 1 (1) 200 g of pseudoboehmite, 20 g of mesoporous carbon and water were mixed to obtain a dispersion (in the dispersion, the content of the pseudoboehmite was 47.6 wt%); a 1 mol / L potassium hydroxide aqueous solution and the obtained dispersion were subjected to concurrent co-precipitation at 60°C, with the dropping speed of the potassium hydroxide aqueous solution being 20 mL / min, until the pH value of the obtained precipitate slurry was 8; then the obtained precipitate slurry was stirred at 65°C with a stirring speed of 40 rpm for 30 min; then the obtained material was aged at 150°C for 12 h, and the obtained material was cooled to 20°C, the solid phase was separated from the aged material by filtration, and the obtained solid phase was washed and dried at 100°C for 240 min to obtain modified pseudoboehmite; (2) 200 g of the modified pseudoboehmite obtained in step (1), 20 g of kaolin, 4 g of sesbania powder (viscosity 2000 centipoise) and 2.4 g of methyl cellulose were mixed, and then kneaded at 25°C for 5 min, followed by rolling and pressing for 30 min after adding 115 g of nitric acid (3 g of 68 wt% nitric acid was diluted with water to prepare), and then extruded into strips using a three-leaf clover hole plate with a diameter of 1.5 mm, followed by drying at 25°C for 18 h, drying at 120°C for 6 h, and then calcining at 600°C for 4 h to obtain a composite carrier; (3) An impregnation solution containing ammonium fluoride, ammonium heptamolybdate and nickel nitrate (in the impregnation solution, the content of the ammonium fluoride was 0.5 wt% in terms of fluoride ions, the content of the ammonium heptamolybdate was 24 wt% in terms of oxides, and the content of the nickel nitrate was 7 wt% in terms of oxides, and the solvent was water) was prepared, and 100 g of the composite carrier was impregnated in 95 mL of the impregnation solution at 60°C for 30 min by using a rotary spray impregnation method, air was introduced into the impregnation reactor after the impregnation was completed, and then dried at 120°C for 8 h and calcined at 550°C for 2 h to obtain a catalyst.
[0070] Example 2 (1) 200 g pseudo-boehmite, 30 g mesoporous carbon and water were mixed to obtain a dispersion liquid (in the dispersion liquid, the content of the pseudo-boehmite was 46.5 wt%); a 2 mol / L potassium carbonate aqueous solution and the obtained dispersion liquid were carried out co-precipitation at 60°C with the dropping speed of the potassium carbonate aqueous solution being 50 mL / min until the pH value of the obtained precipitate slurry was 9; then the obtained precipitate slurry was stirred at 70°C with the stirring speed being 50 rpm for 30 min; then the obtained material was aged at 150°C for 12 h, the obtained material was cooled to 20°C, the solid phase was separated from the aged material by filtration, the obtained solid phase was washed and dried at 110°C for 300 min to obtain a modified pseudo-boehmite; (2) 200 g of the modified pseudo-boehmite obtained in step (1), 30 g of kaolin, 6 g of sesbania powder (viscosity 2000 centipoise) and 3.0 g of methyl cellulose were mixed, and then kneaded at 25°C for 10 min, followed by adding 160 g of a citric acid aqueous solution (prepared by dissolving 10.5 g of citric acid in water) and then rolling for 30 min, and then extruded into strips using a three-leaf clover hole plate with a diameter of 2 mm, followed by drying at 25°C for 24 h, drying at 120°C for 6 h, and then calcining at 650°C for 4 h to obtain a composite carrier; (3) An impregnation liquid containing ammonium fluoride, ammonium heptamolybdate and nickel nitrate (in the impregnation liquid, the content of the ammonium fluoride was 1 wt% in terms of fluoride ions, the content of the ammonium heptamolybdate was 24 wt% in terms of oxides, and the content of the nickel nitrate was 6 wt% in terms of oxides, and the solvent was water) was prepared, 100 g of the composite carrier was impregnated in 100 mL of the impregnation liquid at 70°C for 40 min by using a rotary spray impregnation method, air was introduced into the impregnation reactor after the impregnation was completed, and then dried at 120°C for 10 h and calcined at 550°C for 2 h to obtain a catalyst.
[0071] Example 3 (1) 200 g pseudo-boehmite, 40 g mesoporous carbon and water were mixed to obtain a dispersion liquid (in the dispersion liquid, the content of the pseudo-boehmite was 45.4 wt%); a 2 mol / L potassium bicarbonate aqueous solution and the obtained dispersion liquid were carried out co-precipitation at 60°C with the dropping speed of the potassium bicarbonate aqueous solution being 100 mL / min until the pH value of the obtained precipitate slurry was 10; then the obtained precipitate slurry was stirred at 80°C with the stirring speed being 60 rpm for 30 min; then the obtained material was aged at 150°C for 12 h, the obtained material was cooled to 20°C, the solid phase was separated from the aged material by filtration, the obtained solid phase was washed and dried at 120°C for 360 min to obtain a modified pseudo-boehmite; (2) 200 g of the modified pseudoboehmite, 40 g of kaolin, 8 g of sesbania powder (viscosity of 2000 centipoise), and 4.0 g of methyl cellulose obtained in step (1) are mixed, and kneaded at 25°C for 15 min, followed by roll-pressing for 30 min after adding 155 g of an aqueous citric acid solution (10.2 g of citric acid and 2 g of nitric acid with a concentration of 68 w% diluted with water) and then extrusion-molded using a three-leaf clover hole plate with a diameter of 2.5 mm, followed by drying at 30°C for 18 h, drying at 120°C for 6 h, and then calcining at 700°C for 4 h to obtain a composite carrier; (3) An impregnation solution containing ammonium fluoride, ammonium heptamolybdate, and nickel nitrate (in the impregnation solution, the content of ammonium fluoride is 1.5 wt% in terms of fluoride ions, the content of ammonium heptamolybdate is 25 wt% in terms of oxides, and the content of nickel nitrate is 5 wt% in terms of oxides, and the solvent is water) is prepared, and 100 g of the composite carrier is impregnated in 105 mL of the impregnation solution at 80°C for 30 min by using a rotary spray impregnation method, air is introduced into the impregnation reactor after the impregnation is completed, and then drying at 120°C for 12 h and calcination at 600°C for 2 h are performed to obtain a catalyst.
[0072] Example 4 (1) 200 g of pseudoboehmite, 20 g of mesoporous carbon, and water are mixed to obtain a dispersion (in the dispersion, the content of the pseudoboehmite is 47.6 wt%); a 1 mol / L potassium hydroxide aqueous solution and the obtained dispersion are subjected to concurrent co-precipitation at 60°C at a dropping speed of the potassium hydroxide aqueous solution of 20 mL / min until the pH value of the obtained precipitate slurry is 8; then the obtained precipitate slurry is stirred at 65°C at a stirring speed of 40 rpm for 30 min; and then the obtained material is aged at 150°C for 12 h, the obtained material is cooled to 20°C, the solid phase is separated from the aged material by filtration, and the obtained solid phase is washed and dried at 100°C for 240 min to obtain a modified pseudoboehmite; (2) 200 g of the modified pseudoboehmite, 40 g of kaolin, 8 g of sesbania powder (viscosity of 2000 centipoise), and 4 g of methyl cellulose obtained in step (1) are mixed, and kneaded at 25°C for 15 min, followed by roll-pressing for 30 min after adding 155 g of nitric acid (10.2 g of citric acid and 2 g of nitric acid with a concentration of 68 w% diluted with water) and then extrusion-molded using a three-leaf clover hole plate with a diameter of 3.0 mm, followed by drying at 25°C for 18 h, drying at 120°C for 6 h, and then calcining at 700°C for 4 h to obtain a composite carrier; (3) An impregnation solution containing ammonium fluoride, ammonium heptamolybdate and cobalt nitrate (in the impregnation solution, the content of ammonium fluoride is 1.5 wt% in terms of fluoride ion, the content of ammonium heptamolybdate is 24 wt% in terms of oxide, the content of cobalt nitrate is 7 wt% in terms of oxide, and the solvent is water) is prepared, 100 g of the composite carrier is impregnated in 105 mL of the impregnation solution at 80°C for 30 min by using a rotary spray impregnation method, air is introduced into the impregnation reactor after the impregnation is completed, and then drying at 120°C for 12 h and calcination at 600°C for 2 h are performed to obtain a catalyst.
[0073] Example 5 (1) 200 g of pseudoboehmite, 4 g of mesoporous carbon and water are mixed to obtain a dispersion (in the dispersion, the content of pseudoboehmite is 49.5 wt%); a 0.5 mol / L potassium hydroxide aqueous solution and the obtained dispersion are co-precipitated at 80°C with a dropping speed of the potassium hydroxide aqueous solution of 20 mL / min until the pH value of the obtained precipitation slurry is 8; then the obtained precipitation slurry is stirred at 80°C with a stirring speed of 30 rpm for 20 min; then aging at 180°C for 24 h, the obtained material is cooled to 20°C, the solid phase is separated from the aged material by filtration, and the obtained solid phase is washed and dried at 80°C for 120 min to obtain modified pseudoboehmite; (2) 200 g of the modified pseudoboehmite obtained in step (1), 20 g of kaolin, 8 g of sesbania powder (viscosity is 2000 centipoise) and 4 g of methyl cellulose are mixed, and then kneaded at 25°C for 5 min, followed by adding 100 g of nitric acid (10.2 g of citric acid and 2 g of 68 w% concentrated nitric acid diluted with water) and then rolling for 30 min, and then extruded into a strip by using a three-leaf clover hole plate with a diameter of 1.5 mm, followed by drying at 35°C for 12 h, drying at 150°C for 2 h, and then calcining at 550°C for 4 h to obtain a composite carrier; (3) An impregnation solution containing ammonium fluoride, ammonium heptamolybdate and nickel nitrate (in the impregnation solution, the content of ammonium fluoride is 2 wt% in terms of fluoride ion, the content of ammonium heptamolybdate is 30 wt% in terms of oxide, the content of nickel nitrate is 7 wt% in terms of oxide, and the solvent is water) is prepared, 100 g of the composite carrier is impregnated in 80 mL of the impregnation solution at 60°C for 30 min by using a rotary spray impregnation method, air is introduced into the impregnation reactor after the impregnation is completed, and then drying at 120°C for 12 h and calcination at 600°C for 2 h are performed to obtain a catalyst.
[0074] Example 6 (1) 200 g pseudo-boehmite, 40 g mesoporous carbon and water were mixed to obtain a dispersion liquid (in the dispersion liquid, the content of the pseudo-boehmite was 45.4 wt%); a 3 mol / L potassium hydroxide aqueous solution and the obtained dispersion liquid were subjected to concurrent co-precipitation at 60°C with a dropping speed of the potassium hydroxide aqueous solution of 100 mL / min, until the pH value of the obtained precipitate slurry was 8; then the obtained precipitate slurry was stirred at 80°C with a stirring speed of 60 rpm for 45 min; then the obtained material was aged at 150°C for 12 h, and the obtained material was cooled to 20°C, the solid phase was separated from the aged material by filtration, and the obtained solid phase was washed and dried at 120°C for 360 min to obtain modified pseudo-boehmite; (2) 200 g of the modified pseudo-boehmite obtained in step (1), 40 g of kaolin and 4 g of sesbania powder (viscosity of 2000 centipoise) were mixed and kneaded at 25°C for 15 min, then 160 g of nitric acid (10.2 g of citric acid and 2 g of 68 wt% nitric acid were diluted with water to prepare) was added and rolled for 30 min, and then extruded into strips using a three-leaf clover hole plate with a diameter of 3.0 mm, and then dried at 20°C for 24 h, dried at 150°C for 6 h, and then calcined at 700°C for 6 h to obtain a composite carrier; (3) An impregnation liquid containing ammonium bifluoride, molybdenum trioxide and ammonium metatungstate (in the impregnation liquid, the content of the ammonium bifluoride was 0.5 wt% in terms of fluoride ions, the content of the molybdenum trioxide was 15 wt% in terms of oxides, and the content of the ammonium metatungstate was 3 wt% in terms of oxides, and the solvent was water) was prepared, 100 g of the composite carrier was impregnated in 110 mL of the impregnation liquid at 80°C for 30 min by using a rotary spray impregnation method, air was introduced into the impregnation reactor after the impregnation was completed, and then dried at 100°C for 12 h and calcined at 500°C for 6 h to obtain a catalyst.
[0075] Comparative Example 1 The method of Example 1 was implemented, except that after the impregnation was completed, air was not introduced into the impregnation reactor.
[0076] Comparative Example 2 The method of Example 1 was implemented, except that step (3) was specifically as follows: an impregnation liquid containing ammonium fluoride, ammonium heptamolybdate and nickel nitrate (in the impregnation liquid, the content of the ammonium fluoride was 0.5 wt% in terms of fluoride ions, the content of the ammonium heptamolybdate was 24 wt% in terms of oxides, and the content of the nickel nitrate was 7 wt% in terms of oxides, and the solvent was water) was prepared, 100 g of the composite carrier was placed in 95 mL of the impregnation liquid at 60°C for 30 min, the solid phase was separated by filtration, and then dried at 120°C for 8 h and calcined at 550°C for 2 h to obtain a catalyst.
[0077] Comparative Example 3 The method of Example 1 was followed except that no ammonium fluoride was added to the impregnation solution, specifically in Step (2): an impregnation solution containing ammonium heptamolybdate and nickel nitrate (in the impregnation solution, the content of ammonium heptamolybdate was 24 wt% as calculated as the oxide, the content of nickel nitrate was 7 wt% as calculated as the oxide, and the solvent was water) was prepared, 100 g of the composite carrier was impregnated in 95 mL of the impregnation solution at 60°C for 30 min using a rotary spray impregnation method, air was introduced into the impregnation reactor after the impregnation was completed, and then drying was performed at 120°C for 8 h and calcination was performed at 550°C for 2 h to obtain a catalyst.
[0078] Comparative Example 4 The method of Example 1 was followed except that Step (1) was not performed, and the specific steps were as follows: (1) 200 g of pseudoboehmite, 20 g of kaolin, 4 g of sesbania powder (viscosity of 2000 centipoise), and 2.4 g of methyl cellulose were mixed and kneaded at 25°C for 5 min, 115 g of nitric acid (3 g of 68 wt% concentrated nitric acid diluted with water) was then added and rolled for 30 min, and then extrusion molding was performed using a three-leaf clover hole plate with a diameter of 1.5 mm, followed by drying at 25°C for 18 h, drying at 120°C for 6 h, and then calcination at 600°C for 4 h to obtain a composite carrier; (2) an impregnation solution containing ammonium fluoride, ammonium heptamolybdate, and nickel nitrate (in the impregnation solution, the content of ammonium fluoride was 0.5 wt% as calculated as fluoride ions, the content of ammonium heptamolybdate was 24 wt% as calculated as the oxide, the content of nickel nitrate was 7 wt% as calculated as the oxide, and the solvent was water) was prepared, 100 g of the composite carrier was impregnated in 95 mL of the impregnation solution at 60°C for 30 min using a rotary spray impregnation method, air was introduced into the impregnation reactor after the impregnation was completed, and then drying was performed at 120°C for 8 h and calcination was performed at 550°C for 2 h to obtain a catalyst.
[0079] Test Example (1) The physicochemical properties of the composite carriers prepared in Examples 1-6 and Comparative Examples 1-4 were tested, respectively. The compressive strength was tested by using an intelligent particle strength tester, and the method referred to the industry standard HGT 2783-2020 "Molecular sieve compressive strength test method"; the specific surface area and pore volume were tested by using a full-automatic specific surface and pore analyzer, and the method referred to the national standard GB / T 19587-2017 "Gas adsorption BET method for measuring specific surface area of solid substances"; the mass content of SiO2 was tested by using an X-ray fluorescence spectrometer, and the method referred to the national standard GB / T 30905-2014 "Inorganic chemical products X-ray fluorescence spectrometry", and the mass content of C was tested by using an elemental analyzer, and the method referred to the national standard JYT017-1996 "Elemental analyzer method general rules carbon, hydrogen, nitrogen, sulfur element analysis"; the physicochemical properties of the composite carriers prepared in Examples 1-6 and Comparative Examples 1-4 were recorded in Table 1; the physicochemical properties of the catalysts prepared in Examples 1-6 and Comparative Examples 1-4 were tested, including the compressive strength, specific surface area, pore volume, mass contents of MoO3, NiO, WO3 and CoO, and the testing methods were the same as those of the composite carriers, and the physicochemical properties of the catalysts prepared in Examples 1-6 and Comparative Examples 1-4 were recorded in Table 2; (2) Catalyst activity test: The activity test was carried out on a 100 mL fixed bed hydrogenation device (purchased from Haian County Petroleum Scientific Research Instrument Co., Ltd., model JQ-7); before the activity test, the catalyst was pre-sulfided, and the pre-sulfiding process conditions were as follows: liquid hourly space velocity 0.5 h -1 -1, hydrogen / oil volume ratio 400:1, and total pressure 3.0 MPa; the specific steps of the pre-sulfiding were as follows: (1) the reactor was raised from room temperature to 150°C (bed temperature) at a rate of 10°C / h, and after constant temperature for 4 hours, the sulfidation oil was fed; (2) the temperature was raised to 360°C at a rate of 15°C / h, and constant temperature was maintained for 4 hours. At the beginning and end of constant temperature, the H2S concentration in the tail gas was detected by using a colorimetric tube; (3) after constant temperature at 360°C, the temperature was lowered at a rate of 20°C / h, and the sulfidation oil was continuously fed during the temperature lowering process; the catalyst activity test conditions included: total pressure 3 MPa, liquid hourly space velocity 0.5 h -1 -1, hydrogen / oil volume ratio 400:1, reaction temperature 320°C, and the raw material for activity evaluation experiment was coal-based C9+ component oil, and the activity test results were recorded in Table 3.
[0080] Table 1
[0081] Table 2
[0082] Table 3
[0083] As can be seen from the results of Table 1, the examples 1-6 using the coal-based pyrolysis C9+ component hydrogenation catalysts have higher catalytic performance and anti-coking capacity, and higher desulfurization rates.
[0084] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.
Claims
1. A process for the preparation of a coal-based pyrolysis C9+ component hydrocatalyst, characterized by, The method comprises the following steps: (1) parallel flow co-precipitation of pseudo-boehmite, mesoporous carbon and a precipitant to obtain a precipitate slurry; then aging and separating the solid phase from the obtained precipitate slurry in sequence to obtain modified pseudo-boehmite; (2) mixing and kneading the modified pseudo-boehmite obtained in step (1), kaolin, a binder and a extrusion aid, and then molding, first drying and first calcining to obtain a composite carrier; (3) preparing an impregnation solution containing a fluorinated salt, a first active metal salt and a second active metal salt, and impregnating the composite carrier in the impregnation solution by means of rotary spray impregnation, and then introducing a gas into the impregnation reactor after the impregnation is completed, and then second drying and second calcining.
2. The method of claim 1, wherein, In step (1), the specific process of parallel flow co-precipitation of pseudo-boehmite, mesoporous carbon and a precipitant comprises the following steps: S1, preparing a dispersion liquid containing pseudo-boehmite and mesoporous carbon; S2, parallel flow co-precipitation of a precipitant and the dispersion liquid obtained in step S1; Preferably, the mass ratio of the amount of the pseudo-boehmite to the amount of the mesoporous carbon is 1:(0.02-0.2); Preferably, the precipitant is at least one of a potassium hydroxide aqueous solution, a potassium carbonate aqueous solution and a potassium bicarbonate aqueous solution; Preferably, the conditions of the parallel flow co-precipitation include that the temperature is 60-80℃, and the dropping speed of the precipitant is 20-100mL / min; Preferably, the pH value of the precipitate slurry is 8-10.
3. The method according to claim 1 or 2, characterized in that, In step (1), the conditions of the aging include that the temperature is 150-180℃, and the time is 12-24h.
4. The method according to any one of claims 1 to 3, characterized in that, In step (2), the mass ratio of the amount of the modified pseudo-boehmite to the amount of the kaolin is 1:(0.1-0.2).
5. The method according to any one of claims 1 to 4, characterized in that, In step (2), the binder is an acidic solution; Preferably, the binder is a citric acid aqueous solution and / or nitric acid; Preferably, the mass ratio of the amount of the modified pseudo-boehmite to the amount of the binder is 1:(0.5-0.8).
6. The method according to any one of claims 1 to 5, characterized in that, In step (2), the extrusion aid is sesbania powder and / or methyl cellulose; Preferably, the mass ratio of the amount of the modified pseudo-boehmite to the amount of the extrusion aid is 1:(0.02-0.06).
7. The method according to any one of claims 1 to 6, characterized in that, In step (2), the process of the first drying specifically comprises first drying at 20-35℃ for 12-24h, and then drying at 120-150℃ for 2-6h; Preferably, in step (2), the conditions of the first calcining include that the temperature is 550-700℃, and the time is 4-6h.
8. The method according to any one of claims 1 to 7, characterized in that, In step (3), the fluorinated salt is ammonium fluoride and / or ammonium bifluoride; Preferably, in the impregnation solution, the content of the fluorinated salt in terms of fluoride ions is 0.5wt%-2wt%.
9. The method according to any one of claims 1 to 8, characterized in that, In step (3), the first active metal salt is a molybdenum salt, preferably ammonium heptamolybdate and / or molybdenum trioxide; Preferably, in the impregnation solution, the content of the first active metal salt in terms of oxides is 15wt%-30wt%.
10. The method according to any one of claims 1-9, characterized in that, In step (3), the second active metal salt is at least one of a nickel salt, a tungsten salt and a cobalt salt; Preferably, the nickel salt is nickel nitrate and / or nickel acetate; Preferably, the tungsten salt is ammonium metatungstate; Preferably, the cobalt salt is at least one of cobalt nitrate, cobalt sulfate and cobalt carbonate; Preferably, the content of the second active metal salt in the impregnation solution is 3wt%-7wt% in terms of oxide.
11. The method according to any one of claims 1-10, characterized in that, In step (3), the second drying condition includes: temperature of 100-120℃, time of 2-12h; Preferably, in step (3), the second calcination condition includes: temperature of 500-700℃, time of 2-6h.
12. A coal-based cracked C9+ component hydrogenation catalyst prepared by the method of any one of claims 1-11.
13. A hydrocracking process for coal-based C9+ component oil, characterized by, The coal-based C9+ component oil is subjected to hydroprocessing in the presence of the coal-based cracked C9+ component hydrogenation catalyst of claim 12.