Y / ZSM-22 / P-KIT-1 composite molecular sieve, preparation method thereof, catalyst carrier, catalyst and hydrocracking method

Abstract

The invention relates to the technical field of catalytic cracking, and discloses a Y / ZSM-22 / P-KIT-1 composite molecular sieve, a preparation method thereof, a catalyst carrier, a catalyst and a hydrocracking method. The composite molecular sieve is prepared from the following components in percentage by weight: 20 to 55 weight percent of ZSM-22 molecular sieve, 15 to 30 weight percent of P-KIT-1 molecular sieve and 20 to 65 weight percent of Y molecular sieve, in the catalyst carrier, the content of the amorphous silica-alumina is 20-70%, the content of the micropore alumina is 10-50 wt%, and the content of the composite molecular sieve is 15-80 wt%. When the catalyst containing the composite molecular sieve is used for hydrocracking, the selectivity, the yield and the smoke point of aviation kerosene can be remarkably improved, and tail oil with high viscosity index can be produced at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of catalytic cracking, and in particular to a Y / ZSM-22 / P-KIT-1 composite molecular sieve and a preparation method thereof, a catalyst carrier, a catalyst and a hydrocracking method. Background Art

[0002] Hydrocracking technology is one of the important means of deep processing of intermediate base raw materials. It has many advantages such as strong raw material adaptability, flexible processing scheme, high yield of liquid products, and good product quality. In particular, it has high yield, high smoke point, and low freezing point of high-quality aviation kerosene (3# jet fuel). At the same time, the tail oil with high viscosity index produced is an excellent lubricant base oil raw material. Hydrocracking technology has gradually developed into a key secondary processing technology for modern refining enterprises to directly produce clean oil products and high-quality chemical raw materials from inferior wax oil, and is also the core of refining structure adjustment, transformation and upgrading.

[0003] However, low-quality intermediate raw materials have high density, high dry point, low paraffin content, high cycloalkanes and polycyclic aromatic hydrocarbons content, and are difficult to crack. The core of hydrocracking technology is the hydrocracking catalyst. According to the characteristics of low-quality intermediate raw materials, the acidity and pore structure of the hydrocracking catalyst are optimized, the hydrogenolysis activity and hydrogenation activity are reasonably matched, and the hydrocracking catalyst suitable for producing high-quality jet fuel from low-quality intermediate raw materials is developed to meet the technical needs of refining enterprises.

[0004] Molecular sieve materials are widely used as carrier components of hydrocracking catalysts due to their strong acid centers, large specific surface area, high hydrothermal stability and regular microporous channels. Although traditional molecular sieves have many advantages, their small and single pore structure has a prominent restrictive effect on the diffusion and conversion of macromolecules when faced with the trend of heavy and inferior crude oil.

[0005] CN101618333A provides a method for preparing a Y molecular sieve / silicon dioxide composite material, in which the Y molecular sieve does not participate in the epitaxial growth of silicon dioxide, there is no chemical bond between the Y molecular sieve and silicon dioxide, and silicon dioxide cannot provide acidity, but can only play a selective role in various catalytic reactions, so the acidity of the composite material can only be achieved by adjusting the Y molecular sieve; in addition, the mesopores in the composite material are irregular multi-level pores, and the product selectivity is poor.

[0006] CN109722290A provides a method for reducing the freezing point of high dry point jet fuel, which uses distillate oil with a boiling point of 229-334°C as raw material, passes through a hydrogenation treatment reaction zone, a freezing point reduction reaction zone and a post-hydrogenation refining reaction zone, and then fractionates to obtain jet fuel. The freezing point reduction catalyst contains a molecular sieve, a matrix and a hydrogenation active metal component. This method can only process light diesel fraction raw materials with a narrow fraction range, and the process flow is complicated.

[0007] CN101172243A provides a method for preparing a mesoporous / microporous molecular sieve composite material. In the composite material prepared by the invention, the microporous molecular sieve is wrapped around a porous clay isomerized material. The composite material has both the crystal structure of the microporous molecular sieve and the mesoporous structure of the porous clay isomerized material. It is a dual-porous composite material, but has poor stability and has not been applied to the field of hydrocracking of inferior wax oil raw materials.

[0008] CN113019426A provides a hydrocracking catalyst carrier and a preparation method thereof. The carrier comprises alumina and a Y / Al-SBA-15 composite molecular sieve. When the hydrocracking catalyst containing the carrier is used in a hydrocracking reaction process, the heavy naphtha yield is high, but the medium oil selectivity is poor. Summary of the invention

[0009] The purpose of the present invention is to overcome the problems that when the molecular sieve catalytic carrier in the prior art is used for the hydrocracking of inferior intermediate raw materials, the single and small microporous structure restricts the diffusion and conversion of macromolecules, and the selectivity of aviation kerosene is low during the cracking process, and to provide a Y / ZSM-22 / P-KIT-1 composite molecular sieve and its preparation method, catalyst carrier, catalyst and hydrocracking method. The catalyst containing the composite molecular sieve can significantly improve the selectivity, yield and smoke point of aviation kerosene in the hydrocracking reaction of catalyzing inferior intermediate raw materials, and simultaneously produce tail oil with a high viscosity index.

[0010] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides a Y / ZSM-22 / P-KIT-1 composite molecular sieve, wherein, based on the total weight of the composite molecular sieve, the content of ZSM-22 molecular sieve in the composite molecular sieve is 20-55% by weight, the content of P-KIT-1 molecular sieve is 15-30% by weight, and the content of Y molecular sieve is 20-65% by weight.

[0011] The second aspect of the present invention provides a method for preparing a Y / ZSM-22 / P-KIT-1 composite molecular sieve, wherein the method comprises:

[0012] (1) mixing ZSM-22 molecular sieve, P-KIT-1 molecular sieve, structure directing agent, silicon source and aluminum source to obtain a gel;

[0013] (2) mixing the gel with polyacrylamide and subjecting it to hydrothermal crystallization to obtain the composite molecular sieve precursor I;

[0014] (3) subjecting the composite molecular sieve precursor I to a first drying and a first calcination to obtain the composite molecular sieve precursor II;

[0015] (4) adding the composite molecular sieve precursor II into an ammonium sulfate solution, performing a second drying and a second calcination to obtain the composite molecular sieve.

[0016] The third aspect of the present invention provides a Y / ZSM-22 / P-KIT-1 composite molecular sieve prepared by the preparation method described in the second aspect.

[0017] A fourth aspect of the present invention provides a catalyst carrier, wherein, based on the total weight of the catalyst carrier, the content of amorphous silicon aluminum in the catalyst carrier is 20-70%, the content of small pore alumina is 10-50wt%, and the content of composite molecular sieve is 15-80wt%;

[0018] Wherein, the composite molecular sieve is the Y / ZSM-22 / P-KIT-1 composite molecular sieve described in the first aspect or the third aspect.

[0019] A fifth aspect of the present invention provides a catalyst, wherein, based on the total weight of the catalyst, the content of the catalyst carrier in the catalyst is 70-80% by weight, and the content of the active component is 20-30% by weight;

[0020] Wherein, the catalyst carrier is the catalyst carrier described in the fourth aspect.

[0021] A sixth aspect of the present invention provides a hydrocracking method, the method comprising: subjecting an intermediate base feedstock to a hydrocracking reaction in the presence of a catalyst;

[0022] Wherein, the catalyst is the catalyst described in the fifth aspect of the present invention.

[0023] Through the above technical scheme, the Y / ZSM-22 / P-KIT-1 composite molecular sieve provided by the present invention has a multi-level pore structure, and is prepared by in-situ growth of Y molecular sieve on the one-dimensional pores of ZSM-22 and the three-dimensional pores of P-KIT-1. The inferior intermediate base raw material is shallowly cracked in the amorphous silicon-aluminum macroporous structure to generate hydrocarbons with smaller carbon chains, and then enters the interior of the Y molecular sieve and / or P-KIT-1 molecular sieve with mesoporous pores, and further undergoes a hydrocracking reaction. The generated product containing the aviation kerosene fraction enters the interior of the ZSM-22 microporous molecular sieve for selective isomerization reaction, so that branched hydrocarbons are generated into straight-chain hydrocarbons. These processes can significantly improve the selectivity, yield and smoke point of aviation kerosene. The catalyst containing the Y / ZSM-22 / P-KIT-1 composite molecular sieve of the present invention is used to carry out the hydrocracking reaction of the inferior intermediate base raw material. Compared with the comparative example, from the yield and properties of the cracking product, it can be seen that the catalyst of the present invention can improve the yield of the liquid product in the hydrocracking product of the inferior intermediate base raw material, improve the selectivity, yield and smoke point of the aviation kerosene product, reduce the freezing point of the aviation kerosene, improve the aromatic potential of the obtained heavy naphtha, and simultaneously produce tail oil with a high viscosity index. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0025] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0026] The first aspect of the present invention provides a Y / ZSM-22 / P-KIT-1 composite molecular sieve, wherein, based on the total weight of the composite molecular sieve, the content of ZSM-22 molecular sieve in the composite molecular sieve is 20-55% by weight, the content of P-KIT-1 molecular sieve is 15-30% by weight, and the content of Y molecular sieve is 20-65% by weight.

[0027] The composite molecular sieve of the present invention contains P-modified KIT-1 molecular sieve (P-KIT-1), which can not only improve the acidity of the composite molecular sieve, but also increase the mesopore volume in the composite molecular sieve, promote the diffusion of larger molecules in inferior wax oil in the pores, and better carry out hydrocracking reaction, thereby improving the cracking performance of the catalyst containing the composite molecular sieve.

[0028] According to the present invention, the P-KIT-1 molecular sieve is commercially available, and the content of P in the P-KIT-1 molecular sieve is 2-4 wt % based on the total weight of the P-KIT-1 molecular sieve.

[0029] According to the present invention, preferably, based on the total weight of the composite molecular sieve, in the composite molecular sieve, the content of ZSM-22 molecular sieve is 21.5-50.5% by weight, the content of P-KIT-1 molecular sieve is 18-29% by weight, and the content of Y molecular sieve is 21-60% by weight.

[0030] According to the present invention, in order to improve the acidity and mesoporous content of the catalyst containing the composite molecular sieve, improve the hydrocracking performance of the catalyst, improve the selectivity, yield and smoke point of aviation kerosene, and reduce the freezing point of aviation kerosene, preferably, the specific surface area of ​​the composite molecular sieve is 650-840m 2 / g.

[0031] Preferably, the pore volume of the composite molecular sieve is 0.45-0.68 mL / g.

[0032] Preferably, in the composite molecular sieve, pores with a size of 3-15 nm account for 43-65%, and pores with a size greater than 15 nm account for 8-15%.

[0033] Preferably, the medium-strong acid content of the composite molecular sieve is 0.68-0.85 ml / g.

[0034] In the present invention, the properties of the composite molecular sieve can be obtained through BET and pyridine infrared testing; the composition of the composite molecular sieve can be obtained by calculating the feed amount.

[0035] The present invention has no particular limitation on the preparation method of the composite molecular sieve, as long as the composite molecular sieve having the above composition can be obtained. According to a preferred embodiment of the present invention, the second aspect of the present invention provides a method for preparing a composite molecular sieve, wherein the method comprises the following steps:

[0036] (1) mixing ZSM-22 molecular sieve, P-KIT-1 molecular sieve, structure directing agent, silicon source and aluminum source to obtain a gel;

[0037] (2) mixing the gel with polyacrylamide and subjecting it to hydrothermal crystallization to obtain the composite molecular sieve precursor I;

[0038] (3) subjecting the composite molecular sieve precursor I to a first drying and a first calcination to obtain the composite molecular sieve precursor II;

[0039] (4) adding the composite molecular sieve precursor II into an ammonium sulfate solution, performing a second drying and a second calcination to obtain the composite molecular sieve.

[0040] According to the preparation method of the present invention, the Y / ZSM-22 / P-KIT-1 composite molecular sieve is prepared by in-situ growing a Y molecular sieve on the one-dimensional pores of ZSM-22 and the three-dimensional pores of P-KIT-1. During the formation process, the Y molecular sieve forms a bond with the ZSM-22 molecular sieve and the P-KIT-1 molecular sieve, and is evenly distributed on the surfaces of the ZSM-22 molecular sieve and the P-KIT-1 molecular sieve. Compared with the composite molecular sieve obtained by mechanical mixing, in the composite molecular sieve prepared by the preparation method of the present invention, the three molecular sieves of Y, ZSM-22 and P-KIT-1 can each maintain the original complete pore structure, thereby increasing the proportion of mesopores in the catalyst finally obtained, and the in-situ growth of the Y molecular sieve on the pores of the ZSM-22 molecular sieve and the P-KIT-1 molecular sieve shortens the distance between the molecular sieves with different pore structures, thereby better exerting the synergistic effect between the three different molecular sieves, promoting the hydrocracking performance of the catalyst containing the Y / ZSM-22 / P-KIT-1 composite molecular sieve, improving the selectivity, yield and smoke point of aviation kerosene, and reducing the freezing point of aviation kerosene.

[0041] In the preparation method of the present invention, the raw materials used can be commercially available products or prepared by any existing method.

[0042] According to the preparation method of the present invention, in order to obtain a Y molecular sieve with excellent performance, preferably, the Na 2 O、Al 2 O 3 、SiO 2 , H 2 The molar ratio of O is (5-25):1:(5-20):(200-400).

[0043] The present invention has no particular limitation on the preparation of the structure directing agent, as long as a structure directing agent having the above-mentioned composition can be prepared. According to a preferred embodiment of the present invention, the structure directing agent of the present invention can be prepared in the following specific manner: at room temperature, water glass is dissolved in deionized water, mixed evenly, and then mixed and stirred with the alkali solution of the present invention. After the reaction is complete, the mixture is allowed to stand to obtain the structure directing agent.

[0044] Preferably, the Na in the alkali solution 2 O、Al 2 O 3 , H 2 The molar ratio of O is (10-15):1:(100-200).

[0045] The present invention has no particular limitation on the preparation of the alkali solution, as long as the alkali solution having the above composition can be prepared. According to a preferred embodiment of the present invention, the alkali solution of the present invention can be prepared in the following specific manner: sodium hydroxide, aluminum hydroxide and deionized water are mixed and stirred at room temperature to obtain the alkali solution.

[0046] According to the amount of feed in the preparation method of the present invention, preferably, in the gel, the Na from the structure directing agent, the silicon source and the aluminum source 2 O、Al 2 O 3 、SiO 2 The molar ratio is (2-30):1:(2-100).

[0047] According to the preparation method of the present invention, in order to obtain a Y / ZSM-22 / P-KIT-1 composite molecular sieve with improved mesopore ratio and acidity, in step (1), preferably, in the gel, ZSM-22 molecular sieve, P-KIT-1 molecular sieve, SiO 2 The weight ratio is (0.5-2):(0.5-1):1.

[0048] The present invention has no special requirements for the silicon source, as long as the silicon source is soluble in water. Preferably, the silicon source is selected from at least one of water glass, methyl orthosilicate, ethyl orthosilicate, silica sol, and silicon powder, and water glass is more preferably used.

[0049] The present invention has no special requirements for the aluminum source, as long as the aluminum source is soluble in water. Preferably, the aluminum source is selected from at least one of aluminum oxide, sodium aluminate, aluminum isopropoxide, and aluminum sulfate 18hydrate, and more preferably aluminum sulfate 18hydrate or aluminum oxide.

[0050] The present invention has no particular limitation on the mixing of the ZSM-22 molecular sieve, the P-KIT-1 molecular sieve, the structure directing agent, the silicon source and the aluminum source in step (1). According to a preferred embodiment of the present invention, the mixing in step (1) can be carried out according to the following steps: after the ZSM-22 and P-KIT-1 molecular sieves are mixed and slurried, they are uniformly mixed with the structure directing agent of the present invention, and then the silicon source and the aluminum source are added in parallel.

[0051] According to the preparation method of the present invention, in order to obtain uniform mixing of the components and obtain a gel with high dispersion, preferably, in step (1), an aging step is further included after the mixing, and the aging temperature is 60-90°C and the time is 1-6h.

[0052] According to the preparation method of the present invention, in order to improve the pore performance of the prepared composite molecular sieve, preferably, in step (2), polyacrylamide and SiO in the gel are 2 The weight ratio is 3-7:100.

[0053] According to the preparation method of the present invention, in order to ensure that the polyacrylamide and the gel are mixed evenly and to better play the role of the polyacrylamide as a pore-enlarging agent, preferably, in step (2), the weight average molecular weight of the polyacrylamide is 30,000-100,000 g / mol.

[0054] In the present invention, there is no particular limitation on the form in which the polyacrylamide is added. It can be directly mixed with the gel, or first prepared into a polyacrylamide solution and then mixed with the gel in the form of a solution. According to a preferred embodiment of the present invention, the polyacrylamide is mixed with the gel in the form of a solution.

[0055] Preferably, in step (2), the concentration of the polyacrylamide solution is 0.1-0.5 g / mL.

[0056] The present invention has no particular limitation on the solvent in the polyacrylamide solution, as long as it can dissolve polyacrylamide. According to a preferred embodiment of the present invention, preferably, the solvent in the polyacrylamide solution is deionized water.

[0057] Preferably, the conditions of the hydrothermal crystallization treatment include: temperature of 90-120°C and time of 24-48h.

[0058] According to the preparation method of the present invention, preferably, in step (3), the temperature of the first drying is 100-200° C., more preferably 120-150° C.; the time is 1-6 h, more preferably 2-4 h;

[0059] Preferably, the temperature of the first calcination is 450-600° C., more preferably 500-550° C., and the time is 2-8 h, more preferably 4-6 h.

[0060] According to the preparation method of the present invention, in order to improve the efficiency of the ion exchange reaction, preferably, in step (4), the concentration of the ammonium sulfate solution is 0.5-2 mol / L, more preferably 1 mol / L.

[0061] The present invention has no particular limitation on the solvent in the ammonium sulfate solution, as long as it can dissolve ammonium sulfate. According to a preferred embodiment of the present invention, preferably, the solvent in the ammonium sulfate solution is deionized water.

[0062] Preferably, in step (4), the second drying further includes stirring and washing steps; further preferably, the stirring temperature is 80-90° C. and the stirring time is 1-2 h.

[0063] The present invention has no particular limitation on the washing solvent in step (4), as long as it can wash away the sodium ions in the molecular weight without introducing other ions that may cause pollution. Preferably, the washing solvent in the present invention is deionized water.

[0064] Preferably, the second drying is carried out at a temperature of 100-120° C. and for a time of 2-6 hours.

[0065] Preferably, the second calcination is carried out at a temperature of 500-600° C. and for a time of 2-6 hours.

[0066] The third aspect of the present invention provides a Y / ZSM-22 / P-KIT-1 composite molecular sieve prepared by the preparation method described in the second aspect.

[0067] A fourth aspect of the present invention provides a catalyst carrier, wherein, based on the total weight of the catalyst carrier, the catalyst carrier comprises 20-70 wt% of amorphous silica-alumina, 10-50 wt% of small pore alumina, and 15-80 wt% of a composite molecular sieve;

[0068] Wherein, the composite molecular sieve is the Y / ZSM-22 / P-KIT-1 composite molecular sieve described in the first aspect or the third aspect.

[0069] In the present invention, amorphous silicon aluminum has a purity of 70%, a mesopore (2-50nm) volume of 1.2-1.9mL / g, and a specific surface area of ​​450-600m 2 / g, purchased from Tianjin Kaiwente Technology Co., Ltd.

[0070] Preferably, in amorphous silica-alumina, the pore volumes of pore sizes in various ranges are: the pore volume of pores with a pore diameter of 4-10 nm is 0.45-0.75 mL / g; the pore volume of pores with a pore diameter of 10-20 nm is 0.4-0.7 mL / g; the pore volume of pores with a pore diameter of 20-50 nm is 0.15-0.35 mL / g.

[0071] In the present invention, the small-pore alumina has a purity of 71%, a mesopore (2-50 nm) volume of 0.5-0.95 mL / g, and a specific surface area of ​​200-300 m2 / g, and is purchased from Shandong Henghui.

[0072] Preferably, in small pore alumina, the pore volumes of pores in various ranges of pore size are: the pore volume of pores with a pore size of 4-10 nm is 0.15-0.35 mL / g; the pore volume of pores with a pore size of 10-20 nm is 0.15-0.35 mL / g; the pore volume of pores with a pore size of 20-50 nm is 0.05-0.95 mL / g.

[0073] In the present invention, preferably, the specific surface area of ​​the catalyst carrier is 400-680m2 / g;

[0074] Preferably, the total pore volume of the catalyst carrier is 0.4-0.8 mL / g, wherein the mesopore volume is 0.6-0.75 mL / g and the micropore volume is 0.06-0.1 mL / g.

[0075] Preferably, the average pore size of the catalyst carrier is 5-25 nm.

[0076] And / or, the B / L acid ratio of the catalyst carrier is 2.1-3.5.

[0077] The present invention has no particular limitation on the preparation method of the catalyst carrier, as long as a catalyst carrier having the above composition can be prepared. According to a preferred embodiment of the present invention, the catalyst carrier can be prepared by the following method:

[0078] (a) adding amorphous silicon aluminum, small pore alumina, multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve, and sesbania powder into a large dry pot and stirring to obtain a mixed powder;

[0079] (b) adding citric acid and nitric acid to deionized water to prepare an acidic solution, adding the acidic solution dropwise to the powder obtained in step (a), rolling the powder into blocks, extruding the blocks on a twin-screw extruder, drying the extruded blocks, and calcining the extruded blocks to obtain the catalyst carrier.

[0080] Further preferably, in step (1), the amount of sesbania powder added is 2-6% of the total amount of amorphous silica-alumina, small pore alumina and multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve, calculated as a percentage by weight. According to a preferred embodiment of the present invention, the amount of sesbania powder added is 3% of the total amount of amorphous silica-alumina, small pore alumina and multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve.

[0081] The present invention has no particular limitation on the stirring speed and time of step (a), as long as the raw materials are mixed evenly.

[0082] Further preferably, in step (b), the amount of citric acid added is 2-6% of the total amount of amorphous silica-alumina, small pore alumina and multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve, calculated by weight percentage; the amount of nitric acid added is 2-10% of the total amount of amorphous silica-alumina, small pore alumina and multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve. According to a preferred embodiment of the present invention, the amount of citric acid added is 3% of the total amount of amorphous silica-alumina, small pore alumina and multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve; the amount of nitric acid added is 2% of the total amount of amorphous silica-alumina, small pore alumina and multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve.

[0083] Further preferably, in step (b), the concentration of the acidic solution is 0.05-0.2 g / mL, and further preferably 0.13 g / mL.

[0084] Further preferably, in step (b), the weight ratio of citric acid to nitric acid is 2-6:2-10, and further preferably is 3:5.

[0085] Further preferably, in step (b), the drying temperature is 100-150° C., more preferably 120° C., and the drying time is 2-6 h, more preferably 4 h.

[0086] Further preferably, in step (b), the calcination temperature is 450-600° C., more preferably 550° C., and the calcination time is 2-6 h, more preferably 4 h.

[0087] A fifth aspect of the present invention provides a catalyst, wherein, based on the total weight of the catalyst, the catalyst comprises 70-80 wt% of a catalyst carrier and 20-30 wt% of an active component;

[0088] Wherein, the catalyst carrier is the catalyst carrier described in the fourth aspect.

[0089] The present invention has no particular limitation on the active components in the catalyst, as long as they have catalytic activity for the hydrocracking reaction. According to some preferred embodiments of the present invention, the active components are tungsten oxide and nickel oxide.

[0090] In the present invention, preferably, the specific surface area of ​​the catalyst is 280-320m 2 / g.

[0091] Preferably, the pore volume of the catalyst is 0.4-0.5 mL / g.

[0092] Preferably, the average pore size of the catalyst is 3-15 nm.

[0093] Preferably, the B / L acid ratio of the catalyst is 1.4-3.

[0094] The present invention has no particular limitation on the method for preparing the catalyst, as long as a catalyst having the above composition can be prepared. According to a preferred embodiment of the present invention, the catalyst can be prepared by the following method:

[0095] (s1) adding ammonium metatungstate, nickel nitrate and ethylenediaminetetraacetic acid into a beaker filled with deionized water to dissolve them to obtain an impregnation solution;

[0096] (s2) using a saturated impregnation method to impregnate the Y / ZSM-22 / P-KIT-1 composite molecular sieve carrier of the present invention with the impregnation solution obtained in step (s1), drying, and calcining in an air atmosphere to obtain the catalyst.

[0097] The present invention does not particularly limit the concentration of the impregnation solution in step (s1), as long as the contents of the carrier and the active component in the catalyst obtained after impregnation, drying and calcination are within the range defined by the present invention. According to a preferred embodiment of the present invention, in the impregnation solution, the concentrations of the catalyst active component precursors ammonium metatungstate and nickel nitrate are 1.216 g / mL; the concentration of ethylenediaminetetraacetic acid is 0.052 g / mL.

[0098] The present invention has no particular limitation on the temperature and time of the impregnation in step (s2), as long as the impregnation liquid fully impregnates the catalyst carrier. In some embodiments of the present invention, the impregnation temperature is room temperature and the time is 2 hours.

[0099] Preferably, in step (s2), the drying temperature is 100-150°C and the drying time is 2-6 hours. More preferably, the drying temperature is 120°C and the drying time is 4 hours.

[0100] Preferably, in step (s2), the calcination temperature is 450-600°C and the time is 2-6 hours. More preferably, the drying temperature is 550°C and the time is 4 hours.

[0101] A sixth aspect of the present invention provides a hydrocracking method, the method comprising: subjecting an intermediate base feedstock to a hydrocracking reaction in the presence of a catalyst;

[0102] Wherein, the catalyst is the catalyst described in the fifth aspect.

[0103] Preferably, the intermediate base raw material is a low-quality intermediate base raw material, and at 20°C, the density of the intermediate base raw material is ≮0.9 g / cm 3 , dry point ≯570℃.

[0104] Preferably, the conditions of the hydrocracking reaction include: reaction temperature of 365-385°C, pressure of 10-15 MPa, hydrogen-oil volume ratio of 750-1000:1, volume space velocity of 0.8-1.2 h -1 According to a preferred embodiment of the present invention, further preferably, the temperature of the hydrocracking reaction is 378°C, the pressure is 12.5MPa, the hydrogen-oil volume ratio is 900:1, and the volume space velocity is 1.1h -1 , time is 48h.

[0105] The present invention will be described in detail below through examples.

[0106] ZSM-22 molecular sieve, purity 90%, specific surface area 160-180m 2 / g, pore volume 0.2-0.3mL / g, pore diameter 0.5-0.6nm, purchased from Shandong Qilu Huaxin Hi-Tech Co., Ltd.

[0107] P-KIT-1 molecular sieve, purity 90%, specific surface area 822m 2 / g, pore volume 1.21mL / g, pore diameter 3-50nm, purchased from Zhuoran Environmental Protection Technology Co., Ltd.

[0108] Al-KIT-1 molecular sieve, purity 90%, specific surface area 833m 2 / g, pore volume 1.20mL / g, pore diameter 3-50nm, purchased from Zhuoran Environmental Protection Technology Co., Ltd.

[0109] Small pore alumina, purity 71%, mesopore (2-50nm) volume 0.5-0.95mL / g, specific surface area 200-300m 2 / g, purchased from Shandong Henghui.

[0110] Amorphous silicon aluminum, purity 70%, mesopore (2-50nm) volume 1.2-1.9mL / g, specific surface area 450-600m 2 / g, purchased from Tianjin Kaiwente Technology Co., Ltd.

[0111] Water glass, SiO 2 The content is 25% by weight and was purchased from Xi'an Borun New Materials Environmental Engineering Co., Ltd.

[0112] The properties of the composite molecular sieve, catalyst support and catalyst were obtained through BET and pyridine infrared tests.

[0113] The composition of the composite molecular sieve, catalyst carrier and catalyst is calculated based on the feed amount.

[0114] Example 1

[0115] (1) 800 g of sodium hydroxide, 156 g of aluminum hydroxide, and 1800 g of deionized water were mixed and stirred for 40 min to obtain an alkali solution;

[0116] 1800 g of water glass was dissolved in 2400 g of deionized water, and after being evenly mixed, it was mixed with the prepared alkali solution, stirred for 60 min, and allowed to stand for 40 h after the reaction to obtain a structure directing agent;

[0117] 504 g of ZSM-22 molecular sieve and 420 g of P-KIT-1 molecular sieve were mixed and slurried, and then mixed evenly with the prepared structure directing agent, and then 1200 g of water glass and 1322 g of aluminum sulfate 18hydrate were added in parallel, and aged at 60° C. for 2 h to obtain a gel;

[0118] (2) adding 200 ml of a 0.3 g / mL polyacrylamide solution to the gel obtained in step (1), and performing hydrothermal crystallization at 98° C. for 24 h to obtain a composite molecular sieve precursor I;

[0119] (3) subjecting the composite molecular sieve precursor I obtained in step (2) to a first drying at 120° C. for 2 h, and to a first calcination at 500° C. for 4 h, to obtain a composite molecular sieve precursor II;

[0120] (4) The composite molecular sieve precursor II obtained in step (3) was added to 1200 ml of 1 mol / L ammonium sulfate solution, stirred in an 85°C water bath for 2 h, washed with deionized water, dried at 120°C for 2 h, and calcined at 500°C for 4 h to obtain a multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 1.

[0121] The composite molecular sieve 1 was subjected to BET and pyridine infrared tests. The test results show that the specific surface area of ​​the composite molecular sieve 1 is 824 m 2 / g, the pore volume is 0.66mL / g, the pore size of 3-15nm accounts for 61.3%, the pore size greater than 15nm accounts for 13.5%, and the medium-strong acid content of the composite molecular sieve is 0.78mL / g.

[0122] Example 2

[0123] (1) 960 g of sodium hydroxide, 156 g of aluminum hydroxide, and 2700 g of deionized water were mixed and stirred for 40 min to obtain an alkali solution;

[0124] 1600 g of water glass was dissolved in 1800 g of deionized water, and after being evenly mixed, it was mixed with the prepared alkali solution A, stirred for 60 min, and allowed to stand for 40 h after the reaction to obtain a structure directing agent;

[0125] 1000 g of ZSM-22 molecular sieve and 792 g of P-KIT-1 molecular sieve were mixed and slurried, and then mixed evenly with the prepared structure directing agent B, and then 1800 g of silica sol and 666 g of aluminum sulfate 18hydrate were added in parallel, and aged at 70° C. for 2 h to obtain a gel;

[0126] (2) adding 300 ml of a 0.3 g / mL polyacrylamide solution to the gel obtained in step (1), and performing hydrothermal crystallization at 98° C. for 36 h to obtain a composite molecular sieve precursor I;

[0127] (3) subjecting the composite molecular sieve precursor I obtained in step (2) to a first drying at 120° C. for 2 h, and to a first calcination at 500° C. for 4 h, to obtain a composite molecular sieve precursor II;

[0128] (4) The composite molecular sieve precursor II obtained in step (3) was added to 1800 ml of 1 mol / L ammonium sulfate solution, stirred in an 85°C water bath for 2 h, washed with deionized water, dried at 120°C for 2 h, and calcined at 500°C for 4 h to obtain a multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 2.

[0129] The composite molecular sieve 2 was subjected to BET and pyridine infrared tests. The test results show that the specific surface area of ​​the composite molecular sieve 2 is 819 m 2 / g, the pore volume is 0.65mL / g, the pore size of 3-15nm accounts for 63.4%, the pore size greater than 15nm accounts for 12.7%, and the medium-strong acid content of the composite molecular sieve is 0.81ml / g.

[0130] Example 3

[0131] (1) 1200 g of sodium hydroxide, 156 g of aluminum hydroxide, and 2160 g of deionized water were mixed and stirred for 40 min to obtain an alkali solution;

[0132] 2142 g of water glass was dissolved in 2700 g of deionized water, and after being evenly mixed, it was mixed with the prepared alkali solution A, stirred for 60 min, and allowed to stand for 40 h after the reaction to obtain a structure directing agent;

[0133] 2700 g of ZSM-22 molecular sieve and 1500 g of P-KIT-1 molecular sieve were mixed and slurried, and then mixed evenly with the prepared structure directing agent, and then 3000 g of silica sol and 78 g of alumina were added in parallel, and aged at 90° C. for 2 h to obtain a gel;

[0134] (2) adding 600 ml of a 0.3 g / mL polyacrylamide solution to the gel obtained in step (1), and performing hydrothermal crystallization at 98° C. for 48 h to obtain a composite molecular sieve precursor I;

[0135] (3) subjecting the composite molecular sieve precursor I obtained in step (2) to a first drying at 120° C. for 2 h, and to a first calcination at 500° C. for 4 h, to obtain a composite molecular sieve precursor II;

[0136] (4) The composite molecular sieve precursor II obtained in step (3) was added to 2400 ml of 1 mol / L ammonium sulfate solution, stirred in an 85°C water bath for 2 h, washed with deionized water, dried at 120°C for 2 h, and calcined at 500°C for 4 h to obtain a multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 3.

[0137] The composite molecular sieve 3 was subjected to BET and pyridine infrared tests. The test results show that the specific surface area of ​​the composite molecular sieve 3 is 833 m 2 / g, the pore volume is 0.67mL / g, the pore size of 3-15nm accounts for 63.7%, the pore size greater than 15nm accounts for 14.3%, and the medium-strong acid content of the composite molecular sieve is 0.8ml / g.

[0138] Example 4

[0139] (1) At 25° C., 44 g of amorphous silica-alumina, 20 g of small-pore alumina, 33 g of multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 1, and 3 g of sesbania powder were added to a large crucible and stirred at 1200 rpm for 40 min to obtain a mixed powder;

[0140] 3 g of citric acid and 5 g of nitric acid were added to 60 ml of deionized water to prepare an acidic solution, which was then added dropwise to the obtained mixed powder, crushed into blocks, and extruded on a twin-screw extruder. The extruded strips were dried at 120° C. for 4 hours, and calcined at 550° C. for 4 hours to obtain a catalyst carrier A.

[0141] (2) 77.8 g of ammonium metatungstate, 57.6 g of nickel nitrate, and 5.2 g of ethylenediaminetetraacetic acid were added to a beaker filled with deionized water to dissolve and prepare 100 ml of impregnation solution; 25 ml of the impregnation solution was weighed and used to impregnate 50 g of the carrier by saturation impregnation for 2 h, dried at 120° C. for 4 h, and calcined at 550° C. in an air atmosphere for 4 h to obtain Catalyst A.

[0142] The catalyst carrier A was subjected to BET and pyridine infrared tests. The test results show that the specific surface area of ​​the catalyst carrier A is 668m 2 / g, the total pore volume is 0.76mL / g, the mesopore volume is 0.68mL / g, the micropore volume is 0.06mL / g, the average pore diameter is 16.8nm, and the B / L acid ratio is 2.6.

[0143] The performance parameters of catalyst A were characterized and the results are shown in Table 1.

[0144] Example 5

[0145] (1) At 25° C., 34 g of amorphous silica-alumina, 18 g of small-pore alumina, 45 g of multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve, and 2 and 3 g of sesbania powder were added to a large dry pot and stirred at 1200 rpm for 40 min to obtain a mixed powder;

[0146] 3 g of citric acid and 5 g of nitric acid were added to 60 ml of deionized water to prepare an acidic solution, which was then added dropwise to the obtained mixed powder, crushed into blocks, and extruded on a twin-screw extruder. The extruded strips were dried at 120° C. for 4 hours, and calcined at 550° C. for 4 hours to obtain a catalyst carrier B.

[0147] (2) 77.8 g of ammonium metatungstate, 57.6 g of nickel nitrate, and 5.2 g of ethylenediaminetetraacetic acid were added to a beaker filled with deionized water to dissolve and prepare 100 ml of impregnation solution; 25 ml of the impregnation solution was weighed and used to impregnate 50 g of the carrier by saturation impregnation for 2 h, dried at 120° C. for 4 h, and calcined at 550° C. in an air atmosphere for 4 h to obtain Catalyst B.

[0148] The catalyst carrier B was subjected to BET and pyridine infrared tests. The test results show that the specific surface area of ​​the catalyst carrier B is 647 m 2 / g, the total pore volume is 0.77mL / g, the mesopore volume is 0.7mL / g, the micropore volume is 0.05mL / g, the average pore diameter is 15.6nm, and the B / L acid ratio is 2.8.

[0149] The performance parameters of Catalyst B were characterized and the results are shown in Table 1.

[0150] Example 6

[0151] (1) At 25° C., 32 g of amorphous silica-alumina, 15 g of small-pore alumina, 50 g of multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 3, and 3 g of sesbania powder were added to a large dry pot and stirred at 1200 rpm for 40 min to obtain a mixed powder;

[0152] 3 g of citric acid and 5 g of nitric acid were added to 60 ml of deionized water to prepare an acidic solution, which was then added dropwise to the obtained mixed powder, crushed into blocks, and extruded on a twin-screw extruder. The extruded strips were dried at 120° C. for 4 hours, and calcined at 550° C. for 4 hours to obtain a catalyst carrier C.

[0153] (2) 77.8 g of ammonium metatungstate, 57.6 g of nickel nitrate, and 5.2 g of ethylenediaminetetraacetic acid were added to a beaker filled with deionized water to dissolve and prepare 100 ml of impregnation solution; 25 ml of the impregnation solution was weighed and used to impregnate 50 g of the carrier by saturation impregnation for 2 h, dried at 120° C. for 4 h, and calcined at 550° C. in an air atmosphere for 4 h to obtain Catalyst C.

[0154] The catalyst carrier C was tested by BET and pyridine infrared. The test results show that the specific surface area of ​​the catalyst carrier C is 636m 2 / g, the total pore volume is 0.74mL / g, the mesopore volume is 0.67mL / g, the micropore volume is 0.06mL / g, the average pore diameter is 15.3nm, and the B / L acid ratio is 3.1.

[0155] The performance parameters of Catalyst C were characterized and the results are shown in Table 1.

[0156] Comparative Example 1

[0157] Catalyst D was obtained by following the method of Example 6, except that the multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 2 in step (1) was replaced by Y molecular sieve.

[0158] The performance parameters of Catalyst D were characterized and the results are shown in Table 1.

[0159] Comparative Example 2

[0160] Catalyst E was obtained by following the method of Example 6, except that 600 g of P-KIT-1 molecular sieve in step (1) was replaced by 595 g of Al-KIT-1 molecular sieve.

[0161] The performance parameters of Catalyst E were characterized and the results are shown in Table 1.

[0162] Comparative Example 3

[0163] Catalyst F was obtained by following the method of Example 4, except that 33 g of the multi-level pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 1 in step (1) was replaced with 18 g of Y molecular sieve, 8 g of ZSM-22 molecular sieve and 7 g of P-KIT-1 molecular sieve.

[0164] The performance parameters of Catalyst F were characterized and the results are shown in Table 1.

[0165] The catalysts prepared in Examples 4, 5, 6 and Comparative Examples 1, 2, 3 were tested using standards GB / T 5816, GB / T 21650.2, HG / T3448-2003, and GB / T4324.16. The test results are shown in Table 1:

[0166] Table 1

[0167]

[0168]

[0169] As can be seen from Table 1, compared with the comparative example, the catalyst prepared in the embodiment has a larger specific surface area, pore volume and average pore size, which can provide a larger reaction site and space for the raw materials, which is beneficial to the diffusion and conversion of macromolecules, thereby improving the hydrogenation activity of the catalyst; compared with the comparative example, the catalyst prepared in the embodiment has a higher B / L acid ratio, which provides more cracking active centers for the catalytic cracking of the raw materials; in addition, the catalyst prepared in the embodiment has a multi-level pore structure, and the inferior intermediate base raw materials are shallowly cracked in the amorphous silicon-aluminum macroporous structure to generate smaller carbon chain hydrocarbons, which first enter the interior of the Y molecular sieve and / or P-KIT-1 molecular sieve with mesoporous channels, and further undergo hydrocracking reaction, and the generated product containing the aviation kerosene fraction enters the interior of the ZSM-22 microporous molecular sieve for selective isomerization reaction, so that the branched hydrocarbons are generated into straight-chain hydrocarbons. These processes can significantly improve the selectivity, yield and smoke point of aviation kerosene.

[0170] Test Case

[0171] The catalysts prepared in Examples 4, 5, 6 and Comparative Examples 1, 2, 3 were used to carry out hydrocracking of inferior intermediate base raw materials, and the results were evaluated.

[0172] The specific method is: using inferior intermediate base raw materials, crushing 100 mL of catalysts prepared in Examples 4, 5, 6 and Comparative Examples 1, 2, 3 into particles with a length of 2-3 mm, loading them on a 200 mL fixed bed hydrogenation device, and sulfurizing them with kerosene containing 2% carbon disulfide, wherein the main properties of the inferior intermediate base raw materials are listed in Table 2:

[0173] Table 2

[0174] project Inferior intermediate raw materials Analytical methods <![CDATA[Density (20 °C, g / cm 3 )]]> 0.9065 GB / T 1884 Distillation range(℃) ASTM D1160 IBP / 10% 318 / 374 50％ / 90％ 428 / 495 EBP 565 Sulfur content (μg / g) 6240 ASTM D5453 Nitrogen content (μg / g) 1130 ASTM D2629 Carbon residue (wt%) 0.14 GBT17144 Group composition (wt%) ASTM D2425 Alkanes 21.5 Cycloalkanes 39.1 Aromatics 39.4

[0175] The conditions for hydrocracking are: pressure of 12.5 MPa, cracking reaction temperature of 378°C, hydrogen-oil volume ratio of 900:1, and volume space velocity of 1.1 h -1 , time is 48h.

[0176] The obtained hydrocracking product was cut into actual boiling point fractions to obtain component yields and analysis results as shown in Table 3:

[0177] Table 3

[0178]

[0179]

[0180] It can be seen from Table 3 that under the same process conditions, compared with the catalysts D, E and F prepared in comparative examples 1, 2 and 3, when the catalysts A, B and C prepared in embodiments 4, 5 and 6 of the present invention are used to treat the inferior intermediate base raw materials, the liquid yield is high, the aviation kerosene selectivity is good, the yield is high, the smoke point is high, the freezing point is low, the tail oil viscosity index is high, and the heavy naphtha aromatic potential is high, that is, the catalyst provided by the present invention has excellent hydrocracking performance and good aviation kerosene product selectivity, the smoke point of the aviation kerosene product is 4.7-8.1 mm higher than that of the comparison agent E, and the freezing point is 7-11°C lower than that of the comparison agent E. The properties of the target products of aviation kerosene, chemical raw materials and lubricant base oil are good, which can help the transformation and upgrading of oil refining to chemical industry.

[0181] It can be seen from the above embodiments and comparative examples that the catalyst prepared by the present invention has a large specific surface area, pore volume and pore size. When applied to the hydrocatalytic cracking of inferior intermediate raw materials, the amorphous silicon-alumina macroporous structure and the mesoporous channel structure of Y / P-KIT-1 are beneficial to the diffusion and conversion of macromolecules and have a high catalytic activity. In addition, the ZSM-22 molecular sieve with a one-dimensional channel structure contained in the catalytic carrier increases the isomerization effect of the catalyst, can significantly reduce the freezing point of jet fuel, and increase the smoke point of jet fuel, which is beneficial to improving the selectivity of jet fuel when catalyzing the hydrocracking of inferior intermediate raw materials.

[0182] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A Y / ZSM-22 / P-KIT-1 composite molecular sieve, characterized in that: The composite molecular sieve comprises Y molecular sieve, ZSM-22 molecular sieve and P-KIT-1 molecular sieve; wherein, based on the total weight of the composite molecular sieve, in the composite molecular sieve, the content of ZSM-22 molecular sieve is 20-55% by weight, the content of P-KIT-1 molecular sieve is 15-30% by weight, and the content of Y molecular sieve is 20-65% by weight.

2. The composite molecular sieve according to claim 1, wherein Based on the total weight of the composite molecular sieve, in the composite molecular sieve, the content of ZSM-22 molecular sieve is 21.5-50.5% by weight, the content of P-KIT-1 molecular sieve is 18-29% by weight, and the content of Y molecular sieve is 21-60% by weight.

3. The composite molecular sieve according to claim 1 or 2, wherein: The specific surface area of ​​the composite molecular sieve is 650-840m 2 / g; Preferably, the pore volume of the composite molecular sieve is 0.45-0.68 mL / g; Preferably, in the composite molecular sieve, the pore size of 3-15 nm accounts for 43-65%, and the pore size greater than 15 nm accounts for 8-15%; Preferably, the medium-strong acid content of the composite molecular sieve is 0.68-0.85 mL / g.

4. A method for preparing a Y / ZSM-22 / P-KIT-1 composite molecular sieve, characterized in that: The method comprises: (1) mixing ZSM-22 molecular sieve, P-KIT-1 molecular sieve, structure directing agent, silicon source and aluminum source to obtain a gel; (2) mixing the gel with polyacrylamide and subjecting it to hydrothermal crystallization to obtain the composite molecular sieve precursor I; (3) subjecting the composite molecular sieve precursor I to a first drying and a first calcination to obtain the composite molecular sieve precursor II; (4) adding the composite molecular sieve precursor II into an ammonium sulfate solution, performing a second drying and a second calcination to obtain the composite molecular sieve.

5. The preparation method according to claim 4, wherein In step (1), the molar ratio of Na2O, Al2O3, SiO2 and H2O contained in the structure directing agent is (5-25):1:(5-20):(200-400); Preferably, in the gel, the molar ratio of Na2O, Al2O3, and SiO2 from the structure directing agent, silicon source, and aluminum source is (2-30):1:(2-100); Preferably, in the gel, the weight ratio of ZSM-22 molecular sieve, P-KIT-1 molecular sieve, and SiO2 is (0.5-2): (0.5-1): 1; Preferably, the silicon source is selected from at least one of water glass, methyl orthosilicate, ethyl orthosilicate, silica sol, and silicon powder; Preferably, the aluminum source is selected from at least one of aluminum oxide, sodium metaaluminate, aluminum isopropoxide, and aluminum sulfate 18-hydrate.

6. The preparation method according to claim 4 or 5, wherein: In step (1), an aging step is further included after the mixing, and the aging temperature is 60-90° C. and the time is 1-6 hours.

7. The preparation method according to claim 4, wherein In step (2), the weight ratio of polyacrylamide to SiO2 in the gel is 3-7:100; Preferably, the weight average molecular weight of the polyacrylamide is 30,000-100,000 g / mol; Preferably, the conditions of the hydrothermal crystallization treatment include: temperature of 90-120° C. and time of 24-48 h.

8. The preparation method according to claim 4, wherein In step (3), the first drying temperature is 100-200°C, preferably 120-150°C; the time is 1-6h, preferably 2-4h; Preferably, the temperature of the first calcination is 450-600°C, preferably 500-550°C; the time is 2-8h, preferably 4-6h.

9. The preparation method according to claim 4, wherein: In step (4), the concentration of the ammonium sulfate solution is 0.5-2 mol / L; Preferably, the second drying step further includes stirring and washing steps; Preferably, the stirring temperature is 80-90°C and the time is 1-2h; Preferably, the second drying temperature is 100-120°C and the time is 2-6h; Preferably, the second calcination is carried out at a temperature of 500-600° C. and for a time of 2-6 hours.

10. A Y / ZSM-22 / P-KIT-1 composite molecular sieve prepared by the preparation method according to any one of claims 4 to 9.

11. A catalyst carrier, characterized in that: Based on the total weight of the catalyst carrier, the catalyst carrier comprises 20-70 wt% of amorphous silicon aluminum, 10-50 wt% of small pore alumina, and 15-80 wt% of composite molecular sieve; Wherein, the composite molecular sieve is the Y / ZSM-22 / P-KIT-1 composite molecular sieve as described in any one of claims 1-3 and 10.

12. The catalyst carrier according to claim 11, wherein The specific surface area of ​​the catalyst carrier is 400-680m 2 / g; Preferably, the total pore volume of the catalyst carrier is 0.4-0.8 mL / g, wherein the mesopore volume is 0.6-0.75 mL / g and the micropore volume is 0.06-0.1 mL / g; Preferably, the average pore size of the catalyst carrier is 5-25 nm; And / or, the B / L acid ratio of the catalyst carrier is 2.1-3.

5.

13. A hydrocracking catalyst characterized in that: Based on the total weight of the catalyst, the catalyst comprises 70-80wt% of a catalyst carrier and 20-30wt% of an active component; Wherein, the catalyst carrier is the catalyst carrier according to claim 9 or 10.

14. The catalyst according to claim 13, wherein The specific surface area of ​​the catalyst is 280-320m 2 / g; Preferably, the pore volume of the catalyst is 0.4-0.5 mL / g; Preferably, the average pore size of the catalyst is 3-15 nm; Preferably, the B / L acid ratio of the catalyst is 1.4-3.

15. A hydrocracking method, characterized in that: The method comprises: subjecting the intermediate base raw material to a hydrocracking reaction in the presence of a catalyst; Wherein, the catalyst is the catalyst according to claim 13 or 14.

16. The method according to claim 15, wherein: The density of the intermediate base material at 20°C is ≮0.9 g / cm 3 , dry point ≯570℃.

17. The method according to claim 15 or 16, wherein: The conditions of the hydrocracking reaction include: a reaction temperature of 365-385°C, a pressure of 10-15 MPa, a hydrogen-to-oil volume ratio of 750-1000:1, and a volume space velocity of 0.8-1.2 h -1 .

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