A process for the preparation of a bulk hydrocracking catalyst

Abstract

The application discloses a preparation method of a bulk phase hydrocracking catalyst, and comprises the following contents: (1) a solution containing W, Mo and Al, a beta molecular sieve slurry and a precipitant are parallelly flowed to carry out a gelation reaction, after the reaction is completed, graphene is added to obtain a slurry; (2) a solution containing Ni, Al and Cu and the precipitant are added dropwise into the slurry to carry out a gelation reaction, the obtained slurry is aged to obtain a slurry; (3) the slurry is filtered, dried, rolled, shaped, dried and calcined to obtain the catalyst; the precipitant comprises precipitant A and precipitant B, the precipitant A is a mixed solution of sodium hydroxide and sodium bicarbonate, and the precipitant B is ammonia water. The application well fuses the precipitation and aging process with the formation of each component of the catalyst, simultaneously matches specific precipitants, further controls the particle size of active metal oxides, and makes the catalyst have excellent isomerization performance and aromatic hydrocarbon conversion capacity, and is suitable for application in a hydrocracking process for producing special oils.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of petroleum refining, and particularly relates to a preparation method of a bulk-phase hydrocracking catalyst. BACKGROUND

[0002] The hydrocracking diesel fraction has the characteristics of water-white color, low impurity content, and high saturated hydrocarbon content, and can be used to produce various white oils, rust-proof oils, transformer oils, aluminum cold rolling oils, etc. The hydrocracking tail oil fraction is suitable for being used as a lubricating oil base oil. The industrial white oil has a pour point index of-3 to-9℃ according to different grades, and the aromatic hydrocarbon mass content is required to be no more than 5%. The transformer oil has a pour point index in the range of-10℃ to-50℃ according to different minimum cold operating temperatures in actual applications, and the polycyclic aromatic hydrocarbon content is required to be less than 3%. According to the product index of the special oil, the hydrocracking catalyst needs to have high isomerization performance and high aromatic hydrocarbon conversion capacity. The existing hydrocracking catalyst system is difficult to meet both requirements.

[0003] At present, the acid component commonly used in hydrocracking is Y molecular sieve, beta molecular sieve, and ZSM-5 molecular sieve. The isomerization performance of the beta molecular sieve is the best, and can meet the pour point index requirement of the industrial white oil. However, the conventional supported hydrocracking catalyst and the bulk-phase catalyst prepared by the existing technology are difficult to meet the polycyclic aromatic hydrocarbon content requirement of the industrial white oil.

[0004] The active metal loading of the traditional supported hydrocracking catalyst is generally no more than 30wt%, and the supported catalyst can provide a limited number of active centers. The hydrogenation activity of the catalyst is far from the aromatic hydrocarbon conversion activity required for producing high-value-added special oil products. The bulk-phase hydrocracking catalyst prepared by the coprecipitation method has a high active metal content, but the catalyst surface is small, the active metal oxide particles have different sizes, and the different hydrogenation active metals are randomly distributed, which causes no good coordination between the active metals. The high content of the metal is prone to excessive accumulation of metal particles, resulting in low utilization rate of the active metal. The pores of the oxide particles and the pores of the molecular sieve cannot be interconnected, which weakens the hydrogenation cracking activity of the bulk-phase catalyst. Therefore, the bulk-phase catalyst produced by the existing technology still cannot meet the hydrogenation activity requirement for producing high-value-added special oil products. At the same time, the nitrogen-containing compounds in the hydrocracking raw material have different degrees of poisoning (shielding) effect on the acid centers of the hydrocracking catalyst, which requires improving the nitrogen tolerance of the hydrocracking catalyst. The hydrocracking catalyst with good nitrogen tolerance can improve the adaptability of the catalyst to raw materials and prolong the operation cycle of the industrial device.

[0005] CN114471688A discloses a preparation method of a hydrocracking catalyst, which increases the pore volume and pore size by effective desalination. CN106179462A discloses a hydrocracking catalyst and a preparation method thereof, which respectively adopts a positive addition method and a parallel flow method to prepare precipitate slurries, mixes the two kinds of precipitate slurries uniformly, and performs hydrothermal treatment on the shaped objects in water vapor containing urea. CN103055923A discloses a preparation method of a hydrocracking catalyst. Acidic mixed solution A, alkaline solution B and gas CO2 are added into a reaction tank containing clean water to form a gel. The three methods increase the pore volume and specific surface area of the catalyst by changing the preparation conditions, but easily cause the aggregation of active metals in the catalyst, the oxide particles are large and uneven in size, the utilization rate of active metals is reduced, the active metals are not fully utilized, and the hydrogenation activity cannot meet the standard of industrial white oil products.

[0006] At present, the method for preparing a bulk catalyst improves the hydrogenation activity of the catalyst by increasing the content of active metals and optimizing the physicochemical properties of the catalyst, but does not further improve the utilization rate of active metals of the bulk catalyst, and the hydrogenation activity of the catalyst cannot meet the production of industrial white oil. Therefore, improving the hydrogenation activity of the bulk catalyst and improving the mutual cooperation between the hydrogenation component and the acid component are the keys to meeting the production of high-quality industrial white oil by the bulk hydrocracking catalyst.

[0007] CN111068750A discloses a modified alumina carrier, a preparation method thereof and a hydrorefining catalyst. A pseudo-boehmite precursor slurry, a mesoporous molecular sieve, graphene and an organic alcohol are mixed, aging is performed, and after shaping, drying and calcination, a modified alumina carrier is obtained. CN108067221A discloses a preparation method of a superfine modified fly ash-oxidized graphene-palladium hydrogenation catalyst. A small amount of oxidized graphene is prepared in the preparation process, and the above preparation methods add graphene to the carrier, but graphene is not fully utilized. CN106944065A provides a preparation method of a graphene supported nickel hydrogenation catalyst. Nickel is supported on graphene by an ammonia evaporation method. However, the carrier of the catalyst is oxidized graphene, the cost of the catalyst is greatly increased, and the application prospect is small.

[0008] At present, in view of the low utilization rate of graphene in the hydrogenation catalyst, how to improve the interaction between graphene and hydrogenation active metals, fully play the role of graphene and improve the utilization rate of active metals of the bulk catalyst is a problem to be solved. SUMMARY

[0009] In view of the deficiencies of the prior art, the present application provides a preparation method of a bulk phase hydrocracking catalyst. The present application well integrates the precipitation and aging processes with the formation of each component of the catalyst, and further controls the particle size of the active metal oxide particles by matching specific precipitants, so that the catalyst has excellent isomerization performance and aromatic conversion capacity, and is suitable for application in a hydrocracking process of No. 5 industrial-grade white oil and lubricating oil base oil.

[0010] The preparation method of the bulk phase hydrocracking catalyst of the present application comprises the following contents:

[0011] (1) The W, Mo and Al-containing solution, the beta molecular sieve slurry and the precipitant are subjected to a first gelation reaction in parallel, after the reaction is completed, the graphene is added to obtain a first slurry;

[0012] (2) The Ni, Al and Cu-containing solution and the precipitant are added dropwise to the first slurry to perform a second gelation reaction, and the obtained slurry is aged to obtain a second slurry;

[0013] (3) The second slurry is filtered, dried, rolled, formed, washed, and then dried and calcined to obtain the bulk phase hydrocracking catalyst; wherein the precipitants in step (1) and step (2) are the same, and the precipitants include precipitant A and precipitant B, the precipitant A is a mixed solution of sodium hydroxide and sodium bicarbonate, and the precipitant B is ammonia water.

[0014] In the method of the present application, the concentration of the precipitant A is 7wt%-20wt%, the molar ratio of sodium hydroxide to sodium bicarbonate is 0.2:1-0.8:1, and preferably 0.3:1-0.7:1; the concentration of the precipitant B is 4wt%-8wt%, and the molar ratio of the precipitant B to the precipitant A is 0.05:1-0.45:1, and preferably 0.1:1-0.40:1.

[0015] In the method of the present application, in the W, Mo and Al-containing solution in step (1), the weight concentration of W calculated as WO3 is 5-120g / L, and preferably 10-110g / L, the weight concentration of Mo calculated as MoO3 is 8-120g / L, and preferably 10-100g / L, and the weight concentration of Al calculated as Al2O3 is 2-90g / L, and preferably 6-85g / L; wherein when preparing the W, Mo and Al-containing solution, the commonly used tungsten source is ammonium metatungstate, the molybdenum source is ammonium molybdate, and the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum acetate.

[0016] In the method of the present application, the beta molecular sieve slurry in step (1) is a uniform mixture of beta molecular sieve and deionized water, and the solid-liquid mass ratio is 1:2.5-1:8.0, and preferably 1:3.0-1:7.0.

[0017] In the method, the beta molecular sieve in step (1) has the following properties: the molar ratio of silicon oxide to aluminum oxide is 30-90; the specific surface area is 430-780 m 2 / g, preferably 400-700 m 2 / g; the pore volume is 0.30-0.90 cm 3 / g, preferably 0.35-0.85 cm 3 / g; the infrared acid acid amount is 0.10-0.45 mmol / g, preferably 0.18-0.40 mmol / g.

[0018] In the method, the first gelation reaction in step (1) has the following conditions: the reaction temperature is 30-95°C, preferably 40-95°C, the pH value is 5-6, and the reaction time is 0.1-1.0 hour.

[0019] In the method, the graphene in step (1) can be one or two of single-layer graphene, double-layer graphene, few-layer graphene or multi-layer graphene. The preparation method of the graphene is known to those skilled in the art. For example, the following method can be used: ultrasonic exfoliation of graphite oxide in water for 0.5-3h to prepare an oxidized graphene suspension, then adding hydrazine hydrate and / or sodium borohydride to reduce the oxidized graphene to graphene.

[0020] In the method, the solution containing Ni, Al and Cu in step (2) has the following weight concentrations: the weight concentration of Ni as NiO is 5-145 g / L, preferably 8-135 g / L; the weight concentration of Al as Al2O3 is 5-70 g / L, preferably 8-65 g / L; and the weight concentration of Cu as CuO is 5-80 g / L, preferably 8-75 g / L. When preparing the solution containing Ni, Al and Cu, the nickel source is generally one or more of nickel sulfate, nickel nitrate and nickel chloride; the aluminum source is generally one or more of soluble aluminum salts such as aluminum nitrate, aluminum sulfate and aluminum chloride; and the copper source is generally one or more of copper-containing nitrate and / or acetate.

[0021] In the method, the second gelation reaction in step (2) has the following conditions: the reaction temperature is 30-95°C, preferably 40-95°C, the pH value at the end of the reaction is controlled to be 8.0-12.0, and the reaction time is 0.5-2.5 hours.

[0022] In the method, the aging conditions in step (2) are as follows: the aging temperature is 55-90°C, preferably 65-90°C, the pH value is 8.0-11.0, and the aging time is 1.0-5.0 hours.

[0023] In the method of the present application, in step (2), the Al added by the solution containing Ni, Al and Cu accounts for 5% to 50%, preferably 6% to 45% of the total Al in the obtained hydrocracking catalyst in terms of Al 2 O 3.

[0024] In the method of the present application, the drying, shaping and washing in step (3) can be carried out by conventional methods in the art. The drying conditions are as follows: drying at 40-150°C for 1-48 hours, preferably 50-120°C for 4-36 hours. During the shaping process, conventional shaping aids such as one or more of a peptizing agent, an extrusion aid, etc. can be added as needed. The peptizing agent is one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, etc., and the extrusion aid refers to a substance that is beneficial to extrusion molding, such as one or more of amaranth powder, carbon black, graphite powder, citric acid, etc., and the amount of the extrusion aid is 1wt% to 10wt% of the total material dry basis. Washing is generally carried out using deionized water or a solution containing decomposable salts (such as ammonium acetate, ammonium chloride, ammonium nitrate, etc.) and washed to neutral. The shaped catalyst can be in the form of a sheet, a sphere, a cylindrical strip or a special-shaped strip (three-leaf clover, four-leaf clover), preferably a cylindrical strip or a special-shaped strip (three-leaf clover, four-leaf clover). The catalyst can be in the form of a fine strip with a diameter of 0.8-2.0mm or a thick strip with a diameter of >2.5mm.

[0025] In the method of the present application, the calcination conditions in step (3) are as follows: calcination at 350-650°C for 1-24 hours, preferably 400-600°C for 2-12 hours.

[0026] The present application also provides a bulk hydrocracking catalyst, which comprises a hydrogenation active metal component, amorphous alumina, CuO, graphene and β molecular sieve; the total content of the hydrogenation active metal components Ni, W and Mo in terms of oxides is 39% to 82%, preferably 42% to 75%, based on the weight of the hydrocracking catalyst; the content of amorphous alumina is 5% to 25%, preferably 8% to 23%; the content of CuO is 3% to 16%, preferably 3% to 14%; the content of graphene is 3% to 12%, preferably 3% to 10%; and the content of β molecular sieve is 6% to 20%, preferably 6% to 18%.

[0027] The molar ratio of W / Mo is 1:6 to 24:1, preferably 1:4 to 21:1, the molar ratio of Ni / (Mo+W) is 1:13 to 17:1, preferably 1:10 to 15:1, and the molar ratio of Cu / Ni is 1:8 to 7:10, preferably 1:7 to 6:10.

[0028] The ratio of the weight content of the surface active metal component WO3 to the weight content of the bulk active metal component WO3 is 2.8:1 to 7.2:1, preferably 3.5:1 to 6.5:1, the ratio of the weight content of the surface active metal component MoO3 to the weight content of the bulk active metal component MoO3 is 3.0:1 to 7.0:1, preferably 3.3:1 to 6.6:1, the ratio of the sum of the weight content of the surface active metal components CuO and NiO to the sum of the weight content of the bulk active metal components CuO and NiO is 3.0:1 to 7.5:1, preferably 3.2:1 to 6.8:1, and the ratio of the weight content of graphene in the surface phase to the sum of the weight content of graphene in the bulk phase is 1.8:1 to 4.0:1, preferably 2.0:1 to 3.8:1.

[0029] The pore size distribution of the bulk phase hydrocracking catalyst of the present application is as follows: the pore volume of pores having a diameter of 6 nm or less accounts for 6% to 21% of the total pore volume, the pore volume of pores having a diameter of 6 to 10 nm accounts for 50% to 68% of the total pore volume, the pore volume of pores having a diameter of 10 to 15 nm accounts for 6% to 20% of the total pore volume, and the pore volume of pores having a diameter of 15 nm or more accounts for 6% to 20% of the total pore volume; the specific surface area of the catalyst is 180 to 500 m 2 / g, and the pore volume is 0.25 to 1.0 mL / g.

[0030] In the bulk phase hydrocracking catalyst of the present application, the average particle size of the Ni, W and Mo active metal oxide particles is 10 to 14 nm. Preferably, the particle size distribution of the oxide particles is as follows: the number of particles having a particle size of less than 10 nm accounts for 2% to 16% of the total number of particles, the number of particles having a particle size of 10 nm to 14 nm accounts for 63% to 87% of the total number of particles, and the number of particles having a particle size of more than 14 nm accounts for 7% to 22% of the total number of particles.

[0031] The specific surface area of the bulk phase hydrocracking catalyst of the present application is 180 to 520 m 2 / g, and the pore volume is 0.35 to 0.80 mL / g.

[0032] The bulk phase hydrocracking catalyst of the present application can be used in a hydrocracking process for producing special oils and base oils for lubricating oils, and is particularly suitable for a hydrocracking process for base oil feedstocks of No. 5 industrial grade white oil and high viscosity index lubricating oil.

[0033] The body phase hydrocracking catalyst of the present application is suitable for a wide range of heavy feedstocks, which include one or more of vacuum gas oil, coking gas oil, deasphalted oil, thermal cracking gas oil, catalytic cracking gas oil, catalytic cracking cycle oil and the like various hydrocarbon oils, usually containing hydrocarbons with a boiling point of 250-550 DEG C, and the nitrogen content can be 300-2500 mu g / g, after the pretreatment process by hydrocracking, the nitrogen content in the feed of the body phase hydrocracking catalyst of the present application can be more than 10 mu g / g, further more than 50 mu g / g, and still has high activity, stability and good product quality under the condition of high nitrogen content feed generally not more than 150 mu g / g.

[0034] Compared with the prior art, the present application has the following advantages:

[0035] 1. The catalyst of the present application contains more Ni and Cu and graphene in the surface phase, graphene has a strong hydrogen molecule adsorption capacity, matches the hydrogen overflow property of Ni-Cu, and the combination of the two can effectively activate hydrogen molecules into active hydrogen, improve the role of graphene in the hydrogenation catalyst, and further improve the utilization rate of active metals of the bulk phase catalyst.

[0036] 2. In the method of the present application, the W, Mo and Al-containing solution is first precipitated, and the Ni, Al and Cu-containing solution and the graphene solution are added dropwise in the obtained slurry at a specific pH value, so that the hydrogenation active metals tungsten, nickel and molybdenum are more uniformly dispersed in the catalyst, which is beneficial to improve the hydrogenation saturation activity of W-Ni combination and the hydrogenation denitrification activity of Mo-Ni combination, and more Cu and Ni are exposed in the surface phase, which is beneficial to the role of graphene, and the hydrogenation desulfurization and hydrogenation denitrification of the catalyst are obviously improved. At the same time, the beta molecular sieve is added in the first gelation reaction, which is beneficial to the full contact of the oxide particles with the molecular sieve, improves the diffusion performance of the catalyst and the mutual action of the hydrogenation component and the acid component.

[0037] 3. In the gelation reaction process of the present application, a mixed solution of sodium hydroxide and sodium carbonate and ammonia water are used as precipitants, and by controlling the mass ratio between sodium hydroxide and sodium carbonate and the weight concentration of ammonia water, compared with single precipitants such as ammonia water, sodium hydroxide and sodium carbonate, the problems of small pore volume and specific surface area of the bulk phase catalyst, poor cohesiveness of the gelation material and large oxide particles are effectively overcome, the generated particles are uniform in size, and the mutual action of the acid center and the hydrogenation center is more beneficial.

[0038] 4、The method of the present application can fully contact the active metal with the molecular sieve by comprehensive control of the preparation steps and preparation conditions, and at the same time, the pore volume and pore size of the catalyst are large, the probability of the mutual penetration of the pore channels of the active component carrier and the molecular sieve is improved, the diffusion performance of the catalyst is improved, and the hydrogenation component and the acid component can mutually cooperate. The catalyst with high hydrogenation active sites can hydrogenate more and faster the organic nitrogen-containing compounds which have a great toxic effect on the acid centers of the catalyst, thereby protecting the acid centers of the catalyst and improving the nitrogen resistance of the hydrocracking catalyst, and the properties of the hydrocracking product can be improved. DETAILED DESCRIPTION

[0039] In the present application, the specific surface area and pore volume are determined by low-temperature liquid nitrogen adsorption method, and the mechanical strength is determined by side pressure method.

[0040] In the present application, the average particle size (D50 particle size) and particle size distribution of the active metal oxide microparticles are measured by a nanoparticle size and Zeta potential analyzer (Zetasizer Nano ZS).

[0041] In the present application, the content of the active metal on the surface of the catalyst is determined by X-ray photoelectron spectroscopy (XPS), and the content of the active metal in the bulk of the catalyst is determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The properties of the beta molecular sieve used are shown in Table 7, and the properties of the Y molecular sieve are shown in Table 8.

[0042] Example 1

[0043] Ammonium metatungstate, ammonium molybdate and aluminum chloride were added into dissolving tank 1 containing deionized water to prepare a W, Mo and Al containing solution, in which the weight concentration of W as WO3 was 52 g / L, the weight concentration of Mo as MoO3 was 30 g / L, and the weight concentration of Al as Al2O3 was 16.8 g / L. Nickel chloride, aluminum chloride and copper nitrate were added into dissolving tank 2 containing deionized water to prepare a Ni, Al and Cu containing solution, in which the weight concentration of Ni as NiO was 40 g / L, the weight concentration of Cu as CuO was 14 g / L, and the Al in the Ni, Al and Cu containing solution accounted for 30% of the total Al (as Al2O3) in the obtained hydrocracking catalyst. 26 g of β-molecular sieve was mixed with deionized water at a solid-to-liquid ratio of 1:4 to prepare a β-molecular sieve slurry. Deionized water was added into a reaction tank, and the W, Mo and Al containing solution, precipitant A, precipitant B and the β-molecular sieve slurry were added into the reaction tank to perform a first gelation reaction, the weight concentration of precipitant A was 10 wt%, the molar ratio of sodium hydroxide to sodium bicarbonate was 0.4:1, the weight concentration of precipitant B was 6%, the ratio of the moles of precipitant B to the sum of the moles of precipitant A was 0.25, the pH value of the reaction was controlled at 5.3, the reaction temperature was 62°C, and the reaction time was 0.8 hours. Then, 14 g of graphene was added, and the Ni, Al and Cu containing solution, precipitant A and precipitant B were simultaneously added dropwise into the reaction slurry to perform a second gelation reaction (the precipitants were the same as those in the first gelation reaction), the reaction temperature was unchanged, the reaction time was 1.0 hours, and the pH value of the reaction was controlled at 8.8 at the end of the reaction. A precipitate slurry containing nickel, molybdenum, tungsten, copper, aluminum, graphene and β-molecular sieve was generated. The obtained slurry was aged, the aging temperature was 78°C, the pH value was controlled at 8.5 during aging, the aging time was 2.0 hours, and the aging was ended. The obtained slurry was filtered, the filter cake was dried at 100°C for 9 hours, was rolled and was extruded into a strip. The wet strip after washing was neutralized at room temperature. Then, the washed wet strip was dried at a temperature of 100°C for 9 hours, and the dried material was calcined at 540°C for 4 hours to obtain catalyst A. The catalyst composition and main properties are shown in Table 1.

[0044] Example 2

[0045] Ammonium metatungstate, ammonium molybdate and aluminum chloride were added to a dissolving tank 1 containing deionized water to prepare a W, Mo and Al containing solution, the W, Mo and Al containing solution having a W concentration of 40 g / L as WO3, a Mo concentration of 40 g / L as MoO3, and an Al concentration of 18.2 g / L as Al2O3. Nickel chloride, aluminum chloride and copper nitrate were added to a dissolving tank 2 containing deionized water to prepare a Ni, Al and Cu containing solution, the Ni, Al and Cu containing solution having a Ni concentration of 44 g / L as NiO, a Cu concentration of 12 g / L as CuO, and the Al in the Ni, Al and Cu containing solution accounting for 35% of the total Al (as Al2O3) in the resulting hydrocracking catalyst. Deionized water was added to a reaction tank, and the W, Mo and Al containing solution was added to the reaction tank concurrently with precipitant A, precipitant B and a beta molecular sieve slurry to perform a first gelation reaction, the precipitant A having a concentration of 12 wt%, the molar ratio of sodium hydroxide to sodium bicarbonate being 0.5:1, the precipitant B having a concentration of 5%, the ratio of the moles of the precipitant B to the sum of the moles of the precipitant A being 0.29, the reaction pH being controlled at 5.5, and the reaction temperature being 65°C. After 0.7 hours of reaction, graphene was added, and the Ni, Al and Cu containing solution, the precipitant A and the precipitant B were simultaneously added dropwise to the reaction slurry to perform a second gelation reaction (the precipitant was the same as the precipitant in the first gelation reaction), the reaction temperature being unchanged, the reaction time being 0.9 hours, and the pH being controlled at 9.0 at the end of the reaction. A precipitate slurry containing nickel, molybdenum, tungsten, copper, aluminum, graphene and beta molecular sieve was formed, and the resulting slurry was aged, the aging temperature being 83°C, the pH being controlled at 8.7 during aging, the aging time being 2.3 hours, and the aging being completed. The resulting slurry was filtered, the filter cake was dried for the first time at 100°C for 9 hours, was rolled and was extruded into a strip. The strip was washed with deionized water at room temperature until neutral. The wet strip after washing was dried at 80°C for 9 hours, and the dried material was calcined at 530°C for 5 hours to obtain catalyst B. The catalyst composition and main properties are shown in Table 1.

[0046] Example 3

[0047] Ammonium metatungstate, ammonium molybdate and aluminum chloride were added to a dissolving tank 1 containing deionized water to prepare a W, Mo and Al containing solution, the W, Mo and Al containing solution having a W concentration of 48 g / L as WO3, a Mo concentration of 24 g / L as MoO3, and an Al concentration of 18.0 g / L as Al2O3. Nickel chloride, aluminum chloride and copper nitrate were added to a dissolving tank 2 containing deionized water to prepare a Ni, Al and Cu containing solution, the Ni, Al and Cu containing solution having a Ni concentration of 52 g / L as NiO, a Cu concentration of 16 g / L as CuO, and the Al in the Ni, Al and Cu containing solution accounting for 25% of the total Al (as Al2O3) in the resulting hydrocracking catalyst. Deionized water was added to a reaction tank, and the W, Mo and Al containing solution was added to the reaction tank concurrently with precipitant A, precipitant B and beta molecular sieve slurry to perform a first gelation reaction, the precipitant A having a concentration of 10 wt%, the molar ratio of sodium hydroxide to sodium bicarbonate being 0.45:1, the precipitant B having a concentration of 7%, the ratio of the moles of precipitant B to the sum of the moles of precipitant A being 0.32, the reaction pH being controlled at 5.8, the reaction temperature being 70°C, and the reaction time being 0.6 hours. Graphene was added, and the Ni, Al and Cu containing solution, precipitant A and precipitant B were simultaneously added dropwise to the reaction slurry to perform a second gelation reaction (the precipitant was the same as that in the first gelation reaction), the reaction temperature being unchanged, the reaction time being 1.2 hours, and the reaction pH being controlled at 9.4 at the end of the reaction. A precipitate slurry containing nickel, molybdenum, tungsten, copper, aluminum, graphene and beta molecular sieve was formed, and the resulting slurry was aged, the aging temperature being 83°C, the pH being controlled at 8.3 during aging, the aging time being 2.2 hours, and the aging being completed. The resulting slurry was filtered, the filter cake was dried for the first time at 120°C for 8 hours, was rolled and was extruded into a strip. The strip was washed with deionized water at room temperature until neutral. The wet strip after washing was dried at a temperature of 80°C for 10 hours, and the dried material was calcined at 550°C for 5 hours to obtain catalyst C. The catalyst composition and main properties are shown in Table 1.

[0048] Example 4

[0049] Ammonium metatungstate, ammonium molybdate and aluminum chloride were added into dissolving tank 1 containing deionized water to prepare a W, Mo and Al containing solution, in which the weight concentration of W as WO3 was 44 g / L, the weight concentration of Mo as MoO3 was 28 g / L, and the weight concentration of Al as Al2O3 was 17.4 g / L. Nickel chloride, aluminum chloride and copper nitrate were added into dissolving tank 2 containing deionized water to prepare a Ni, Al and Cu containing solution, in which the weight concentration of Ni as NiO was 48 g / L, the weight concentration of Cu as CuO was 16 g / L, and the Al in the Ni, Al and Cu containing solution accounted for 38% of the total Al (as Al2O3) in the obtained hydrocracking catalyst. Deionized water was added into a reaction tank, and the W, Mo and Al containing solution was added into the reaction tank in parallel flow with precipitant A, precipitant B and beta molecular sieve slurry to perform a first gelation reaction, the weight concentration of precipitant A was 13 wt%, the molar ratio of sodium hydroxide to sodium bicarbonate was 0.42:1, the weight concentration of precipitant B was 5%, the molar ratio of precipitant B to the sum of moles of precipitant A was 0.27, the reaction pH value was controlled at 5.5, the reaction temperature was 53°C, and the reaction time was 0.7 hours. Then, graphene was added, and the Ni, Al and Cu containing solution, precipitant A and precipitant B were simultaneously added dropwise into the reaction slurry to perform a second gelation reaction (the precipitant was the same as that in the first gelation reaction), the reaction temperature was unchanged, the reaction time was 1.2 hours, and the pH value was controlled at 9.5 at the end of the reaction. A precipitate slurry containing nickel, molybdenum, tungsten, copper, aluminum, graphene and beta molecular sieve was generated, and the obtained slurry was aged, the aging temperature was 88°C, the pH value was controlled at 9.2 during aging, the aging time was 2.5 hours, and the aging was ended. The obtained slurry was filtered, the filter cake was dried for the first time at 90°C for 10 hours, was rolled and was extruded into a strip. The strip was washed with deionized water at room temperature until neutral. Then, the washed wet strip was dried at a temperature of 100°C for 9 hours, and the dried material was calcined at 510°C for 5 hours to obtain catalyst D. The catalyst composition and main properties are shown in Table 1.

[0050] Comparative Example 1

[0051] According to the method disclosed in CN101239324A, reference agent E with an active metal oxide content of 76% was prepared, the components and active metal contents were the same as those in Example 1, the molecular sieve was beta molecular sieve, and the specific steps were as follows:

[0052] (1) Respectively, the nickel chloride, ammonium molybdate, aluminum chloride solution, into the dissolving tank containing deionized water, the mass concentration of Ni in the solution is 52 g / L as NiO, the weight concentration of Mo is 32 g / L as MoO3, the mass concentration of Al is 22 g / L as Al2O3, add 2000 mL of pure water dilution; (2) Under stirring, add ammonia water until the pH value is 5.2; (3) Prepare a sodium tungstate solution containing 68 g / l of WO3, and add it to the mixture under stirring; (4) Continue to add ammonia water until the pH value is 7.8; (5) The whole gelation process should be carried out at 62℃; (6) The mixture is aged at 78℃ for 4 hours; Before aging, add the β molecular sieve used in the preparation method, the β molecular sieve accounts for 13% of the total weight of the catalyst, the properties are shown in Table 4, and the aging is finished; (7) Filter, dry in a 100℃ oven for 9 hours, roll, extrude into strips with a 3mm diameter hole plate; Wash with ammonium acetate solution with pH=8.8 at room temperature; Then dry in an 80℃ oven for 10 hours, calcine at 540℃ for 4 hours, to obtain the catalyst E, the catalyst composition and properties are shown in Table 1.

[0053] Comparative Example 2

[0054] According to the preparation method disclosed in CN106179462A, a reference agent F with an active metal oxide content of 76% is prepared, and the acid component is β molecular sieve, and the specific process is as follows:

[0055] A mixed solution A was prepared by dissolving nickel chloride and aluminum chloride solution in deionized water, the weight concentration of NiO in the mixed solution A was 52 g / L, and the weight concentration of Al2O3 was 15.4 g / L. A mixed solution B was prepared by dissolving ammonium metatungstate, ammonium molybdate and aluminum chloride solution in deionized water, the weight concentration of WO3 in the mixed solution B was 68 g / L, the weight concentration of MoO3 was 32 g / L, and the weight concentration of Al2O3 was 6.6 g / L. 10% (by weight) ammonia water was added to solution A under stirring, the gelation temperature was kept at 62 °C, the pH value was controlled at 7.8 at the end of the reaction, and the gelation time was controlled at 0.8 hour, to form a slurry I containing nickel and aluminum precipitates. Deionized water was added to the reaction tank, and 10% (by weight) ammonia water and solution B were added to the reaction tank in parallel flow, the gelation temperature was kept at 62 °C, the pH value was controlled at 7.8 during the parallel flow gelation reaction, and the gelation time was controlled at 1.0 hour, to form a slurry II containing tungsten, molybdenum and aluminum precipitates. The two slurry containing precipitates were mixed and aged, the aging time was 4.0 hours, the aging temperature was 78 °C, and the pH value was controlled at 7.6, then the filter cake was hydrothermally treated in steam containing urea, the molar ratio of urea to total active metal atoms was 7:1, the temperature was 250 °C, the pressure was 4.0 MPa, and the treatment time was 3 hours, then the filter cake was slurried, the mixture slurry was stirred uniformly with a β molecular sieve suspension, filtered, the filter cake was dried at 100 °C for 9 hours, rolled, and extruded into a strip. The wet strip was washed with deionized water at room temperature until neutral, then the washed wet strip was dried at 80 °C for 10.0 hours. The dried material was calcined at 540 °C for 4 hours to obtain catalyst F. The catalyst composition, pore distribution and main properties are shown in Table 1.

[0056] Comparative Example 3

[0057] A reference agent G identical to Example 1 of the patent was prepared, except that the acidic component was Y molecular sieve, and the catalyst composition and main properties are shown in Table 1.

[0058] Comparative Example 4

[0059] A reference agent H identical to Example 1 was prepared, except that Al and Cu were added in the first gelation reaction. The specific preparation process is as follows:

[0060] Ammonium metatungstate, ammonium molybdate, copper nitrate and aluminum chloride were added into dissolving tank 1 containing deionized water to prepare a solution containing W, Mo, Al and Cu, wherein the weight concentration of W in the form of WO3 was 52 g / L, the weight concentration of Mo in the form of MoO3 was 30 g / L, the weight concentration of Cu in the form of CuO was 14 g / L, and the weight concentration of Al in the form of Al2O3 was 24 g / L. Nickel chloride was added into dissolving tank 2 containing deionized water to prepare a solution containing Ni, wherein the weight concentration of Ni in the form of NiO was 40 g / L. 26 g of β molecular sieve was mixed with deionized water at a solid-to-liquid ratio of 1:4 to prepare a β molecular sieve slurry. Deionized water was added into a reaction tank, and the solution containing W, Mo, Cu and Al, precipitant A, precipitant B and the β molecular sieve slurry were added into the reaction tank to perform a first gelation reaction, wherein the weight concentration of precipitant A was 10 wt%, the molar ratio of sodium hydroxide to sodium bicarbonate was 0.4:1, the weight concentration of precipitant B was 6%, the molar ratio of precipitant B to the sum of moles of precipitant A was 0.25, the pH value of the reaction was controlled at 5.3, the reaction temperature was 62°C, and the reaction time was 0.8 h. Then, 14 g of graphene was added, and the solution containing Ni, precipitant A and precipitant B were simultaneously added dropwise into the reaction slurry to perform a second gelation reaction (the precipitants were the same as those in the first gelation reaction), wherein the reaction temperature was unchanged, the reaction time was 1.0 h, and the pH value of the reaction was controlled at 8.8 at the end of the reaction. A slurry containing a precipitate of Ni, Mo, W, Cu, Al, graphene and β molecular sieve was prepared, and the slurry was aged, wherein the aging temperature was 78°C, the pH value of the slurry was controlled at 8.5 during the aging, the aging time was 2.0 h, and the aging was ended. The slurry was filtered, the filter cake was dried at 100°C for 9 h, was rolled and was extruded into a strip. The wet strip was washed with deionized water until neutral at room temperature. Then, the washed wet strip was dried at 100°C for 9 h, and the dried material was calcined at 540°C for 4 h to obtain catalyst H. The composition and main properties of the catalyst are shown in Table 1.

[0061] Comparative Example 5

[0062] The same as in Example 1, the active metal oxide content was 76%, and Reference Agent I was prepared without graphene and copper oxide.

[0063] Comparative Example 6

[0064] The same as in Example 1, Reference Agent J was prepared by using precipitant A for the precipitation reaction.

[0065] Comparative Example 7

[0066] The same as in Example 1, Reference Agent K was prepared by using precipitant B for the precipitation reaction.

[0067] Example 5

[0068] The present embodiment is catalyst activity evaluation experiment of the present application, and comparison with comparative catalyst. Respectively, the present application catalyst A, B, C, D and comparative catalyst E, F, G, H, I, J, K are used in 200ml small hydrogenation device to carry out comparison and evaluation test, and the comparison and evaluation test is carried out in 200ml small hydrogenation device, and the evaluation conditions are: total reaction pressure 15.7MPa, hydrogen oil volume ratio 1200:1, liquid hourly space velocity 1.6h -1 , reaction temperature 375℃, 385℃, and the evaluation raw material is vacuum gas oil, and its main properties are shown in table 4, and the evaluation results are shown in table 5-6.

[0069] From table 1-3, it can be seen that the catalyst of the present application contains graphene, and the active metal is more. The catalyst activity evaluation process conditions and the evaluation results can be seen that, compared with the comparative catalyst, the catalyst of the present application has high isomerization performance and high aromatic saturation performance in the treatment of heavy oil hydrocracking process, can produce 5 industrial grade white oil and lubricating oil base oil, and the comparative catalyst cannot have high isomerization performance and high aromatic saturation performance at the same time. The hydrocracking catalyst of the present application still has good stability and good product quality under the condition of high nitrogen content feed. Compared with the body phase catalyst (reference agent I) prepared by the same method without graphene, the metal oxide content of the catalyst of the present application is 6-10m% lower than that of the body phase catalyst (reference agent I) without graphene when the hydrogenation activity is equivalent.

[0070] Table 1 catalyst composition and properties prepared by example and comparative example

[0071] Catalyst No. A B C D E F NiO, wt% 20 22 26 24 26 26 WO3, wt% 26 20 24 22 34 34 MoO3, wt% 15 20 12 14 16 16 CuO, wt% 7 6 8 8 - - Al203, wt% 12 14 12 14 11 11 SiO2, wt% 13 12 10 12 13 13 Graphene, wt% 7 6 8 6 - - Specific surface area, m 2 / g]] 405 410 415 400 228 377 Pore volume, mL / g 0.438 0.448 0.456 0.428 0.323 0.410 Pore distribution < 6 nm 15.12 14.38 13.38 16.53 62.47 35.16 6 nm ~ 10 nm 59.54 59.87 60.14 58.91 18.54 35.14 10 nm ~ 15 nm 12.90 13.01 13.14 12.31 10.51 16.02 > 15 nm 12.44 12.74 13.34 12.25 8.48 13.68

[0072] Table 1 catalyst composition and properties prepared by example and comparative example

[0073] Catalyst No. G H I J K NiO, wt% 20 20 26 20 20 WO3, wt% 26 26 34 26 26 MoO3, wt% 15 15 16 15 15 CuO, wt% 7 7 - 7 7 Al203, wt% 12 12 11 12 12 SiO2, wt% 13 13 13 13 13 Graphene, wt% 7 7 - 7 7 Specific surface area, m 2 / g]] 402 395 392 394 179 Pore volume, mL / g 0.436 0.423 0.420 0.421 0.282 Pore distribution < 6 nm 15.24 16.37 17.18 16.23 67.23 6 nm ~ 10 nm 59.06 58.91 58.51 58.14 19.05 10 nm ~ 15 nm 12.92 12.32 11.94 13.18 7.86 > 15 nm 12.78 12.40 12.37 11.45 5.86

[0074] Table 2 weight content ratio of active metal oxide in catalyst surface phase and body phase

[0075] Catalyst No. A B C D Table phase I W Bulk phase I W ]]> 5.48 5.64 5.81 5.36 Table phase I Mo Bulk phase I Mo ]]> 5.12. 5.23 5.35 5.08 Table phase I Cu+Ni Bulk phase I Cu+Ni ]]> 5.89 5.98 6.15 5.74 Table phase I 石墨烯 Bulk phase I 石墨烯 ]]> 2.87 2.99 3.25 2.78

[0076] Table 2 (continued)

[0077] Catalyst No. E F G H I J K Table phase I W Bulk phase I W ]]> 1.08 4.34 5.41 5.14 5.39 1.02 0.98 Table phase I Mo Bulk phase I Mo ]]> 1.06 4.18 5.06 4.98 5.08 1.04 0.92 Table phase I Cu+Ni Bulk phase I Cu+Ni ]]> - - 5.82 - 1.55 1.01 0.95 Table phase I 石墨烯 Bulk phase I 石墨烯 ]]> - - 2.83 - 2.43 0.95 0.92

[0078] Table 3 average particle size and particle size distribution of oxide particles of catalyst obtained by each example

[0079] Catalyst No. A B C D E F Core-shell composite oxide particle average particle size, nm 12.7 12.9 12.4 12.2 26.5 28.9 Oxide particle size distribution, % Particle size less than 10 nm 8.89 8.28 8.05 8.01 2.36 2.03 Particle size 10 nm - 14 nm 77.64 76.91 78.67 78.97 10.98 8.56 Particle size greater than 14 nm 13.47 14.81 13.28 13.02 86.66 89.41

[0080] Table 3 (continued) average particle size and particle size distribution of core-shell composite oxide particles of catalyst obtained by each example

[0081] Catalyst No. G H I J K Core-shell composite oxide particle average particle size, nm 12.8 15.8 13.5 15.0 35.3 Core-shell composite oxide particle size distribution, % Particle size less than 10 nm 8.82 7.15 7.86 8.82 8.13 Particle size 10 nm - 14 nm 77.55 72.62 77.89 71.62 6.68 Particle size greater than 14 nm 13.63 20.23 14.25 19.56 85.19

[0082] Table 4. Main properties of the feed oils

[0083] Feed oil Middle East vacuum gas oil Density (20°C) / g-cm -3 ]] 0.9236 Distillation range / °C IBP / EBP 316 / 531 S, wt% 1.96 N, wt% 0.36 BMCI value 50.1 Mass spectrum composition, wt% Paraffins 20.0 Naphthenes 30.2 Aromatics 49.8

[0084] Table 5. Evaluation results of the catalysts of the examples and comparative examples (operation for 250 hours)

[0085] Catalyst A B C D E F Reaction temperature, °C 375 375 375 375 375 375 Nitrogen content in feed, pg / g 118 140 107 100 118 118 82 ~ 132 °C heavy naphtha Aromatics, wt% 58.4 58.3 58.0 58.8 61.3 61.0 132 ~ 282 °C marine fuel Smoke point / mm 29.6 29.8 30.1 29.3 24.8 23.7 Aromatics, v% 1.7 1.4 1.1 2.1 12.8 11.7 282 ~ 370 °C diesel Pour point / °C -7 -8 -8 -7 -7 -7 Aromatics / wt% 1.8 1.6 1.4 2.2 15.6 14.1 > 370 °C tail oil BMCI value 5.2 5.0 4.8 5.7 26.9 25.1 Viscosity index 123 125 126 120 89 92

[0086] Table 5. Evaluation results of the catalysts of the examples and comparative examples (operation for 250 hours) (continued)

[0087] Catalyst G H I J K Reaction temperature, °C 375 375 375 375 375 Nitrogen content in feed, pg / g 118 118 118 118 118 82 ~ 132 °C heavy naphtha Aromatics, wt% 58.5 60.1 58.5 60.8 60.4 132 ~ 282 °C marine fuel Smoke point / mm 29.6 25.2 29.5 23.3 23.7 Aromatics, v% 1.7 10.5 1.9 19.6 17.9 282 ~ 370 °C diesel Pour point / °C 3 -8 -7 -8 -8 Aromatics / wt% 1.9 10.8 2.1 18.6 17.5 > 370 °C tail oil BMCI value 5.3 15.6 5.4 23.6 21.4 Viscosity index 122 104 123 94 98

[0088] Table 6. Evaluation results of the catalysts of the examples and comparative examples (operation for 2000 hours)

[0089] Catalyst A B E F Reaction temperature, °C 375 375 385 385 Nitrogen content in feed, pg / g 118 140 118 118 82 ~ 132 °C heavy naphtha Aromatics, wt% 58.3 58.5 62.2 62.0 132 ~ 282 °C marine fuel Smoke point / mm 29.4 29.6 20.1 20.5 Aromatics, v% 1.9 1.8 20.8 20.2 282 ~ 370 °C diesel Pour point / °C -7 -7 -7 -8 Aromatics / wt% 2.0 1.8 19.4 18.5 > 370 °C tail oil BMCI value 5.4 5.3 33.1 30.8 Viscosity index 120 121 80 83

[0090] Table 7. Properties of the β molecular sieves in the examples and comparative examples

[0091] Silica-alumina mole ratio 80.5 Specific surface area, m 2 / g]]> 621 Pore volume, mL / g 0.55 Infrared total acid, mmol / g 0.43 Na2O, wt% 0.080

[0092] Table 8. Properties of the Y molecular sieves used in the present application

[0093] Molecular sieve properties Y Relative crystallinity, % 110 Unit cell parameter, nm 2.431 molar ratio of SiO2 / Al2O3 80.8 Specific surface area, m 2 / g]]> 896 Pore volume, mL / g 0.510 Infrared total acid, mmol / g 0.248 B acid / L acid 11.64 Na2O, wt% <0.01

Claims

1. A process for the preparation of a body phase hydrocracking catalyst, characterized in that The method comprises the following steps: (1) a solution containing W, Mo and Al, a beta molecular sieve slurry and a precipitant are subjected to a first gelation reaction in parallel, after the reaction is completed, graphene is added to obtain a first slurry; (2) a solution containing Ni, Al and Cu and a precipitant are added dropwise into the first slurry to perform a second gelation reaction, and the obtained slurry is subjected to aging to obtain a second slurry; (3) the second slurry is subjected to filtering, drying, rolling, molding, washing, drying and calcination to obtain a bulk phase hydrocracking catalyst; wherein the precipitant in step (1) and step (2) is the same, the precipitant comprises precipitant A and precipitant B, the precipitant A is a mixed solution of sodium hydroxide and sodium bicarbonate, and the precipitant B is ammonia water; the concentration of the precipitant A is 7wt%-20wt%, the molar ratio of sodium hydroxide to sodium bicarbonate is 0.2:1-0.8:1; the concentration of the precipitant B is 4wt%-8wt%, and the molar ratio of the precipitant B to the precipitant A is 0.05:1-0.45:1; the beta molecular sieve slurry in step (1) is a uniform mixture of beta molecular sieve and deionized water, and the solid-liquid mass ratio is 1:2.5-1:8.0; the pH value of the first gelation reaction in step (1) is 5-6; and the pH value of the second gelation reaction in step (2) is controlled to be 8.0-12.0 at the end of the reaction.

2. The method of claim 1, wherein: In the solution containing W, Mo and Al in step (1), the weight concentration of W in the form of WO3 is 5-120g / L, the weight concentration of Mo in the form of MoO3 is 8-120g / L, and the weight concentration of Al in the form of Al2O3 is 2-90g / L; wherein when the solution containing W, Mo and Al is prepared, the tungsten source is ammonium metatungstate, the molybdenum source is ammonium molybdate, and the aluminum source is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum acetate.

3. The method of claim 1, wherein: The β molecular sieve in step (1) has the following properties: the molar ratio of silicon oxide to aluminum oxide is 30-90, the specific surface area is 430-780 m 2 / g, the pore volume is 0.30-0.90 cm 3 / g, and the infrared acid acid amount is 0.10-0.45 mmol / g.

4. The method of claim 1, wherein: The reaction temperature of the first gelation reaction in step (1) is 30-95℃, and the reaction time is 0.1-1.0 hours.

5. The method of claim 1, wherein: The graphene in step (1) is one or two of single-layer graphene, double-layer graphene, few-layer graphene or multi-layer graphene.

6. The method of claim 1, wherein: In the solution containing Ni, Al and Cu in step (2), the weight concentration of Ni in the form of NiO is 5-145g / L, the weight concentration of Al in the form of Al2O3 is 5-70g / L, and the weight concentration of Cu in the form of CuO is 5-80g / L.

7. The method of claim 1, wherein: The reaction temperature of the second gelation reaction in step (2) is 30-95℃, and the reaction time is 0.5-2.5 hours.

8. The method of claim 1, wherein: The aging conditions in step (2) are as follows: the aging temperature is 55-90℃, the pH value is 8.0-11.0, and the aging time is 1.0-5.0 hours.

9. The method of claim 1, wherein: In step (2), the Al contained in the solution containing Ni, Al and Cu accounts for 5%-50% of the total Al in the bulk phase hydrocracking catalyst in the form of Al2O3.

10. A body phase hydrocracking catalyst prepared by the process of any one of claims 1 to 9, characterized by: The body-phase hydrocracking catalyst comprises a hydrogenation active metal component, amorphous alumina, CuO, graphene and beta molecular sieve; the total content of the hydrogenation active metal components Ni, W and Mo in oxide form is 39-82% by weight of the body-phase hydrocracking catalyst, the content of the amorphous alumina is 5-25%, the content of the CuO is 3-16%, the content of the graphene is 3-12%, and the content of the beta molecular sieve is 6-20%; the molar ratio of W / Mo is 1:6-24:1, the molar ratio of Ni / (Mo+W) is 1:13-17:1, and the molar ratio of Cu / Ni is 1:8-7:10; the ratio of the weight content of the surface-phase active metal component WO3 to the weight content of the body-phase active metal component WO3 is 2.8:1-7.2:1, the ratio of the weight content of the surface-phase active metal component MoO3 to the weight content of the body-phase active metal component MoO3 is 3.0:1-7.0:1, and the ratio of the sum of the weight content of the surface-phase active metal components CuO and NiO to the sum of the weight content of the body-phase active metal components CuO and NiO is 3.0:1-7.5:1; the ratio of the weight content of the graphene in the surface phase to the sum of the weight content of the graphene in the body phase is 1.8:1-4.0:

1.

11. The catalyst of claim 10, wherein: The pore size distribution of the bulk phase hydrocracking catalyst is as follows: the pore volume of the pores with a diameter of 6 nm or less accounts for 6% to 21% of the total pore volume, the pore volume of the pores with a diameter of 6 to 10 nm accounts for 50% to 68% of the total pore volume, the pore volume of the pores with a diameter of 10 to 15 nm accounts for 6% to 20% of the total pore volume, and the pore volume of the pores with a diameter of 15 nm or more accounts for 6% to 20% of the total pore volume; the specific surface area of the bulk phase hydrocracking catalyst is 180 to 500 m 2 / g, and the pore volume is 0.25 to 1.0 mL / g.

12. The catalyst of claim 10, wherein: The average particle size of the Ni, W and Mo active metal oxide particles is 10-14 nm; the particle size distribution of the Ni, W and Mo active metal oxide particles is as follows: the number of particles with a particle size less than 10 nm accounts for 2-16% of the total number of particles, the number of particles with a particle size of 10-14 nm accounts for 63-87% of the total number of particles, and the number of particles with a particle size greater than 14 nm accounts for 7-22% of the total number of particles.

13. Use of the body-phase hydrocracking catalyst prepared by the method of any one of claims 1-9 in a hydrocracking process for producing base oils of special oils and lubricating oils.

14. Use of the body-phase hydrocracking catalyst prepared by the method of any one of claims 1-9 in a hydrocracking process for producing base oils of No. 5 industrial-grade white oil and high-viscosity-index lubricating oil.