Beta / KCC-1 mesoporous composite molecular sieve and its preparation, hydrocracking catalyst and its preparation and application

Abstract

The present invention provides a kind of Beta / KCC-1 mesoporous composite molecular sieve and its preparation, hydrocracking catalyst and its preparation and application, wherein, the composite molecular sieve has a core-shell structure, including Beta molecular sieve and KCC-1 mesoporous material, KCC-1 mesoporous material is tightly wrapped outside the Beta molecular sieve, and the surface morphology of the composite molecular sieve is fibrous. The present invention compounds microporous material Beta molecular sieve and mesoporous material KCC-1, gives full play to the respective advantages of microporous material and mesoporous material, so that the composite molecular sieve has excellent diffusion performance, suitable acid properties, pore structure. The Beta / KCC-1 composite hydrocracking catalyst prepared using the composite molecular sieve as a carrier is a new catalyst material, and its catalytic activity and selectivity for the hydrocracking reaction of tetralin are relatively high, showing higher conversion rate, yield and product selectivity.

Description

Technical Field

[0001] The present invention relates to a Beta / KCC-1 mesoporous composite molecular sieve and its preparation, a hydrocracking catalyst and its preparation and application, and belongs to the technical field of petrochemical industry, in particular the technical field of hydrocracking. Background Art

[0002] Hydrocracking technology has become an important means of regulating the structure and quality of petroleum products, addressing the lightweighting of heavy oils and upgrading the quality of light oils. Hydrocracking catalysts are dual-function catalysts, requiring both hydrogenation and cracking performance. Beta molecular sieves, with their suitable pore structure, acidic properties, and excellent stability, are often used as the acidic component of hydrocracking catalysts. As crude oil quality continues to decline, the pores of Beta molecular sieves restrict the diffusion of heavy oils. Conventional hydrocracking catalysts often modify Beta molecular sieves to improve their pore distribution. However, when processing heavy oils with high sulfur and nitrogen content and complex molecular structures, the inherent limitations of Beta molecular sieves as microporous molecular sieves hinder the diffusion of polycyclic aromatic hydrocarbons within the pores. Since their initial development in 1992, mesoporous materials have remained a hot topic in catalytic material research. The large pore size and high specific surface area of mesoporous materials enhance the accessibility of catalyst active sites, thereby improving the catalyst's diffusion performance. Therefore, mesoporous materials hold great promise for applications in macromolecular catalysis, adsorption separation, and other fields. However, the acid properties of mesoporous materials are poor and cannot meet the cracking performance requirements of hydrocracking catalysts. Therefore, combining microporous molecular sieves and mesoporous materials to prepare mesoporous and microporous composite molecular sieve materials with good comprehensive performance can effectively solve the major challenges brought by crude oil heaviness to catalytic research.

[0003] Therefore, providing a new type of Beta / KCC-1 mesoporous composite molecular sieve and its preparation, hydrocracking catalyst and its preparation and application has become a technical problem that needs to be solved urgently in this field. Summary of the Invention

[0004] In order to solve the above-mentioned shortcomings and deficiencies, an object of the present invention is to provide a Beta / KCC-1 mesoporous composite molecular sieve and its preparation, a hydrocracking catalyst and its preparation and application.

[0005] In order to achieve the above objectives, on the one hand, the present invention provides a Beta / KCC-1 mesoporous composite molecular sieve, wherein the Beta / KCC-1 mesoporous composite molecular sieve has a core-shell structure, including a Beta molecular sieve and a KCC-1 mesoporous material, the KCC-1 mesoporous material is tightly wrapped around the Beta molecular sieve, and the surface morphology of the Beta / KCC-1 mesoporous composite molecular sieve is fibrous.

[0006] As a specific embodiment of the Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the specific surface area of the Beta / KCC-1 mesoporous composite molecular sieve is 450-600 m 2 ·g -1 , pore diameter is 6-10 nm, pore volume is 0.5-1.0 cm 3 ·g -1 And the average particle size is 250 to 750 nm.

[0007] The Beta / KCC-1 mesoporous and microporous composite molecular sieve described above has suitable acidity and a dual pore structure of the micropores of the Beta molecular sieve and the mesopores of the KCC-1 molecular sieve. The mesoporous material KCC-1 has a unique three-dimensional fiber pore structure, which can effectively improve the accessibility of active sites and enhance the catalyst diffusion performance, while having good thermal and hydrothermal stability.

[0008] On the other hand, the present invention also provides a method for preparing the above-mentioned Beta / KCC-1 mesoporous composite molecular sieve, wherein the preparation method comprises:

[0009] Step (1): adding a surfactant and a hydrolyzing agent into water and completely dissolving them to obtain a first mixed solution;

[0010] Step (2): adding the Beta molecular sieve obtained by calcination or without calcination into an organic solvent and dissolving it, then adding an organosilicon source and mixing them uniformly to obtain a second mixed solution;

[0011] Step (3): fully mixing the first mixed solution and the second mixed solution, adding a cosurfactant and mixing them evenly to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0012] The molar ratio of surfactant, hydrolyzing agent, water, organic solvent, co-surfactant and organosilicon source calculated as SiO2 is 0.05-0.5:0.2-2.0:80-300:15-60:0.5-5.0:1; the mass ratio of Beta molecular sieve and organosilicon source calculated as SiO2 is 0.10-2.50:1;

[0013] Step (4): subjecting the Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion to hydrothermal crystallization treatment, centrifuging and washing, and then drying and calcining to obtain the Beta / KCC-1 mesoporous composite molecular sieve.

[0014] As a specific embodiment of the preparation method described above of the present invention, in step (1), the surfactant includes one or a combination of cetyltrimethylammonium bromide, tetramethoxysilane, cetylpyridinium bromide, cetyltrimethylammonium chloride and decanyltrimethylammonium chloride.

[0015] As a specific embodiment of the above-mentioned preparation method of the present invention, in step (1), the hydrolyzing agent includes one or a combination of urea, organic amine, triethanolamine and ammonia water.

[0016] In step (1) of the method for preparing the Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the complete dissolution can be achieved by stirring. In some embodiments of the present invention, the stirring can be performed at room temperature.

[0017] As a specific embodiment of the preparation method described above of the present invention, in step (2), the organic solvent includes one or a combination of cyclohexane, toluene, 1-octadecene, diethyl ether, octane and styrene.

[0018] As a specific embodiment of the preparation method described above, in step (2), the organic silicon source includes one or a combination of tetraethyl silicate, tetraethoxysilane and tetramethoxysilane.

[0019] In step (2) of the method for preparing the Beta / KCC-1 mesoporous composite molecular sieve described above, the dissolution can be achieved by ultrasonic treatment, and the uniform mixing can be achieved by stirring. The present invention does not make specific requirements on the stirring conditions in step (2), such as the stirring time, and can be reasonably adjusted as needed. In some preferred embodiments of the present invention, the stirring time can be, for example, 5 to 30 minutes.

[0020] As a specific embodiment of the preparation method described above, in step (2), the Beta molecular sieve is a Beta molecular sieve obtained by calcination or without calcination, preferably the Beta molecular sieve is a Beta molecular sieve obtained without calcination. When the Beta molecular sieve is a Beta molecular sieve obtained by calcination, the calcination temperature can be 500-600°C, and the calcination time can be 3-6 hours.

[0021] In step (2) of the method for preparing the Beta / KCC-1 mesoporous composite molecular sieve described above, the Beta molecular sieve obtained without calcination can be prepared by a preparation method comprising the following steps:

[0022] Step 1): Add sodium chloride, potassium chloride, and template to water, stir until completely dissolved, then add silicon source and continue stirring;

[0023] Step 2): adding an alkali source and an aluminum source to water and stirring until completely dissolved, mixing the solution obtained in step 2) with the solution obtained in step 1), stirring and then allowing to stand for aging to obtain a silica-alumina gel;

[0024] Step 3): The silica-alumina gel is subjected to hydrothermal crystallization treatment, and after being naturally cooled, centrifuged, washed, and dried to obtain Beta molecular sieve.

[0025] In some preferred embodiments of the present invention, the Beta molecular sieve obtained without calcination can be prepared by a preparation method comprising the following specific steps:

[0026] Step 1): Sodium chloride, potassium chloride, and a template are added to water and stirred at room temperature until completely dissolved. While stirring, a silicon source is added and stirring is continued;

[0027] Step 2): adding an alkali source and an aluminum source to water, stirring at room temperature until completely dissolved, mixing the solution obtained in step 2) with the solution obtained in step 1), stirring until the mixture becomes a gel, and allowing it to stand and age to obtain a silica-alumina gel;

[0028] Step 3): The silica-alumina gel is placed in a crystallization kettle lined with polytetrafluoroethylene and subjected to hydrothermal crystallization treatment. After natural cooling, the gel is centrifuged, washed, and dried to obtain Beta molecular sieve.

[0029] In step 1) of preparing the Beta molecular sieve, the template agent may be tetraethylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide, etc., the silicon source may be fumed silica, tetraethyl orthosilicate, silica sol, etc., and the stirring time after adding the silicon source may be 0.5 to 1 hour.

[0030] In step 2) of preparing the Beta molecular sieve, the alkali source may be sodium hydroxide, potassium hydroxide, etc., the aluminum source may be sodium aluminate, aluminum sulfate, aluminum nitrate, etc., the water used may be deionized water, ultrapure water, distilled water, etc., the stirring temperature after mixing may be 20 to 45° C., the stirring time after mixing may be 0.5 to 3 h, the aging temperature may be 25 to 50° C., and the aging time may be 6 to 48 h.

[0031] In step 3) of preparing the Beta molecular sieve, the temperature of the hydrothermal crystallization treatment can be 125-160° C., the time of the hydrothermal crystallization treatment can be 1-5 days, the washing is washing until the pH value is less than 9, the drying temperature can be 50-80° C., and the drying time can be 4-12 hours. The ingredient composition of the Beta molecular sieve, calculated as oxides, is Na2O:K2O:(TEA)2O:Al2O3:SiO2:H2O, which can be 0.25-5:0.5-2:5-30:1:30-70:500-1000.

[0032] As a specific embodiment of the preparation method described above of the present invention, in step (3), the co-surfactant includes one or a combination of n-pentanol, isopropanol, n-butanol, 1-butyl-3-methylimidazolium trifluoromethanesulfonate and ethanol.

[0033] In step (3) of the preparation method of the Beta / KCC-1 mesoporous composite molecular sieve described above, the second mixed solution is added to the first mixed solution for thorough mixing. Wherein, the thorough mixing and uniform mixing in step (3) can be achieved by stirring. The present invention does not make specific requirements on the stirring conditions, such as stirring time, for achieving thorough mixing and uniform mixing in step (3), and can be reasonably adjusted as needed. In some preferred embodiments of the present invention, the stirring times for the thorough mixing and the uniform mixing can be, for example, 5 to 20 minutes and 15 to 40 minutes, respectively.

[0034] As a specific embodiment of the preparation method described above, in step (4), the temperature of the hydrothermal crystallization treatment is 60 to 120° C., and the time is 2 to 20 hours.

[0035] As a specific embodiment of the above-mentioned preparation method of the present invention, in step (4), the drying temperature is 25 to 90° C. and the drying time is 4 to 12 hours.

[0036] As a specific embodiment of the above-mentioned preparation method of the present invention, in step (4), the calcination temperature is 450-650° C. and the calcination time is 4-8 hours.

[0037] In step (4) of the method for preparing the Beta / KCC-1 mesoporous composite molecular sieve described above, the washing agent used in the washing step can be reasonably selected as needed. For example, in some preferred embodiments of the present invention, the washing agent can be deionized water, acetone, ethanol, etc.

[0038] The present invention synthesizes a mesoporous material KCC-1 having a regular fiber pore structure through template self-assembly. By introducing Beta molecular sieve seed crystals, the mesoporous material KCC-1 and Beta molecular sieve jointly form a mesoporous composite molecular sieve. The resulting Beta / KCC-1 mesoporous composite molecular sieve has the characteristics of high hydrothermal stability, adjustable acidity, and a reasonable pore distribution. In addition, during the preparation of the Beta / KCC-1 mesoporous composite molecular sieve, the acidity of the composite molecular sieve can be flexibly controlled by adjusting the amount of Beta molecular sieve added. At the same time, the particle size and pore structure properties of the Beta / KCC-1 mesoporous composite molecular sieve can be effectively controlled by adjusting the concentration of the hydrolyzing agent and surfactant, the time and temperature of the hydrothermal crystallization, the ratio of the organic solvent to water, and the stirring time, thereby achieving excellent diffusion performance. The unique fiber structure on the surface of the Beta / KCC-1 mesoporous composite molecular sieve can effectively improve the accessibility of the catalyst active sites, enhance the dispersion of the active components, and produce more hydrogenation active sites, thereby achieving a good match between the hydrogenation performance and cracking performance of the catalyst using the Beta / KCC-1 mesoporous composite molecular sieve as a carrier, thereby improving the comprehensive performance of the catalyst and facilitating its widespread use in industry.

[0039] On the other hand, the present invention also provides an H-type Beta / KCC-1 mesoporous composite molecular sieve, which is obtained by subjecting the above-mentioned Beta / KCC-1 mesoporous composite molecular sieve to ion exchange using an ammonium salt solution, and then drying and calcining the product.

[0040] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the ammonium salt includes one or a combination of ammonium nitrate, ammonium chloride and ammonium sulfate.

[0041] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the concentration of the ammonium salt solution is 1 to 4 mol / L.

[0042] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the mass ratio of the Beta / KCC-1 mesoporous composite molecular sieve to the ammonium salt solution is 1:5-20.

[0043] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the temperature of the ion exchange is 55-95° C., and the time is 0.5-5 h.

[0044] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the number of ion exchanges is 2 to 4 times.

[0045] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the drying temperature is 60-100° C. and the drying time is 7-12 hours.

[0046] As a specific embodiment of the above-mentioned H-type Beta / KCC-1 mesoporous composite molecular sieve of the present invention, the calcination temperature is 450-650° C. and the calcination time is 1-6 hours.

[0047] The H-type Beta / KCC-1 mesoporous composite molecular sieve described above can be prepared according to a preparation method comprising the following steps:

[0048] First, ammonium salt is added to water and stirred to form an ammonium salt solution. Then, the Beta / KCC-1 mesoporous composite molecular sieve and the ammonium salt solution are mixed to perform ion exchange. After cooling, the mixture is filtered and washed until it is close to neutral, completing one ion exchange. After multiple ion exchanges, the mixture is finally dried and calcined in sequence to obtain the H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0049] The pH value after filtration and washing during the preparation process is 7-9.

[0050] On the other hand, the present invention also provides a hydrocracking catalyst (also referred to as Beta / KCC-1 composite hydrocracking catalyst), comprising a carrier and a metal active component supported on the carrier, wherein the carrier is the H-type Beta / KCC-1 mesoporous composite molecular sieve described above, and the metal active component comprises a Group VIII metal and a Group VIB metal; based on the total weight of the hydrocracking catalyst as 100%, the contents of the Group VIII metal and the Group VIB metal in terms of oxides are 4-8 wt% and 10-20 wt%, respectively.

[0051] As a specific embodiment of the hydrocracking catalyst described above, the Group VIII metal includes nickel and / or cobalt, and the Group VIB metal includes molybdenum and / or tungsten.

[0052] On the other hand, the present invention also provides a method for preparing the hydrocracking catalyst described above, wherein the preparation method comprises:

[0053] The precursor salt of the Group VIII metal and the precursor salt of the Group VIB metal are added to deionized water and stirred until clear and transparent to prepare an impregnation solution. Then, the H-type Beta / KCC-1 mesoporous composite molecular sieve is impregnated in the impregnation solution for equal volume impregnation, and then the hydrocracking catalyst is obtained through aging, drying and calcination.

[0054] As a specific embodiment of the preparation method described above, the precursor salt of the Group VIII metal includes a nitrate of the Group VIII metal, and the precursor salt of the Group VIB metal includes an ammonium acid or ammonium meta-acid of the Group VIB metal. For example, in some specific embodiments of the present invention, the nitrate of the Group VIII metal may be nickel nitrate and / or cobalt nitrate, and the ammonium acid or ammonium meta-acid of the Group VIB metal may be ammonium molybdate and / or ammonium metatungstate.

[0055] As a specific embodiment of the above preparation method of the present invention, wherein the stirring is carried out at 50-100° C. and the stirring time is 0.5-2 h.

[0056] In the above-mentioned preparation method of the hydrocracking catalyst of the present invention, during the impregnation process, the impregnation liquid can be added dropwise to the H-type Beta / KCC-1 mesoporous composite molecular sieve for equal volume impregnation. In some preferred embodiments of the present invention, the addition is performed in small amounts and multiple times.

[0057] As a specific embodiment of the above preparation method of the present invention, the aging temperature is 20-35° C., and the aging time is 2-10 h.

[0058] As a specific embodiment of the above preparation method of the present invention, the drying temperature is 60-100° C., and the drying time is 5-12 hours.

[0059] As a specific embodiment of the above preparation method of the present invention, the calcination temperature is 450-650° C., and the calcination time is 4-8 hours.

[0060] In the present invention, the stirring time involved in the preparation of Beta molecular sieve, KCC-1 and Beta / KCC-1 mesoporous composite molecular sieve can be reasonably adjusted as needed. For example, in some preferred embodiments of the present invention, the stirring speed can be 200 to 1000 r / s.

[0061] In the final aspect, the present invention also provides the use of the above hydrocracking catalyst in catalytic hydrocracking of tetralin.

[0062] As a specific implementation of the above application of the present invention, the application includes the following steps:

[0063] Step 1: tableting and screening the hydrocracking catalyst, and then loading it into a reactor;

[0064] Step 2: pre-sulfiding the hydrocracking catalyst before the reaction;

[0065] Step 3: using the presulfurized hydrocracking catalyst to catalyze the hydrocracking reaction of tetralin;

[0066] Step 4: Determine the content of each component in the liquid product obtained after the hydrocracking reaction by gas chromatography-mass spectrometry (GC-MS).

[0067] As a specific embodiment of the above application of the present invention, in step 1, the tableting pressure is 20-30 MPa and the time is 10-20 minutes. In step 1, the tableting can be performed using a powder tablet press.

[0068] As a specific embodiment of the above application of the present invention, in step 1, the mesh size of the screening is 10-20 mesh or 20-40 mesh.

[0069] As a specific embodiment of the above application of the present invention, in step 1, the loading amount of the hydrocracking catalyst is 0.5 to 1.5 g.

[0070] As a specific embodiment of the above application of the present invention, in step 1, the reactor may be a high-pressure hydrogenation microreactor.

[0071] As a specific embodiment of the above application of the present invention, in step 2, the presulfurization liquid used for presulfurization is a cyclohexane mixed solution with a CS2 content of 1.5 to 5 wt%, the presulfurization pressure is 4 to 6 MPa, the hydrogen-to-oil volume ratio is 500 to 700:1, and the liquid hourly space velocity is 1 to 5 h -1 The pre-vulcanization temperature can be 200-350°C, and the pre-vulcanization time can be 2-12 hours.

[0072] As a specific embodiment of the above application of the present invention, in step 3, the temperature of the hydrocracking reaction is 340-400°C, the pressure is 6-8 MPa, and the liquid hourly space velocity is 0.8-1.2 h -1 , the hydrogen-to-oil volume ratio can be 1000-1500:1.

[0073] Compared with the prior art, the beneficial technical effects achieved by the present invention include at least:

[0074] The Beta / KCC-1 mesoporous composite molecular sieve provided by the present invention has a core-shell structure, comprising a Beta molecular sieve and a KCC-1 mesoporous material. The KCC-1 mesoporous material is tightly wrapped around the Beta molecular sieve, and the surface morphology of the Beta / KCC-1 mesoporous composite molecular sieve is fibrous. The present invention combines the microporous Beta molecular sieve and the mesoporous KCC-1 material to obtain the Beta / KCC-1 mesoporous composite molecular sieve, fully leveraging the respective advantages of the microporous and mesoporous materials. This Beta / KCC-1 mesoporous composite molecular sieve has excellent diffusion performance, suitable acidic properties, and a pore structure. The Beta / KCC-1 composite hydrocracking catalyst prepared using the Beta / KCC-1 mesoporous and microporous composite molecular sieve as a carrier is a new type of catalyst material. The mesoporous and microporous composite material in the catalyst can fully utilize the respective advantages of microporous materials and mesoporous materials. The outer layer mesoporous material with larger pore size and weaker acidity can complete the pre-cracking of macromolecular raw materials. After pre-cracking, the macromolecules are more likely to enter the inner layer microporous material with smaller pore size and stronger acidity. Finally, the outer layer mesoporous material and the inner layer endoporous material jointly realize the gradual reaction of hydrocracking.

[0075] The Beta / KCC-1 composite hydrocracking catalyst of the present invention has high catalytic activity and selectivity for the hydrocracking reaction of tetralin, exhibits higher conversion rate, yield and product selectivity, and has potential application value in the petrochemical field. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0077] Figure 1 This is the XRD spectrum of the Beta / KCC-1 mesoporous composite molecular sieve prepared in Example 1 of the present invention.

[0078] Figure 2 This is the XRD spectrum of the Beta molecular sieve prepared in Comparative Example 1.

[0079] Figure 3 This is the XRD spectrum of the mesoporous material KCC-1 molecular sieve prepared in Comparative Example 2.

[0080] Figure 4 This is the N2- adsorption-desorption isotherm of the Beta / KCC-1 mesoporous composite molecular sieve prepared in Example 1 of the present invention.

[0081] Figure 5This is the N2- adsorption-desorption isotherm diagram of the Beta molecular sieve prepared in Comparative Example 1.

[0082] Figure 6 This is the N2- adsorption-desorption isotherm diagram of the mesoporous material KCC-1 molecular sieve prepared in Comparative Example 2.

[0083] Figure 7 This is the pore size distribution diagram of the Beta / KCC-1 mesoporous and microporous composite molecular sieve prepared in Example 1 of the present invention.

[0084] Figure 8 This is the pore size distribution diagram of the Beta molecular sieve prepared in Comparative Example 1.

[0085] Figure 9 This is the pore size distribution diagram of the mesoporous material KCC-1 molecular sieve prepared in Comparative Example 2.

[0086] Figure 10 This is a scanning electron microscope (SEM) spectrum of the Beta / KCC-1 mesoporous composite molecular sieve prepared in Example 1 of the present invention.

[0087] Figure 11 This is a scanning electron microscope (SEM) spectrum of the Beta molecular sieve prepared in Comparative Example 1.

[0088] Figure 12 This is a scanning electron microscope (SEM) spectrum of the mesoporous material KCC-1 molecular sieve prepared in Comparative Example 2.

[0089] Figure 13 This is a transmission electron microscope (TEM) spectrum of the Beta / KCC-1 mesoporous composite molecular sieve prepared in Example 1 of the present invention.

[0090] Figure 14 This is the transmission electron microscope (TEM) spectrum of the Beta molecular sieve prepared in Comparative Example 1.

[0091] Figure 15 This is the transmission electron microscope (TEM) spectrum of the mesoporous material KCC-1 molecular sieve prepared in Comparative Example 2.

[0092] Figure 16 These are the ZLC diffusion curves and fitting curve spectra of the Beta / KCC-1 mesoporous and microporous composite molecular sieve prepared in Example 1 of the present invention, the Beta molecular sieve prepared in Comparative Example 1, and the mesoporous material KCC-1 molecular sieve prepared in Comparative Example 2. DETAILED DESCRIPTION

[0093] It should be noted that the term "comprise" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method, system, product or apparatus that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or are inherent to these processes, methods, products or apparatus.

[0094] The "range" disclosed in the present invention is given in the form of a lower limit and an upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundaries of a particular range. All ranges defined in this way are combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, a range of 60-120 and 80-110 is listed for a particular parameter, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, then the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0095] In the present invention, unless otherwise specified, the numerical range "ab" is an abbreviation for any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" are listed in this invention, and "0-5" is merely an abbreviation for these numerical combinations.

[0096] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in the present invention can be combined with each other to form a new technical solution.

[0097] In the present invention, unless otherwise specified, all technical features and preferred features mentioned in the present invention can be combined with each other to form a new technical solution.

[0098] In the present invention, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method comprising steps (a) and (b) indicates that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method further comprising step (c) indicates that step (c) may be added to the method in any order, for example, the method may comprise steps (a), (b) and (c), or may comprise steps (a), (c) and (b), or may comprise steps (c), (a) and (b), etc.

[0099] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with the attached table, drawings and examples. The following embodiments are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0100] Beta / KCC-1 mesoporous composite molecular sieve embodiment

[0101] Example 1

[0102] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0103] Preparation of Beta molecular sieve:

[0104] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0105] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0106] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0107] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0108] Step (1): add 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0109] Step (2): 1.5 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, ultrasonicated for 2 h, and then 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0110] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0111] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK1.

[0112] Example 2

[0113] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0114] Preparation of Beta molecular sieve:

[0115] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0116] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0117] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0118] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0119] Step (1): add 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0120] Step (2): 1 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, and after ultrasonication for 2 h, 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0121] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0122] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK2.

[0123] Example 3

[0124] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0125] Preparation of Beta molecular sieve:

[0126] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0127] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0128] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0129] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0130] Step (1): add 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0131] Step (2): 2 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, ultrasonicated for 2 h, and then 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0132] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0133] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK3.

[0134] Example 4

[0135] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0136] Preparation of Beta molecular sieve:

[0137] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0138] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0139] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0140] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0141] Step (1): add 3.06 g of hexadecyltrimethylammonium bromide and 2.67 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0142] Step (2): 1.5 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, ultrasonicated for 2 h, and then 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0143] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0144] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK4.

[0145] Example 5

[0146] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0147] Preparation of Beta molecular sieve:

[0148] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0149] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0150] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0151] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0152] Step (1): Add 3.06 g of hexadecyltrimethylammonium bromide and 3.14 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0153] Step (2): 1.5 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, ultrasonicated for 2 h, and then 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0154] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0155] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK5.

[0156] Example 6

[0157] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0158] Preparation of Beta molecular sieve:

[0159] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0160] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0161] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0162] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0163] Step (1): Add 4.59 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0164] Step (2): 1.5 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, and after ultrasonication for 2 h, 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0165] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0166] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK6.

[0167] Example 7

[0168] This embodiment provides a Beta / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0169] Preparation of Beta molecular sieve:

[0170] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0171] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0172] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0173] Preparation of Beta / KCC-1 mesoporous composite molecular sieve:

[0174] Step (1): Add 5.37 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved;

[0175] Step (2): 1.5 g of the microporous material Beta1 prepared above was added to 90 ml of cyclohexane solvent, and after ultrasonication for 2 h, 7.48 ml of tetraethyl silicate was added and stirred at room temperature for 15 min;

[0176] Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0177] Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the Beta / KCC-1 mesoporous composite molecular sieve, which was recorded as carrier BK7.

[0178] The difference between Example 1, Example 2 and Example 3 of the present invention is that the amount of microporous material Beta1 is different, the difference between Example 1, Example 4 and Example 5 of the present invention is that the amount of urea (hydrolyzing agent) is different, and the difference between Example 1, Example 6 and Example 7 of the present invention is that the amount of hexadecyltrimethylammonium bromide (surfactant) is different.

[0179] Beta / KCC-1 composite hydrocracking catalyst example

[0180] Example 1-1

[0181] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0182] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK1 was used as a carrier and the BK1 and ammonium chloride aqueous solution were mixed at a mass ratio of BK1:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0183] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT1.

[0184] Example 1-2

[0185] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0186] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK2 was used as a carrier and the BK2 and ammonium chloride aqueous solution were mixed at a mass ratio of BK2:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0187] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT2.

[0188] Examples 1-3

[0189] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0190] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK3 was used as a carrier and the BK3 and ammonium chloride aqueous solution were mixed at a mass ratio of BK3:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring conditions at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0191] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT3.

[0192] Examples 1-4

[0193] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0194] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK4 was used as a carrier and the BK4 and ammonium chloride aqueous solution were mixed at a mass ratio of BK4:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring conditions at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0195] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT4.

[0196] Examples 1-5

[0197] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0198] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK5 was used as a carrier and the BK5 and ammonium chloride aqueous solution were mixed at a mass ratio of BK5:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0199] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT5.

[0200] Examples 1-6

[0201] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0202] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK6 was used as a carrier and the BK6 and ammonium chloride aqueous solution were mixed at a mass ratio of BK6:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0203] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT6.

[0204] Examples 1-7

[0205] This embodiment provides a NiW / Beta / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0206] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of BK7 was used as a carrier and the BK7 and ammonium chloride aqueous solution were mixed at a mass ratio of BK7:ammonium chloride aqueous solution = 1:10. Ion exchange was performed at 80°C for 1.5 hours under stirring at a speed of 350 r / s. The mixture was filtered and washed until the pH value was 8. After three ion exchanges, the mixture was dried at 80°C for 10 hours and calcined at 550°C for 3 hours to obtain an H-type Beta / KCC-1 mesoporous composite molecular sieve.

[0207] 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80°C and a stirring speed of 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5 h, dried at 90°C for 10 h, and calcined at 550°C for 6 h to obtain a NiW / Beta / KCC-1 composite hydrocracking catalyst with a catalyst composition of 10 wt% WO3, 5 wt% NiO and 85 wt% carrier, recorded as CAT7.

[0208] Comparative Example 1

[0209] This comparative example 1 provides a Beta molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0210] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0211] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0212] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140°C for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, dried at 70°C for 12 hours, and calcined at 550°C for 6 hours to obtain Beta molecular sieve, which was recorded as Beta-s.

[0213] Comparative Example 2

[0214] This comparative example provides a mesoporous material KCC-1 molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0215] 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea were added to 90 ml of deionized water, and stirred at 400 rpm for 15 min at room temperature until completely dissolved to obtain a first mixed solution;

[0216] 7.48 ml of tetraethyl silicate was added to 90 ml of cyclohexane solvent, and stirred at 500 rpm for 15 min at room temperature to obtain a second mixed solution;

[0217] The second mixed solution was added to the first mixed solution, stirred at 700 rpm for 15 min at room temperature, 5 ml of n-pentanol was added, and stirred at 400 rpm for 30 min at room temperature to obtain a KCC-1 mesoporous molecular sieve precursor emulsion;

[0218] The KCC-1 mesoporous molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged, washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours to obtain the mesoporous material KCC-1 molecular sieve, which was recorded as Ks.

[0219] Comparative Example 3

[0220] This comparative example provides a NiW / Beta hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0221] 1. Preparation of Beta molecular sieve:

[0222] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0223] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0224] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0225] 2. Preparation of H-type Beta molecular sieve:

[0226] Step 4): Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L, use 2 g of Beta1 as a carrier and mix Beta1 and the ammonium chloride aqueous solution at a mass ratio of Beta1:ammonium chloride aqueous solution = 1:10, perform ion exchange at 80°C for 1.5 hours under stirring conditions at a stirring speed of 350 r / s, filter and wash to a pH value of 8, perform ion exchange three times, dry at 80°C for 10 hours, and calcine at 550°C for 3 hours to obtain H-type Beta molecular sieve.

[0227] 3. Hydrothermal pickling treatment:

[0228] Step 5): hydrothermally treating the H-type Beta molecular sieve at 650° C. and 0.3 MPa for 2 h to obtain the hydrothermally treated Beta molecular sieve;

[0229] Step 6): The Beta molecular sieve after hydrothermal treatment was mixed with a 1.5 mol / L hydrochloric acid solution at a solid-liquid ratio (mass ratio) of 1:10, and stirred at 80°C for 3 hours under a stirring condition of a stirring speed of 400 r / s, filtered and washed until neutral, dried at 70°C for 10 hours, and calcined at 500°C for 4 hours to obtain a carrier, which was recorded as carrier a.

[0230] 4. Preparation of NiW / Beta Hydrocracking Catalyst:

[0231] Step 7): 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80° C. and 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated onto 1.5 g of carrier a, aged at 25° C. for 5 h, dried at 90° C. for 10 h, and calcined at 550° C. for 6 h to obtain a NiW / Beta hydrocracking catalyst having a catalyst composition of 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CATA.

[0232] Comparative Example 4

[0233] This comparative example provides a NiW / Beta hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0234] 1. Preparation of Beta molecular sieve:

[0235] Step 1): 0.47 g of sodium chloride, 1.29 g of potassium chloride, and 90.2 g of tetraethylammonium hydroxide (25 wt%) were added to 52.7 g of deionized water and stirred at room temperature until completely dissolved. 30.27 g of fumed silica was added while stirring and stirring was continued for 30 minutes;

[0236] Step 2): 0.37 g of sodium hydroxide and 1.69 g of sodium metaaluminate were added to 18 g of water, stirred at room temperature until completely dissolved, and then added with the solution prepared in step 1), mixed, stirred at 25° C. for 1 hour until the mixture became gel-like, and aged at 35° C. for 6 hours to prepare a silica-alumina gel;

[0237] Step 3): The silica-alumina gel was placed in a crystallization kettle lined with polytetrafluoroethylene, hydrothermally crystallized at 140° C. for 2 days, cooled naturally, centrifuged, washed until the pH value was less than 9, and dried at 70° C. for 12 hours to obtain Beta molecular sieve, which was recorded as Beta1.

[0238] 2. Preparation of H-type Beta molecular sieve:

[0239] Step 4): Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L, use 2 g of Beta1 as a carrier and mix Beta1 and the ammonium chloride aqueous solution at a mass ratio of Beta1:ammonium chloride aqueous solution = 1:10, perform ion exchange at 80°C for 1.5 hours under stirring conditions at a stirring speed of 350 r / s, filter and wash to a pH value of 8, perform ion exchange three times, dry at 80°C for 10 hours, and calcine at 550°C for 3 hours to obtain H-type Beta molecular sieve.

[0240] 3. Hydrothermal alkali washing treatment:

[0241] Step 5): hydrothermally treating the H-type Beta molecular sieve at 650° C. and 0.3 MPa for 2 h to obtain the hydrothermally treated Beta molecular sieve;

[0242] Step 6): The hydrothermally treated Beta molecular sieve was mixed with a 0.5 mol / L sodium hydroxide solution at a solid-liquid ratio (weight ratio) of 1:10, and stirred at 70 ° C for 2 h under stirring conditions of a stirring speed of 400 r / s. After filtration and washing until neutral, it was dried at 70 ° C for 10 h and calcined at 500 ° C for 4 h to obtain a carrier, which was recorded as carrier b.

[0243] 4. Preparation of NiW / Beta Hydrocracking Catalyst:

[0244] Step 7): 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80° C. and 400 r / s for 1 h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated onto 1.5 g of carrier b, aged at 25° C. for 5 h, dried at 90° C. for 10 h, and calcined at 550° C. for 6 h to obtain a NiW / Beta hydrocracking catalyst having a catalyst composition of 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CATB.

[0245] Characterization test case

[0246] In this test example, BK1 prepared in Example 1 of the present invention was subjected to XRD, N2- adsorption and desorption, scanning electron microscopy, transmission electron microscopy, diffusion performance and other analyses. The XRD results are as follows: Figure 1 As shown, the N2- adsorption-desorption isotherm is as follows Figure 4 The pore size distribution results are shown in Figure 7 The scanning electron microscopy results are shown in Figure 10 The transmission electron microscopy results are shown in Figure 13 The diffusion performance results are shown in Figure 16 shown.

[0247] In this test example, the Beta-s prepared in Comparative Example 1 was analyzed by XRD, N2-adsorption and desorption, scanning electron microscopy, and diffusion performance. The XRD results are shown in the figure. Figure 2 As shown, the N2- adsorption-desorption isotherm is as follows Figure 5 The pore size distribution results are shown in Figure 8 The scanning electron microscopy results are shown in Figure 11 The transmission electron microscopy results are shown in Figure 14 The diffusion performance results are shown in Figure 16 shown.

[0248] In this test example, the Ks prepared in Comparative Example 2 was analyzed by XRD, N2- adsorption and desorption, scanning electron microscopy, transmission electron microscopy, and diffusion properties. The XRD results are as follows: Figure 3 As shown, the N2- adsorption-desorption isotherm is as follows Figure 6 The pore size distribution results are shown in Figure 9 The scanning electron microscopy results are shown in Figure 12 The transmission electron microscopy results are shown in Figure 15 The diffusion performance results are shown in Figure 16 shown.

[0249] From the above results, it can be seen that the Beta / KCC-1 mesoporous composite molecular sieve provided in Example 1 of the present invention, that is, BK1, has a core-shell structure, including a Beta molecular sieve and a KCC-1 mesoporous material, the KCC-1 mesoporous material is tightly wrapped around the Beta molecular sieve, and the surface morphology of the Beta / KCC-1 mesoporous composite molecular sieve is fibrous. It can be seen that the embodiment of the present invention successfully composites the Beta molecular sieve with the KCC-1 material, and the Beta / KCC-1 mesoporous composite molecular sieve has a physical structure similar to that of the microporous Beta molecular sieve; the surface morphology of the KCC-1 material and the Beta / KCC-1 mesoporous composite molecular sieve are both fibrous, indicating that their unique morphology is retained before and after the composite.

[0250] This test example also measured the average particle size, specific surface area, pore size and pore volume data of the Beta / KCC-1 mesoporous composite molecular sieve provided in Examples 1 to 7 of the present invention, the Beta molecular sieve provided in Comparative Example 1, the mesoporous material KCC-1 molecular sieve provided in Comparative Example 2, the hydrothermal acid-treated Beta molecular sieve provided in Comparative Example 3, i.e., carrier a, and the hydrothermal alkali-treated Beta molecular sieve provided in Comparative Example 4, i.e., carrier b. The results are shown in Table 1 below.

[0251] Table 1

[0252]

[0253] As can be seen from Table 1 above, the Beta / KCC-1 mesoporous and microporous composite molecular sieve prepared in the embodiment of the present invention has increased specific surface area, pore volume and pore diameter compared with the microporous Beta molecular sieve, which effectively improves the pore structure properties of the material and can also accurately control the particle size of the composite molecular sieve.

[0254] This test example also measured the effective diffusion coefficient data of the Beta / KCC-1 mesoporous composite molecular sieve provided in Example 1, namely BK1, the Beta molecular sieve provided in Comparative Example 1, namely Beta-s, and the mesoporous material KCC-1 molecular sieve provided in Comparative Example 2, namely Ks. The results are shown in Table 2 below.

[0255] Table 2

[0256] project Effective diffusion coefficient Example 1 5.28E-04 Comparative Example 1 1.39E-04 Comparative Example 2 2.07E-03

[0257] Combine Figure 16 As can be seen from Table 2, the relationship between the effective diffusion coefficients is: Comparative Example 2 > Example 1 > Comparative Example 1, which shows that when the mesoporous composite molecular sieve provided by the embodiment of the present invention is used as a hydrocracking catalyst carrier, compared with traditional microporous material carriers, the mesoporous composite molecular sieve provided by the embodiment of the present invention can effectively improve the diffusion ability of the reactant molecules in the pores.

[0258] Performance test case

[0259] This test example evaluated the hydrocracking reaction of tetralin catalyzed by CAT1 to CAT7 provided in Examples 1 to 7 of the present invention and CATA and CATB provided in Comparative Examples 3 to 4. The evaluation was carried out on a fixed-bed microreactor. During the evaluation, the conversion rate, yield and selectivity of the hydrocracking of each catalyst were investigated. The experimental data obtained are shown in Table 3 below.

[0260] The specific steps of the evaluation process are as follows:

[0261] Step 1: First, CAT1 to CAT7 provided in Examples 1 to 7 of the present invention and CATA and CATB provided in Comparative Examples 3 to 4 were respectively tableted using a powder tabletting machine at a pressure of 25 MPa for 10 minutes, and then sieved into 20-40 meshes, and 1 g was taken and loaded into a high-pressure hydrogenation microreactor;

[0262] Step 2: Before the hydrocracking reaction, the above catalysts were presulfided. The presulfiding liquid used for presulfiding was a cyclohexane mixed solution with a CS2 content of 1.5 wt%. The presulfiding conditions were: hydrogen pressure 6 MPa, hydrogen-to-oil volume ratio 600:1, liquid hourly space velocity 2.5 h -1 , 230℃ for 2h, 320℃ for 3h;

[0263] Step 3: The above catalysts were used to catalyze the hydrocracking reaction of tetralin in a high-pressure hydrogenation microreactor, wherein the reaction temperature was 380°C, the reaction pressure was 6 MPa, and the liquid hourly space velocity was 1 h -1 , the volume ratio of hydrogen to oil is 1200:1;

[0264] Step 4: Use gas chromatography-mass spectrometry GC-MS to determine the content of each component in the liquid product obtained from the hydrocracking reaction.

[0265] Table 3

[0266]

[0267]

[0268] The hydrocracking catalytic reaction results for tetralin using each catalyst, as shown in Table 3, indicate that the Beta / KCC-1 composite hydrocracking catalyst provided in this embodiment of the present invention achieves significantly higher conversion, alkylbenzene yield, and alkylbenzene selectivity than a hydrocracking catalyst prepared using a conventional modified Beta molecular sieve as a support. Therefore, this novel composite hydrocracking catalyst provided in this embodiment of the present invention has significant potential for industrial application.

[0269] In summary, the Beta / KCC-1 mesoporous composite molecular sieve provided in the embodiment of the present invention has a core-shell structure, including a Beta molecular sieve and a KCC-1 mesoporous material, wherein the KCC-1 mesoporous material is tightly wrapped around the Beta molecular sieve, and the surface morphology of the Beta / KCC-1 mesoporous composite molecular sieve is fibrous. In the embodiment of the present invention, the microporous material Beta molecular sieve and the mesoporous material KCC-1 are compounded to obtain the Beta / KCC-1 mesoporous composite molecular sieve, giving full play to the respective advantages of the microporous material and the mesoporous material, so that the Beta / KCC-1 mesoporous composite molecular sieve has excellent diffusion performance, suitable acid properties, and pore structure. The Beta / KCC-1 composite hydrocracking catalyst prepared using the Beta / KCC-1 mesoporous and microporous composite molecular sieve as a carrier is a new type of catalyst material. The mesoporous and microporous composite material in the catalyst can fully utilize the respective advantages of microporous materials and mesoporous materials. The outer layer mesoporous material with larger pore size and weaker acidity can complete the pre-cracking of macromolecular raw materials. After pre-cracking, the macromolecules are more likely to enter the inner layer microporous material with smaller pore size and stronger acidity. Finally, the outer layer mesoporous material and the inner layer endoporous material jointly realize the gradual reaction of hydrocracking.

[0270] The Beta / KCC-1 composite hydrocracking catalyst provided in the embodiment of the present invention has high catalytic activity and selectivity for the hydrocracking reaction of tetralin, exhibits higher conversion rate, yield and product selectivity, and has potential application value in the petrochemical field.

[0271] The above description is merely a specific embodiment of the present invention and should not be construed as limiting the scope of the invention. Therefore, substitutions of equivalent components, or equivalent changes and modifications made within the scope of patent protection, should still fall within the scope of this patent. Furthermore, the technical features of this invention may be freely combined with one another, with other technical inventions, and with other technical inventions.

Claims

1. A hydrocracking catalyst comprising a carrier and a metal active component supported on the carrier, characterized in that: Based on the total weight of the hydrocracking catalyst being 100%, the catalyst comprises 10 wt% WO3, 5 wt% NiO, and 85 wt% of a carrier, wherein the carrier is an H-type Beta / KCC-1 mesoporous composite molecular sieve, and the H-type Beta / KCC-1 mesoporous composite molecular sieve is prepared by mixing 2 g of the Beta / KCC-1 mesoporous composite molecular sieve with a 1 mol / L ammonium chloride aqueous solution at a mass ratio of Beta / KCC-1 mesoporous composite molecular sieve to ammonium chloride aqueous solution of 1:10, performing ion exchange at 80°C for 1.5 hours, filtering and washing to a pH of 8, performing ion exchange three times, drying at 80°C for 10 hours, and calcining at 550°C for 3 hours. Among them, the specific surface area of Beta / KCC-1 mesoporous composite molecular sieve is 504.43m 2 ·g -1 , pore diameter is 6.43 nm, pore volume is 0.61 cm 3 ·g -1 The average particle size is 302 nm and is prepared by the following steps: Step (1): add 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water and stir at room temperature until completely dissolved; Step (2): 2 g of the prepared microporous material Beta1 was added to 90 ml of cyclohexane solvent, and after ultrasonic treatment for 2 h, 7.48 ml of tetraethyl silicate was added, and stirred at room temperature for 15 min. The microporous material Beta1 was a microporous material Beta1 that had not been calcined or amine exchanged. Step (3): adding the solution obtained in step (2) to the solution obtained in step (1), stirring at room temperature for 15 minutes, adding 5 ml of n-pentanol, and stirring at room temperature for 30 minutes to obtain a Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion; Step (4): The Beta / KCC-1 mesoporous composite molecular sieve precursor emulsion was hydrothermally treated at 120°C for 5 hours, centrifuged and washed with deionized water, dried at 70°C for 10 hours, and calcined at 550°C for 6 hours.

2. The method for preparing the hydrocracking catalyst according to claim 1, wherein The preparation method comprises: 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate were dissolved in deionized water, stirred at 80° C. and a stirring speed of 400 r / s for 1 hour until the solution became clear and transparent, and the volume of the solution was fixed to 1.8 ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5 g of H-type Beta / KCC-1 mesoporous composite molecular sieve, aged at 25° C. for 5 hours, dried at 90° C. for 10 hours, and calcined at 550° C. for 6 hours to obtain the hydrocracking catalyst.

3. Use of the hydrocracking catalyst according to claim 1 in catalytic hydrocracking of tetralin, characterized in that: The application includes the following specific steps: Step 1: First, the hydrocracking catalyst is pressed into tablets at a pressure of 25 MPa for 10 minutes using a powder tablet press, and then sieved into 20-40 mesh, and 1 g is taken and loaded into a high-pressure hydrogenation microreactor; Step 2: Before the hydrocracking reaction, the hydrocracking catalyst is presulfided, wherein the presulfiding liquid used for presulfiding is a cyclohexane mixed solution with a CS2 content of 1.5 wt%. The presulfiding conditions are: hydrogen pressure 6 MPa, hydrogen-oil volume ratio 600:1, liquid hourly space velocity 2.5 h -1 , 230℃ for 2h, 320℃ for 3h; Step 3: Using the hydrocracking catalyst to catalyze the hydrocracking reaction of tetralin in a high-pressure hydrogenation microreactor, wherein the reaction temperature is 380°C, the reaction pressure is 6 MPa, and the liquid hourly space velocity is 1 h -1 , the volume ratio of hydrogen to oil is 1200:1; Step 4: Use gas chromatography-mass spectrometry GC-MS to determine the content of each component in the liquid product obtained from the hydrocracking reaction.

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