Y / zsm-22 / p-kit-1 composite molecular sieve, preparation method thereof, catalyst carrier, catalyst and hydrocracking method

Abstract

The present application relates to catalytic cracking technical field, disclose a kind of Y / ZSM-22 / P-KIT-1 Composite Molecular Sieve and its preparation method, catalyst carrier, catalyst and hydrocracking method.The content of ZSM-22 molecular sieve in the composite molecular sieve is 20-55wt%, the content of P-KIT-1 molecular sieve is 15-30wt%, the content of Y molecular sieve is 20-65wt% according to weight percentage calculation;The content of amorphous silicon aluminum in the catalyst carrier is 20-70wt%, the content of small pore alumina is 10-50wt%, and the content of the composite molecular sieve is 15-80wt%.When the catalyst containing the composite molecular sieve is used for hydrocracking, the selectivity, yield and smoke point of aviation fuel can be significantly improved, and high viscosity index tail oil is also produced.

Description

TECHNICAL FIELD

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

[0002] Hydrocracking technology is one of the important means for deep processing of intermediate base stocks, which has many advantages such as strong adaptability to raw materials, flexible processing scheme, high yield of liquid products, good product quality, etc. In particular, it has high yield of high-quality aviation kerosene (3# jet fuel) with high smoke point and low freezing point, and it also produces tail oil with high viscosity index, which is an excellent lubricating oil base stock. 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 poor waxy oil, and is also the core of refining structural adjustment and transformation and upgrading.

[0003] However, poor intermediate base stocks have large density, high dry point, low paraffin, and high content of naphthenes and polycyclic aromatics, which makes cracking difficult. The core of hydrocracking technology is the hydrocracking catalyst. According to the characteristics of poor intermediate base stocks, the acid and pore structure of the hydrocracking catalyst are optimized, and the hydrogenolysis activity and hydrogenation activity are reasonably matched to develop a hydrocracking catalyst suitable for producing high-quality aviation kerosene from poor intermediate base stocks, so as 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 sites, 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 significant impact on the diffusion and conversion of large molecules when facing the trend of heavy and poor feedstock oil.

[0005] CN101618333A provides a preparation method of Y molecular sieve / silica composite material. In this method, the Y-type molecular sieve does not participate in the crystal growth of silica, there is no chemical bond between the Y-type molecular sieve and silica, and silica cannot provide acidity. Therefore, the composite material can only play a shape-selective role in various catalytic reactions, and 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 aviation kerosene. The method uses a distillate oil with a boiling point of 229-334℃ as a raw material, and through a hydroprocessing reaction zone, a freezing point reduction reaction zone and a post-hydrogenation refining reaction zone, jet fuel is obtained after fractionation. The freezing point reduction catalyst contains a molecular sieve, a substrate and a hydrogenation active metal component. This method can only process light diesel distillate raw materials with a narrow distillation range, and the process flow is complex.

[0007] CN101172243A provides a preparation method of mesoporous / microporous molecular sieve composite material, the composite material prepared by the invention has microporous molecular sieve wrapped around the porous clay isomer material, the composite material has both the crystal structure of the microporous molecular sieve and the mesoporous structure of the porous clay isomer material, belongs to a dual-pore composite material, but the stability is poor, and it cannot be applied to the hydrocracking field of poor wax oil raw material.

[0008] CN113019426A provides a hydrocracking catalyst carrier and a preparation method thereof, the carrier includes alumina and 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 middle oil selectivity is poor. SUMMARY

[0009] The purpose of the present application is to overcome the problems of the prior art, such as the single and small microporous structure of the molecular sieve catalyst carrier, which restricts the diffusion and conversion of large molecules, and the low selectivity of jet fuel in the cracking process when the catalyst carrier is applied to the hydrocracking of poor intermediate base raw material, and to provide a Y / ZSM-22 / P-KIT-1 composite molecular sieve and a preparation method thereof, a catalyst carrier, a catalyst, and a hydrocracking method. The catalyst containing the composite molecular sieve can significantly improve the selectivity, yield, and smoke point of jet fuel, and simultaneously produce tail oil with high viscosity index in the catalytic hydrocracking reaction of poor intermediate base raw material.

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

[0011] The second aspect of the present application provides a preparation method of 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 hydrothermally crystallizing to obtain the composite molecular sieve precursor I;

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

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

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

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

[0018] The catalyst carrier is the catalyst carrier of the fourth aspect.

[0019] The fifth aspect of the present application provides a catalyst, wherein the content of the catalyst carrier in the catalyst is 70-80 wt% and the content of the active component is 20-30 wt% based on the total weight of the catalyst.

[0020] The catalyst carrier is the catalyst carrier of the fourth aspect.

[0021] The sixth aspect of the present application provides a method for hydrocracking, which comprises: performing hydrocracking reaction on an intermediate base raw material in the presence of a catalyst.

[0022] The catalyst is the catalyst of the fifth aspect of the present application.

[0023] By the technical scheme, the Y / ZSM-22 / P-KIT-1 composite molecular sieve provided by the application has a multi-level pore structure, is prepared by in-situ growth of Y molecular sieve on one-dimensional pore channels of ZSM-22 and three-dimensional pore channels of P-KIT-1. The inferior intermediate base raw material is cracked in the amorphous silicon-aluminum macropore structure to generate hydrocarbons with smaller carbon chains, and then enters the interior of the Y molecular sieve and / or the P-KIT-1 molecular sieve with mesopore channels to further generate a hydrocracking reaction, the generated product containing the aviation kerosene fraction enters the interior of the ZSM-22 microporous molecular sieve to generate a shape-selective isomerization reaction, so that the branched hydrocarbons are generated into straight-chain hydrocarbons, and these processes can significantly improve the selectivity, yield and smoke point of the aviation kerosene. The catalyst containing the Y / ZSM-22 / P-KIT-1 composite molecular sieve is used for 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 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 aromaticity of the heavy naphtha obtained, and simultaneously produce tail oil with a high viscosity index. DETAILED DESCRIPTION

[0024] The endpoints of the ranges and any values claimed herein are not to be understood as being limited to the exact values recited as implicitly disclosed by the above description. Ranges can be expressed as from one value and / or to another value. When such ranges are expressed, other intermediates can be present and are implicitly disclosed. For example, when the stated range is from about 1 to about 10, it is intended that legal equivalents (e.g., from about 1.2 to about 9.8, from 1 to 9.9, from 1.1 to 10, from 1.5 to 9, and etc.) along with the explicit disclosed values and claims are fully to be encompassed. It is specifically intended that the end points of the ranges and any intervening values be included.

[0025] The specific embodiments of the present application will be described in detail below. It should be understood that the specific embodiments described herein are merely illustrative and explanatory and are not to be construed as limiting the application.

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

[0027] The P-modified KIT-1 molecular sieve (P-KIT-1) contained in the composite molecular sieve of the present application can not only improve the acidity of the composite molecular sieve, but also improve the mesopore volume of the composite molecular sieve, can promote the diffusion of larger molecules in the pore channels in the inferior waxy oil, and better perform the hydrocracking reaction, thereby improving the cracking performance of the catalyst containing the composite molecular sieve.

[0028] According to the application, 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 application, preferably, the content of the ZSM-22 molecular sieve in the composite molecular sieve is 21.5-50.5 wt%, the content of the P-KIT-1 molecular sieve is 18-29 wt%, and the content of the Y molecular sieve is 21-60 wt% based on the total weight of the composite molecular sieve.

[0030] According to the application, in order to improve the acidity and mesopore content of the composite molecular sieve, improve the hydrocracking performance of the catalyst containing the composite molecular sieve, improve the selectivity, yield and smoke point of the aviation kerosene, and reduce the freezing point of the aviation kerosene, preferably, the specific surface area of the composite molecular sieve is 650-840 m 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, the proportion of the pore size of 3-15 nm is 43-65%, and the proportion of the pore size greater than 15 nm is 8-15%.

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

[0034] In the application, the properties of the composite molecular sieve can be obtained by BET and pyridine infrared testing, and the composition of the composite molecular sieve can be calculated by the amount of the raw materials.

[0035] The preparation method of the composite molecular sieve is not particularly limited in the application, as long as the composite molecular sieve with the above composition can be prepared, according to a preferred embodiment of the application, the second aspect of the application 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 hydrothermal crystallization to obtain the composite molecular sieve precursor I;

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

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

[0040] According to the preparation method of the application, the Y / ZSM-22 / P-KIT-1 composite molecular sieve is prepared by in-situ growth of Y molecular sieve on the one-dimensional channel of ZSM-22 and the three-dimensional channel of P-KIT-1, and the Y molecular sieve forms a bond with the ZSM-22 molecular sieve and the P-KIT-1 molecular sieve during the formation process and is uniformly distributed on the surface of the ZSM-22 molecular sieve and the P-KIT-1 molecular sieve. Compared with the composite molecular sieve obtained by mechanical mixing, the three kinds of molecular sieves Y, ZSM-22 and P-KIT-1 can maintain the original complete channel structure in the composite molecular sieve prepared by the preparation method of the application, the proportion of mesopores in the finally prepared catalyst is improved, the Y molecular sieve is in-situ grown on the channel of the ZSM-22 molecular sieve and the P-KIT-1 molecular sieve, the distance between the molecular sieves with different channel structures is shortened, the synergistic effect between the three kinds of different molecular sieves is better, the hydrocracking performance of the catalyst containing the Y / ZSM-22 / P-KIT-1 composite molecular sieve is promoted, the selectivity, yield and smoke point of the aviation kerosene are improved, and the freezing point of the aviation kerosene is reduced.

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

[0042] According to the preparation method of the application, in order to prepare Y molecular sieve with excellent performance, preferably, the molar ratio of Na2O, Al2O3, SiO2 and H2O in the structure directing agent is (5-25):1:(5-20):(200-400).

[0043] The preparation of the structure directing agent is not particularly limited in the application, as long as the structure directing agent with the above composition can be prepared, according to a preferred embodiment of the application, the preparation of the structure directing agent of the application can be carried out in the following specific manner: at room temperature, the water glass is dissolved in deionized water, mixed uniformly, then mixed and stirred with the lye of the application, after the reaction is completed, the structure directing agent is obtained after standing.

[0044] Preferably, the molar ratio of Na2O, Al2O3 and H2O in the lye is (10-15):1:(100-200).

[0045] The preparation of the lye is not particularly limited in the application, as long as the lye with the above composition can be prepared, according to a preferred embodiment of the application, the preparation of the lye of the application can be carried out in the following specific manner: at room temperature, the sodium hydroxide, aluminum hydroxide and deionized water are mixed and stirred to obtain the lye.

[0046] According to the preparation method of the present application, in order to obtain the Y / ZSM-22 / P-KIT-1 composite molecular sieve with improved mesopore ratio and acidity, preferably, in the step (1), the weight ratio of the ZSM-22 molecular sieve, the P-KIT-1 molecular sieve and SiO2 in the gel is (0.5-2):(0.5-1):1.

[0047] According to the preparation method of the present application, in order to obtain the Y / ZSM-22 / P-KIT-1 composite molecular sieve with improved mesopore ratio and acidity, preferably, in the step (1), the weight ratio of the ZSM-22 molecular sieve, the P-KIT-1 molecular sieve and SiO2 in the gel is (0.5-2):(0.5-1):1.

[0048] The present application does not have special requirements for the silicon source, as long as the silicon source can be dissolved 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 further preferably, the silicon source is water glass.

[0049] The present application does not have special requirements for the aluminum source, as long as the aluminum source can be dissolved in water, preferably, the aluminum source is selected from at least one of alumina, sodium metaaluminate, aluminum isopropylate and aluminum sulfate octadecahydrate, and further preferably, the aluminum source is aluminum sulfate octadecahydrate or alumina.

[0050] The present application does not have special requirements for 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 the step (1), according to a preferred embodiment of the present application, the mixing in the step (1) can be carried out according to the following steps: the ZSM-22 and the P-KIT-1 molecular sieve are mixed and treated by beating, then mixed uniformly with the structure directing agent of the present application, and then the silicon source and the aluminum source are added in parallel flow.

[0051] According to the preparation method of the present application, in order to obtain the Y / ZSM-22 / P-KIT-1 composite molecular sieve with improved mesopore ratio and acidity, preferably, in the step (1), the weight ratio of the ZSM-22 molecular sieve, the P-KIT-1 molecular sieve and SiO2 in the gel is (0.5-2):(0.5-1):1.

[0052] According to the preparation method of the present application, in order to improve the pore performance of the prepared composite molecular sieve, preferably, in the step (2), the weight ratio of the polyacrylamide to SiO2 in the gel is 3-7:100.

[0053] According to the preparation method of the present application, in order to ensure the uniform mixing of the polyacrylamide and the gel and better play the role of the polyacrylamide as a pore expanding agent, preferably, in the step (2), the weight average molecular weight of the polyacrylamide is 30-100 thousand g / mol.

[0054] In the present application, the form of adding the polyacrylamide is not particularly limited, which can be directly mixed with the gel, or the polyacrylamide solution can be prepared first and then mixed with the gel in the form of solution. According to a preferred embodiment of the present application, the polyacrylamide is mixed with the gel in the form of solution.

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

[0056] The solvent in the polyacrylamide solution is not particularly limited in the present application, as long as it can dissolve the polyacrylamide. According to a preferred embodiment of the present application, preferably, the solvent in the polyacrylamide solution is deionized water.

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

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

[0059] Preferably, the temperature of the first calcination is 450-600℃, further preferably 500-550℃; the time is 2-8 h, further preferably 4-6 h.

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

[0061] The solvent in the ammonium sulfate solution is not particularly limited in the present application, as long as it can dissolve the ammonium sulfate. According to a preferred embodiment of the present application, preferably, the solvent in the ammonium sulfate solution is deionized water.

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

[0063] The solvent for washing in step (4) is not particularly limited in the present application, as long as it can wash away the sodium ions in the molecule and does not introduce other ions that can cause pollution. Preferably, the solvent for washing in the present application is deionized water.

[0064] Preferably, the temperature of the second drying is 100-120℃, and the time is 2-6 h.

[0065] Preferably, the second calcination is performed at a temperature of 500-600℃ for 2-6h.

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

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

[0068] The composite molecular sieve is the Y / ZSM-22 / P-KIT-1 composite molecular sieve of the first aspect or the third aspect.

[0069] In the present application, the 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 450-600m2 / g, and is purchased from Tianjin Kevin Technology Co., Ltd. 2 / g, and is purchased from Tianjin Kevin Technology Co., Ltd.

[0070] Preferably, in the amorphous silicon aluminum, the pore volumes of the pores in each pore size range are respectively: the pore volume of the pores with a pore size of 4-10nm is 0.45-0.75mL / g; the pore volume of the pores with a pore size of 10-20nm is 0.4-0.7mL / g; and the pore volume of the pores with a pore size of 20-50nm is 0.15-0.35mL / g.

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

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

[0073] Preferably, the specific surface area of the catalyst carrier is 400-680m 2 / g.

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

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

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

[0077] The preparation method of the catalyst carrier is not particularly limited in the present application, as long as the catalyst carrier with the above composition can be prepared. According to a preferred embodiment of the present application, the catalyst carrier can be prepared by the following method:

[0078] (a) adding amorphous silica-alumina, small-pore alumina, hierarchical-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 into deionized water to prepare an acidic solution, and adding the acidic solution into the powder prepared in step (a) dropwise, and rolling into blocks, and extruding on a double-screw extruder, and drying the extruded strips, and calcining 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 hierarchical-pore Y / ZSM-22 / P-KIT-1 composite molecular sieve, and according to a preferred embodiment of the present application, the amount of sesbania powder added is 3% of the total amount of amorphous silica-alumina, small-pore alumina, and hierarchical-pore Y / ZSM-22 / P-KIT-1 composite molecular sieve.

[0081] The stirring speed and time in step (a) are not particularly limited in the present application, as long as the raw materials are mixed uniformly.

[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 hierarchical-pore Y / ZSM-22 / P-KIT-1 composite molecular sieve; and the amount of nitric acid added is 2-10% of the total amount of amorphous silica-alumina, small-pore alumina, and hierarchical-pore Y / ZSM-22 / P-KIT-1 composite molecular sieve. According to a preferred embodiment of the present application, the amount of citric acid added is 3% of the total amount of amorphous silica-alumina, small-pore alumina, and hierarchical-pore Y / ZSM-22 / P-KIT-1 composite molecular sieve; and the amount of nitric acid added is 2% of the total amount of amorphous silica-alumina, small-pore alumina, and hierarchical-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 3:5.

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

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

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

[0088] Preferably, the catalyst carrier is the catalyst carrier according to the fourth aspect.

[0089] The present application does not have a particular limitation on the active component in the catalyst, as long as it has catalytic activity for hydrocracking reaction. According to some preferred embodiments of the present application, the active component is tungsten oxide and nickel oxide.

[0090] Preferably, the specific surface area of the catalyst is 280-320m 2 / g.

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

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

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

[0094] The present application does not have a particular limitation on the preparation method of the catalyst, as long as it can prepare the catalyst with the above composition. According to one preferred embodiment of the present application, the catalyst can be prepared by the following method:

[0095] (s1) adding ammonium metatungstate, nickel nitrate and ethylenediaminetetraacetic acid into a beaker containing deionized water for dissolution to obtain an impregnation solution;

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

[0097] The concentration of the impregnation solution in step (s1) is not particularly limited in the present application, as long as the impregnation solution can sufficiently impregnate the catalyst carrier, so that the content of the catalyst carrier and the active component in the catalyst obtained after drying and calcination is within the range defined in the present application. According to a preferred embodiment of the present application, the concentration of the catalyst active component precursor ammonium metatungstate and nickel nitrate in the impregnation solution is 1.216 g / mL, and the concentration of ethylenediaminetetraacetic acid is 0.052 g / mL.

[0098] The temperature and time of the impregnation in step (s2) are not particularly limited in the present application, as long as the impregnation solution can sufficiently impregnate the catalyst carrier. In some embodiments of the present application, the temperature of the impregnation is room temperature, and the time is 2 h.

[0099] Preferably, in step (s2), the temperature of the drying is 100-150℃, and the time is 2-6 h, and further preferably, the temperature of the drying is 120℃, and the time is 4 h.

[0100] Preferably, in step (s2), the temperature of the calcination is 450-600℃, and the time is 2-6 h, and further preferably, the temperature of the drying is 550℃, and the time is 4 h.

[0101] The sixth aspect of the present application provides a method for hydrocracking, the method comprising: performing a hydrocracking reaction on an intermediate base raw material in the presence of a catalyst;

[0102] The catalyst is the catalyst described in the fifth aspect.

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

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

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

[0106] The ZSM-22 molecular sieve has a purity of 90%, a specific surface area of 160-180 m 2 / g, a pore volume of 0.2-0.3 mL / g, and a pore size of 0.5-0.6 nm, and is purchased from Shandong Qilu Huaxin Gaokeli Co., Ltd.

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

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

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

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

[0111] Water glass, SiO2content 25% by weight, purchased from Xi'an Plunxin Material Environmental Engineering Co., Ltd.

[0112] The properties of the composite molecular sieve, catalyst carrier and catalyst are obtained by BET and pyridine infrared testing.

[0113] The composition of the composite molecular sieve, catalyst carrier and catalyst is calculated according to the amount of the raw materials.

[0114] Example 1

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

[0116] Take 1800 g of water glass and dissolve it in 2400 g of deionized water, and then mix it with the prepared lye, stir for 60 min, and let it stand for 40 h after 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 treated by beating, then mixed uniformly with the prepared structure directing agent, and then co-currently added with 1200 g of water glass and 1322 g of aluminum sulfate octadecahydrate, and aged at 60°C for 2 h to obtain a gel;

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

[0119] (3) The composite molecular sieve precursor I obtained in step (2) is subjected to first drying at 120 DEG C for 2h and first calcination at 500 DEG C for 4h to obtain composite molecular sieve precursor II;

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

[0121] The BET and pyridine infrared tests are performed on the composite molecular sieve 1, and from the test results, it can be known that the specific surface area of the composite molecular sieve 1 is 824m 2 / g, the pore volume is 0.66mL / g, the proportion of the pore size of 3-15nm is 61.3%, the proportion of the pore size greater than 15nm is 13.5%, and the medium-strong acid acid amount of the composite molecular sieve is 0.78mL / g.

[0122] Example 2

[0123] (1) 960g of sodium hydroxide, 156g of aluminum hydroxide, and 2700g of deionized water are mixed and stirred for 40min to obtain a lye;

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

[0125] 1000g of ZSM-22 molecular sieve and 792g of P-KIT-1 molecular sieve are mixed and treated by beating, and then mixed uniformly with the prepared structure directing agent B, followed by adding 1800g of silica sol and 666g of aluminum sulfate octadecahydrate in parallel flow, and aging at 70 DEG C for 2h to obtain a gel;

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

[0127] (3) The composite molecular sieve precursor I obtained in step (2) is subjected to first drying at 120 DEG C for 2h and first calcination at 500 DEG C for 4h to obtain composite molecular sieve precursor II;

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

[0129] The BET and pyridine infrared tests are performed on the composite molecular sieve 2, and from the test results, it can be known that the specific surface area of the composite molecular sieve 2 is 819 m 2 / g, the pore volume is 0.65 mL / g, the proportion of the pore size of 3-15 nm is 63.4%, the proportion of the pore size greater than 15 nm is 12.7%, and the medium-strong acid acid amount of the composite molecular sieve is 0.81 ml / g.

[0130] Example 3

[0131] (1) 1200 g of sodium hydroxide, 156 g of aluminum hydroxide, and 2160 g of deionized water are mixed and stirred for 40 min to obtain a lye;

[0132] 2700 g of ZSM-22 molecular sieve and 1500 g of P-KIT-1 molecular sieve are mixed and treated by beating, then mixed uniformly with the prepared structure directing agent, and then 3000 g of silica sol and 78 g of alumina are added in parallel flow, and aged at 90°C for 2h to obtain a gel;

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

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

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

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

[0137] The BET and pyridine infrared tests were performed on the composite molecular sieve 3, and the test results showed that the specific surface area of the composite molecular sieve 3 was 833 m 2 / g, the pore volume was 0.67 mL / g, the proportion of the pore size of 3-15 nm was 63.7%, the proportion of the pore size greater than 15 nm was 14.3%, and the medium-strong acid acid amount of the composite molecular sieve was 0.8 ml / g.

[0138] Example 4

[0139] (1) 44 g of amorphous silicon aluminum, 20 g of small-pore alumina, 33 g of hierarchical 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 a speed of 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 added dropwise to the prepared mixed powder and rolled into a block, and then extruded on a double screw extruder. The extruded strip was dried at 120 DEG C for 4 hours and calcined at 550 DEG 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 dissolved in a beaker containing deionized water to prepare 100 ml of impregnation solution; 25 ml of the impregnation solution was weighed, and a saturated impregnation method was used to impregnate 50 g of the carrier for 2 h, and then dried at 120 DEG C for 4 h and calcined at 550 DEG C in an air atmosphere for 4 h to prepare the catalyst A.

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

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

[0144] Example 5

[0145] (1) 34 g of amorphous silicon aluminum, 18 g of small-pore alumina, 45 g of hierarchical pore Y / ZSM-22 / P-KIT-1 composite molecular sieve 2, and 3 g of sesbania powder were added to a large crucible and stirred at a speed of 1200 rpm for 40 min to obtain a mixed powder;

[0146] 3g of citric acid and 5g of nitric acid were added to 60ml of deionized water to form an acidic solution, which was added dropwise to the mixed powder prepared, and rolled into a block shape, and extruded on a double screw extruder, and the extruded strip was dried at 120°C for 4 hours and calcined at 550°C for 4 hours to obtain catalyst carrier B;

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

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

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

[0150] Example 6

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

[0152] 3g of citric acid and 5g of nitric acid were added to 60ml of deionized water to form an acidic solution, which was added dropwise to the mixed powder prepared, and rolled into a block shape, and extruded on a double screw extruder, and the extruded strip was dried at 120°C for 4 hours and calcined at 550°C for 4 hours to obtain catalyst carrier C;

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

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

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

[0156] Comparative Example 1

[0157] According to the method of Example 6, except that the hierarchical Y / ZSM-22 / P-KIT-1 composite molecular sieve 2 in step (1) was replaced by Y molecular sieve, catalyst D was obtained.

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

[0159] Comparative Example 2

[0160] According to 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, catalyst E was obtained.

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

[0162] Comparative Example 3

[0163] According to the method of Example 4, except that 33 g of the hierarchical Y / ZSM-22 / P-KIT-1 composite molecular sieve 1 in step (1) was replaced by 18 g of Y molecular sieve, 8 g of ZSM-22 molecular sieve and 7 g of P-KIT-1 molecular sieve, catalyst F was obtained.

[0164] The performance parameters of the 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 by using standard GB / T 5816, GB / T 21650.2, HG / T3448-2003 and GB / T4324.16, and 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 examples, the catalysts prepared in the examples have larger specific surface area, pore volume and average pore diameter, which can provide larger reaction sites and space for the raw materials, and is beneficial to the diffusion and conversion of macromolecules, thereby improving the hydrogenation activity of the catalyst; compared with the comparative examples, the catalysts prepared in the examples have higher B / L acid ratio, which provides more cracking active centers for the catalytic cracking of the raw materials; in addition, the catalysts prepared in the examples have hierarchical pore structure, and the small carbon chain hydrocarbons generated by shallow cracking of the inferior intermediate base raw material in the amorphous silicon aluminum macroporous structure first enter the interior of the Y molecular sieve and / or P-KIT-1 molecular sieve with mesoporous channels, and further undergo hydrocracking reaction to generate products containing the aviation kerosene fraction, which then enter the interior of the ZSM-22 microporous molecular sieve for shape-selective isomerization to generate straight-chain hydrocarbons from branched-chain hydrocarbons, and these processes can significantly improve the selectivity, yield and smoke point of the aviation kerosene.

[0170] Test example

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

[0172] Specifically, 100 mL of the catalyst prepared in Examples 4, 5, 6 and Comparative Examples 1, 2 and 3 was crushed into particles with a length of 2-3 mm, and was loaded on a 200 mL fixed-bed hydrogenation device, and was sulfided with kerosene containing 2% carbon disulfide, wherein the main properties of the inferior intermediate base raw material are listed in Table 2:

[0173] Table 2

[0174] Item Poor quality middle base stock Analytical method Density (20°C, g / cm 3 )]]> 0.9065 GB / T 1884 Distillation range (°C) 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 Paraffins 21.5 Naphthenes 39.1 Aromatics 39.4

[0175] The conditions for hydrocracking were as follows: the pressure was 12.5 MPa, the cracking reaction temperature was 378°C, the hydrogen / oil volume ratio was 900:1, the volume space velocity was 1.1 h -1 , and the time was 48 h.

[0176] The obtained hydrocracking product was cut by the true boiling point fraction to obtain the component yield and analysis results as shown in Table 3:

[0177] Table 3

[0178]

[0179]

[0180] As shown in Table 3, under the same process conditions, compared with catalysts D, E, and F prepared in Comparative Examples 1, 2, and 3, catalysts A, B, and C prepared in Examples 4, 5, and 6 of this invention exhibit higher liquid yield, better selectivity for jet fuel, higher yield, higher smoke point, lower freezing point, higher viscosity index of tail oil, and higher aromatic potential of heavy naphtha when treating inferior intermediate base feedstocks. In other words, the catalysts provided by this invention have excellent hydrocracking performance and good selectivity for jet fuel products. The smoke point of the jet fuel products is 4.7-8.1 mm higher than that of the comparative agent E, and the freezing point is 7-11 °C lower than that of the comparative agent E. The target products, such as jet fuel, chemical raw materials, and lubricating oil base oil, have good properties and can help the refining industry transform and upgrade to the chemical industry.

[0181] As can be seen from the above examples and comparative examples, the catalyst prepared by the present invention has a large specific surface area, pore volume, and pore size. When applied to the hydrocracking of inferior intermediate feedstocks, the amorphous silica-alumina macroporous structure and the mesoporous channel structure of Y / P-KIT-1 are conducive to the diffusion and transformation of macromolecules, resulting in high catalytic activity. In addition, the ZSM-22 molecular sieve with a one-dimensional channel structure contained in the catalyst support increases the isomerization effect of the catalyst, which can significantly reduce the freezing point of jet fuel and increase its smoke point. This is beneficial to improving the selectivity of jet fuel when catalytically hydrocracking inferior intermediate feedstocks.

[0182] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within 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, the content of the ZSM-22 molecular sieve in the composite molecular sieve is 20-55% by weight, the content of the P-KIT-1 molecular sieve is 15-30% by weight, and the content of the Y molecular sieve is 20-65% by weight, based on the total weight of the composite molecular sieve; The preparation method of the composite molecular sieve comprises: (1) mixing ZSM-22 molecular sieve, P-KIT-1 molecular sieve, a structure directing agent, a silicon source and an aluminum source to obtain a gel; (2) mixing the gel with polyacrylamide and hydrothermally crystallizing to obtain the composite molecular sieve precursor I; (3) performing first drying and first calcination on the composite molecular sieve precursor I to obtain the composite molecular sieve precursor II; (4) adding the composite molecular sieve precursor II into an ammonium sulfate solution, performing second drying and second calcination to obtain the composite molecular sieve; 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).

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

3. The composite molecular sieve of claim 1 or 2, wherein, The specific surface area of the composite molecular sieve is 650-840 m 2 / g; And / or, the pore volume of the composite molecular sieve is 0.45-0.68 mL / g; And / or, in the composite molecular sieve, the proportion of the pore size of 3-15 nm is 43-65%, and the proportion of the pore size greater than 15 nm is 8-15%; And / or, the medium-strong acid amount 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, a structure directing agent, a silicon source and an aluminum source to obtain a gel; (2) mixing the gel with polyacrylamide and hydrothermally crystallizing to obtain the composite molecular sieve precursor I; (3) performing first drying and first calcination on the composite molecular sieve precursor I to obtain the composite molecular sieve precursor II; (4) adding the composite molecular sieve precursor II into an ammonium sulfate solution, performing second drying and second calcination to obtain the composite molecular sieve; 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).

5. The production method according to claim 4, wherein, In the gel, the molar ratio of Na2O, Al2O3 and SiO2 from the structure directing agent, the silicon source and the aluminum source is (2-30):1:(2-100); And / or, 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; And / or, the silicon source is selected from at least one of water glass, methyl orthosilicate, ethyl orthosilicate, silica sol and silicon powder; And / or, the aluminum source is selected from at least one of aluminum oxide, sodium metaaluminate, aluminum isopropoxide, and aluminum sulfate octadecahydrate.

6. The production method according to claim 4 or 5, wherein, In step (1), the mixing is further followed by an aging step, wherein the aging is performed at a temperature of 60-90℃ for 1-6h.

7. The production method according to claim 4, wherein In step (2), the weight ratio of polyacrylamide to SiO2 in the gel is 3-7:100; And / or, the weight average molecular weight of the polyacrylamide is 30-100 kg / mol; And / or, the hydrothermal crystallization treatment is performed at a temperature of 90-120℃ for 24-48h.

8. The production method according to claim 4, wherein In step (3), the first drying is performed at a temperature of 100-200℃ for 1-6h; And / or, the first calcination is performed at a temperature of 450-600℃ for 2-8h.

9. The production method according to claim 8, wherein In step (3), the first drying is performed at a temperature of 120-150℃ for 2-4h; And / or, the first calcination is performed at a temperature of 500-550℃ for 4-6h.

10. The production method according to claim 4, wherein, In step (4), the concentration of the ammonium sulfate solution is 0.5-2 mol / L; And / or, the second drying is further preceded by a step of stirring and washing; And / or, the stirring is performed at a temperature of 80-90℃ for 1-2h; And / or, the second drying is performed at a temperature of 100-120℃ for 2-6h; And / or, the second calcination is performed at a temperature of 500-600℃ for 2-6h.

11. A catalyst support, characterized by, The catalyst carrier comprises 20-70 wt% of amorphous silica-alumina, 10-50 wt% of small-pore alumina, and 15-80 wt% of the composite molecular sieve, based on the total weight of the catalyst carrier. The composite molecular sieve is the Y / ZSM-22 / P-KIT-1 composite molecular sieve according to any one of claims 1-3.

12. The catalyst support of claim 11, wherein, The specific surface area of the catalyst carrier is 400-680 m 2 / g; And / or, 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. And / or, the average pore diameter 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, The catalyst comprises 70-80 wt% of the catalyst carrier and 20-30 wt% of the active component, based on the total weight of the catalyst. The catalyst carrier is the catalyst carrier according to claim 11 or 12.

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

15. A process for hydrocracking characterized in that, The method comprises: performing a hydrocracking reaction on an intermediate base raw material in the presence of a catalyst. The catalyst is the catalyst according to claim 13 or 14.

16. The method of claim 15, wherein, The intermediate base raw material has a density ≧ 0.9 g / cm3 at 20°C 3 and a dry point ≧ 570°C.

17. The method of 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 / oil volume ratio of 750-1000: 1, a volume space velocity of 0.8-1.2 h -1 .

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