Y / KCC-1 meso-microporous composite molecular sieve and preparation thereof, hydrocracking catalyst and preparation and application thereof

Abstract

The invention provides a Y / KCC-1 meso-microporous composite molecular sieve and preparation thereof, a hydrocracking catalyst and preparation and application thereof, the Y / KCC-1 meso-microporous composite molecular sieve has a core-shell structure and comprises a Y molecular sieve and a KCC-1 mesoporous material, the Y molecular sieve is tightly wrapped by the KCC-1 mesoporous material, and the surface appearance of the Y / KCC-1 meso-microporous composite molecular sieve is fibrous. According to the invention, the microporous material Y molecular sieve and the mesoporous material KCC-1 are compounded, and respective advantages of the microporous material and the mesoporous material are fully exerted, so that the composite molecular sieve has excellent diffusion performance, proper acid property and pore structure. The Y / KCC-1 composite hydrocracking catalyst prepared by taking the composite molecular sieve as a carrier is a novel catalyst material, has high catalytic activity and selectivity on hydrocracking reaction of 1-methylnaphthalene, and shows higher conversion rate, yield and product selectivity.

Description

Technical Field

[0001] The invention relates to a Y / 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 to the technical field of hydrocracking. Background Art

[0002] At present, hydrocracking technology has become an important measure to optimize the structure of petroleum products and enhance market resilience. The development of hydrocracking catalysts with molecular sieve materials as carriers is the main direction of hydrocracking process research and development. The properties of molecular sieves are crucial to the catalytic performance of catalysts. Molecular sieve catalysts are mostly based on Y molecular sieves, Beta molecular sieves, ZSM-5 molecular sieves, etc. These materials have suitable surface structures, pore size distributions and acid properties. However, with the increasing heaviness of oil products, the narrow pore size of microporous molecular sieves limits their application as carriers for hydrocracking catalysts. In 1992, mesoporous molecular sieves were first developed. They have a high specific surface area and a large pore size, which is conducive to the dispersion of active components. At the same time, they greatly reduce the limiting effect of the pores on the reactant and product molecules, and significantly enhance the diffusion and transmission capacity. Hydrocracking catalysts need to have suitable hydrogenation performance and strong cracking performance, and require the carrier material to have suitable acid properties, but the acidity of mesoporous materials is weak and cannot be used as a carrier material alone. Compounding mesoporous materials with microporous materials to prepare meso-microporous composite materials can effectively improve the limitation of narrow pore size of microporous materials, while solving the problem of weak acidity of mesoporous materials, providing new ideas for the further development of hydrocracking catalysts.

[0003] In recent years, research on composite hydrocracking catalysts includes the composite of Y molecular sieve with mesoporous molecular sieves such as SBA-15 and MCM-41. However, the pores of such mesoporous materials are tubular pore structures with only two ends open, which limits the accessibility of the internal surface of the pores.

[0004] Therefore, providing a new type of Y / 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

[0005] In order to solve the above-mentioned shortcomings and deficiencies, the object of the present invention is to provide a Y / KCC-1 mesoporous composite molecular sieve and its preparation, a hydrocracking catalyst and its preparation and application.

[0006] In order to achieve the above objectives, on the one hand, the present invention provides a Y / KCC-1 mesoporous composite molecular sieve, wherein the Y / KCC-1 mesoporous composite molecular sieve has a core-shell structure, including a Y molecular sieve and a KCC-1 mesoporous material, the KCC-1 mesoporous material is tightly wrapped around the Y molecular sieve, and the surface morphology of the Y / KCC-1 mesoporous composite molecular sieve is fibrous.

[0007] As a specific embodiment of the Y / KCC-1 mesoporous composite molecular sieve described above in the present invention, the specific surface area of ​​the Y / KCC-1 mesoporous composite molecular sieve is 590 to 800 m 2 ·g -1 , pore diameter is 7.4~10nm, pore volume is 0.4~1.0cm 3 ·g -1 And the average particle size is 150-750nm.

[0008] In the above-mentioned Y / KCC-1 mesoporous and microporous composite molecular sieve of the present invention, the mesoporous material KCC-1 has a unique three-dimensional fiber pore structure, which can effectively improve the accessibility of active sites, enhance the diffusion performance of the catalyst, and has good thermal and hydrothermal stability.

[0009] On the other hand, the present invention also provides a method for preparing the above-mentioned Y / KCC-1 mesoporous composite molecular sieve, wherein the preparation method comprises:

[0010] Step (1): adding a surfactant and a hydrolyzing agent into water and dissolving them completely to obtain a first mixed solution;

[0011] Step (2): adding the Y molecular sieve obtained by calcination or without calcination into an organic solvent to dissolve it, and then adding an organic silicon source and mixing them uniformly to obtain a second mixed solution;

[0012] Step (3): after the first mixed solution and the second mixed solution are fully mixed, a co-surfactant is added and mixed evenly to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0013] 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 Y molecular sieve and organosilicon source calculated as SiO2 is 0.10-2.50:1;

[0014] Step (4): subjecting the Y / KCC-1 mesoporous composite molecular sieve precursor emulsion to hydrothermal crystallization treatment, centrifuging and washing after the hydrothermal crystallization treatment, and then drying and calcining to obtain the Y / KCC-1 mesoporous composite molecular sieve.

[0015] 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.

[0016] As a specific embodiment of the preparation method described above of the present invention, in step (1), the hydrolyzing agent includes one or a combination of urea, organic amine, triethanolamine and ammonia water.

[0017] In the preparation method of the Y / KCC-1 mesoporous composite molecular sieve described above in step (1), the complete dissolution can be achieved by stirring. In some embodiments of the present invention, the stirring can be carried out at room temperature. As a specific embodiment of the preparation method described above in the present invention, in step (2), the organic solvent includes one or a combination of cyclohexane, toluene, 1-octadecene, 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 the step (2) of the preparation method of the Y / 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 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 of the present invention, in step (2), the Y molecular sieve is a Y molecular sieve obtained by calcination or without calcination, wherein, when calcining, the calcination temperature can be 500-600°C, and the calcination time can be 3-6h. Preferably, the Y molecular sieve is preferably a Y molecular sieve obtained without calcination. In step (2) of the preparation method of the Y / KCC-1 mesoporous composite molecular sieve described above of the present invention, the Y molecular sieve obtained without calcination can be prepared by a preparation method comprising the following steps:

[0021] Step 1): adding an alkali source and an aluminum source to water, and then adding a silicon source, stirring to form a seed gel precursor, and preparing a seed gel of a microporous material Y molecular sieve through aging;

[0022] Step 2): mixing an alkali source, an aluminum source and a silicon source to form a reaction mixture, adding the seed gel obtained in step 1) to the reaction mixture, stirring and aging, to form a reactant gel;

[0023] Step 3): The reactant gel is subjected to hydrothermal crystallization treatment, and after the treatment, it is centrifuged, washed, and then dried to obtain a microporous material Y molecular sieve.

[0024] In some preferred embodiments of the present invention, the Y molecular sieve obtained without calcination can be prepared by a preparation method comprising the following specific steps:

[0025] Step 1): adding an alkali source and an aluminum source to water, stirring at room temperature until completely dissolved, adding a silicon source under stirring, stirring to form a seed gel precursor, and then aging to obtain a seed gel of a microporous material Y molecular sieve;

[0026] Step 2): adding an alkali source and an aluminum source to water, stirring at room temperature until completely dissolved, and then adding a silicon source while stirring rapidly until a uniform gel state is obtained to obtain a reaction mixture, adding the seed gel obtained in step 1) to the reaction mixture, stirring, and aging to form a reactant gel;

[0027] Step 3): The reactant gel obtained in step 2) is subjected to hydrothermal crystallization treatment, centrifuged, washed, and then dried to obtain the microporous material Y molecular sieve.

[0028] In step 1) of preparing the Y molecular sieve, the alkali source can be sodium hydroxide and sodium carbonate, the aluminum source can be sodium aluminate, aluminum oxide, aluminum nitrate and aluminum chloride, and the silicon source can be sodium silicate, silica sol, tetraethyl orthosilicate and nano-silicon dioxide. After adding the silicon source, the stirring time can be 5 to 30 minutes, the aging temperature can be 20 to 55°C, and the aging time can be 10 to 36 hours. The molar ratio of each component in the seed gel of the microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=10 to 20:1:5-27:200 to 450.

[0029] In step 2) of preparing the Y molecular sieve, the alkali source can be sodium hydroxide and sodium carbonate, the aluminum source can be sodium aluminate, aluminum oxide, aluminum nitrate and aluminum chloride, and the silicon source can be sodium silicate, silica sol, tetraethyl orthosilicate and nano-silicon dioxide. The stirring time after adding the silicon source can be 5 to 20 minutes (calculated as oxide), the molar ratio of the reaction mixture is Na2O:Al2O3:SiO2:H2O=4 to 10:1:6 to 20:150 to 800, the amount of seed gel added can be 2 to 5% of the total mass of the reactant gel, the aging temperature can be 20 to 35°C, the aging time can be 8 to 24 hours (calculated as oxide), and the molar ratio of the reactant gel is Na2O:Al2O3:SiO2:H2O=2 to 14:1:8 to 20:180 to 600.

[0030] In step 3) of preparing the Y molecular sieve, the temperature of the hydrothermal crystallization treatment can be 90-140°C, and the time of the hydrothermal crystallization treatment can be 5-24 hours; the washing is washing until the pH value is 8-10; the drying temperature can be 35-110°C, and the drying time can be 5-12 hours; calculated as oxide, the silicon-aluminum molar ratio SiO2 / Al2O3 of the Y molecular sieve can be 5-20:1.

[0031] 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.

[0032] In step (3) of the method for preparing the Y / 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 more preferred embodiments of the present invention, the stirring time for the thorough mixing and the uniform mixing can be, for example, 5 to 20 minutes and 15 to 40 minutes, respectively.

[0033] As a specific embodiment of the preparation method described above of the present invention, in step (4), the temperature of the hydrothermal crystallization treatment is 60 to 120° C., and the time is 2 to 20 hours.

[0034] As a specific embodiment of the above 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.

[0035] As a specific embodiment of the preparation method described above of the present invention, in step (4), the calcination temperature is 450-650° C. and the calcination time is 4-8 hours.

[0036] In step (4) of the preparation method of the Y / KCC-1 mesoporous composite molecular sieve described above, the washing agent used in the washing 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.

[0037] The Y / KCC-1 mesoporous composite molecular sieve of the present invention is prepared by compounding the microporous material Y molecular sieve as a seed with the mesoporous material KCC-1 under hydrothermal conditions, and has excellent thermal and hydrothermal stability. In addition, the acidity of the Y / KCC-1 mesoporous composite molecular sieve can be flexibly controlled by regulating the amount of the Y molecular sieve added. The Y / KCC-1 mesoporous composite molecular sieve presents a structural form in which the microporous material Y molecular sieve is tightly wrapped by mesoporous fibers, i.e., fibrous KCC-1, and has a unique fiber pore structure, which is conducive to reducing the diffusion resistance of reactants and products, effectively enhancing the diffusion performance of the catalyst, improving the reaction rate, and avoiding overreaction. In the preparation process, the particle size and pore structure properties of the Y / KCC-1 mesoporous composite molecular sieve can also be regulated by adjusting the addition concentration of the hydrolyzing agent and the surfactant, the time and temperature of the hydrothermal crystallization, the addition ratio of the organic solvent and water, and the stirring time, so that it has excellent diffusion performance, thereby improving the catalytic performance and product quality of the catalyst with it as the carrier.

[0038] On the other hand, the present invention also provides an H-type Y / KCC-1 mesoporous composite molecular sieve, which is obtained by subjecting the above-mentioned Y / KCC-1 mesoporous composite molecular sieve to ion exchange using an ammonium salt solution, and then drying and calcining the product.

[0039] As a specific embodiment of the H-type Y / KCC-1 mesoporous composite molecular sieve described above, the ammonium salt includes one or a combination of ammonium nitrate, ammonium chloride and ammonium sulfate.

[0040] As a specific embodiment of the above-mentioned H-type Y / KCC-1 mesoporous composite molecular sieve of the present invention, the concentration of the ammonium salt solution is 1-4 mol / L.

[0041] As a specific embodiment of the H-type Y / KCC-1 mesoporous composite molecular sieve described above in the present invention, the mass ratio of the Y / KCC-1 mesoporous composite molecular sieve to the ammonium salt solution is 1:5-20.

[0042] As a specific embodiment of the H-type Y / KCC-1 mesoporous composite molecular sieve described above, the ion exchange temperature is 55 to 95° C. and the time is 0.5 to 5 hours.

[0043] As a specific embodiment of the H-type Y / KCC-1 mesoporous composite molecular sieve described above, the number of ion exchanges is 2 to 4 times.

[0044] As a specific embodiment of the above-mentioned H-type Y / 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.

[0045] As a specific embodiment of the H-type Y / KCC-1 mesoporous composite molecular sieve described above in the present invention, the calcination temperature is 450-650° C. and the calcination time is 1-6 hours.

[0046] The H-type Y / KCC-1 mesoporous composite molecular sieve described above can be prepared according to a preparation method comprising the following steps:

[0047] First, add ammonium salt into water and stir to form an ammonium salt solution. Then, mix the Y / KCC-1 mesoporous composite molecular sieve with the ammonium salt solution to perform ion exchange. After cooling, filter and wash until it is close to neutral, completing an ion exchange. After multiple ion exchanges, finally dry and roast in sequence to obtain the H-type Y / KCC-1 mesoporous composite molecular sieve.

[0048] In the preparation process, the pH value after filtration and washing is 7-9.

[0049] On the other hand, the present invention also provides a hydrocracking catalyst, comprising a carrier and a metal active component loaded on the carrier, wherein the carrier is the H-type Y / 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 4-8wt% and 10-20wt%, respectively.

[0050] As a specific embodiment of the hydrocracking catalyst described above in the present invention, the Group VIII metal includes nickel and / or cobalt, and the Group VIB metal includes molybdenum and / or tungsten.

[0051] On the other hand, the present invention also provides a method for preparing the above-mentioned hydrocracking catalyst, wherein the preparation method comprises:

[0052] The precursor salt of the VIII group metal and the precursor salt of the VIB group metal are added to deionized water and stirred until clear and transparent to obtain an impregnation solution, and then the H-type Y / KCC-1 mesoporous composite molecular sieve is impregnated in the impregnation solution for equal volume impregnation, followed by aging, drying and calcination to obtain the hydrocracking catalyst.

[0053] As the preparation method of the hydrocracking catalyst described above in the present invention, the precursor salt of the VIII group metal includes the nitrate of the VIII group metal, etc., and the precursor salt of the VIB group metal includes the ammonium acid or ammonium meta-acid of the VIB group metal, etc. For example, in some specific embodiments of the present invention, the nitrate of the VIII group metal can be nickel nitrate and / or cobalt nitrate, etc., and the ammonium acid or ammonium meta-acid of the VIB group metal can be ammonium molybdate and / or ammonium metatungstate, etc.

[0054] In the method for preparing the hydrocracking catalyst described above, the stirring is carried out at 50-100° C. for 0.5-2 h.

[0055] In the above-mentioned preparation method of the hydrocracking catalyst of the present invention, during the impregnation process, the impregnation liquid can be dripped onto the H-type Y / KCC-1 mesoporous composite molecular sieve for equal volume impregnation. In some preferred embodiments of the present invention, the dripping is a small amount of multiple dripping.

[0056] As the preparation method of the hydrocracking catalyst described above in the present invention, the aging temperature is 20 to 35° C., and the aging time is 2 to 10 hours.

[0057] In the above-mentioned method for preparing the hydrocracking catalyst of the present invention, the drying temperature is 60-100° C. and the drying time is 5-12 hours.

[0058] As the preparation method of the hydrocracking catalyst described above in the present invention, the calcination temperature is 450-650° C. and the calcination time is 4-8 hours.

[0059] In the present invention, the stirring time involved in the preparation of Y molecular sieve, KCC-1 and Y / 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.

[0060] In the last aspect, the present invention also provides the use of the above-mentioned hydrocracking catalyst (also referred to as Y / KCC-1 composite hydrocracking catalyst) in catalyzing the hydrocracking of 1-methylnaphthalene.

[0061] As a specific implementation of the above application of the present invention, the application includes the following steps:

[0062] Step 1: tableting and screening the hydrocracking catalyst, and then loading it into a reactor;

[0063] Step 2: pre-sulfiding the hydrocracking catalyst before the hydrocracking reaction;

[0064] Step 3: using the presulfurized hydrocracking catalyst to catalyze 1-methylnaphthalene for hydrocracking reaction;

[0065] Step 4: Determine the content of each component in the liquid product obtained after the hydrocracking reaction by gas chromatography-mass spectrometry (GC-MS).

[0066] 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 min. In step 1, the tableting can be performed using a powder tablet press.

[0067] As a specific implementation of the above application of the present invention, in step 1, the mesh size of the sieving is 10-20 meshes or 20-40 meshes.

[0068] As a specific implementation 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.

[0069] As a specific implementation of the above application of the present invention, in step 1, the reactor may be a high-pressure hydrogenation microreactor.

[0070] As a specific embodiment of the above application of the present invention, in step 2, the presulfidation liquid used for presulfidation is a cyclohexane mixed solution with a CS2 content of 1.5 to 5 wt%, the presulfidation 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 2-12h.

[0071] As a specific embodiment of the above application of the present invention, in step 3, the temperature of the hydrocracking reaction is 380-480°C, the pressure is 6-8 MPa, and the liquid hourly space velocity is 0.5-10 h -1 , the hydrogen-to-oil volume ratio can be 1000-1500:1.

[0072] Compared with the prior art, the beneficial technical effects that can be achieved by the present invention include at least:

[0073] The Y / KCC-1 mesoporous composite molecular sieve provided by the present invention has a core-shell structure, including a Y molecular sieve and a KCC-1 mesoporous material tightly wrapped outside the Y molecular sieve. The present invention composites the microporous material Y molecular sieve and the mesoporous material KCC-1 to obtain the Y / KCC-1 mesoporous composite molecular sieve, giving full play to the respective advantages of the microporous material and the mesoporous material, so that the Y / KCC-1 mesoporous composite molecular sieve has excellent diffusion performance, suitable acid properties, and pore structure. The Y / KCC-1 composite hydrocracking catalyst prepared with the Y / KCC-1 mesoporous composite molecular sieve as a carrier is a new catalyst material, which has high catalytic activity and selectivity for the hydrocracking reaction of 1-methylnaphthalene, and shows higher conversion rate, yield and product selectivity, and has potential application value in the field of petrochemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the description of the embodiments will be briefly introduced below. 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 creative work.

[0075] Figure 1 This is the XRD spectrum of the Y / KCC-1 composite molecular sieve, namely YK1, prepared in Example 1 of the present invention.

[0076] Figure 2 This is the XRD diagram of the Y molecular sieve prepared in Comparative Example 1 of the present invention, namely, Yc.

[0077] Figure 3 This is the XRD diagram of KCC-1 molecular sieve, namely Kc, prepared in Comparative Example 2 of the present invention.

[0078] Figure 4 This is the N2- adsorption-desorption isotherm diagram of the Y / KCC-1 composite molecular sieve, namely YK1, prepared in Example 1 of the present invention.

[0079] Figure 5 This is the N2- adsorption-desorption isotherm diagram of the Y molecular sieve, namely Yc, prepared in Comparative Example 1 of the present invention.

[0080] Figure 6 This is the N2- adsorption-desorption isotherm diagram of the KCC-1 molecular sieve, i.e., Kc, prepared in Comparative Example 2 of the present invention.

[0081] Figure 7 This is the pore size distribution diagram of the Y / KCC-1 composite molecular sieve, namely YK1, prepared in Example 1 of the present invention.

[0082] Figure 8This is the pore size distribution diagram of the Y molecular sieve, namely Yc, prepared in Comparative Example 1 of the present invention.

[0083] Fig. 9 This is the pore size distribution diagram of KCC-1 molecular sieve, namely Kc, prepared in Comparative Example 2 of the present invention.

[0084] Fig.10 This is a scanning electron microscope (SEM) spectrum of the Y / KCC-1 composite molecular sieve, namely YK1, prepared in Example 1 of the present invention.

[0085] Fig.11 This is a scanning electron microscope (SEM) spectrum of the Y molecular sieve, namely Yc, prepared in Comparative Example 1 of the present invention.

[0086] Fig.12 This is a scanning electron microscope (SEM) spectrum of the KCC-1 molecular sieve, namely Kc, prepared in Comparative Example 2 of the present invention.

[0087] Fig.13 This is a transmission electron microscope (TEM) spectrum of the Y / KCC-1 composite molecular sieve, namely YK1, prepared in Example 1 of the present invention.

[0088] Fig.14 This is a transmission electron microscope (TEM) spectrum of the KCC-1 molecular sieve, namely Kc, prepared in Comparative Example 2 of the present invention.

[0089] Fig.15 ZLC diffusion curves and fitting curve spectra of the Y / KCC-1 composite molecular sieve prepared in Example 1 of the present invention, namely YK1, the Y molecular sieve prepared in Comparative Example 1, namely Yc, and the KCC-1 molecular sieve prepared in Comparative Example 2, namely Kc. DETAILED DESCRIPTION

[0090] It should be noted that the term "comprises" 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 device 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 inherent to these processes, methods, products or devices.

[0091] "Scope" disclosed in the present invention is given in the form of lower limit and 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, for a specific parameter, a range of 60-120 and 80-110 is listed, 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.

[0092] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in the present invention, and "0-5" is just an abbreviation of these numerical combinations.

[0093] 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.

[0094] 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.

[0095] 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 includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0096] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the attached table, drawings and examples. The following described 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 ordinary technicians in the field without making creative work are within the scope of protection of the present invention. If the specific conditions are not specified in the embodiments, they are carried out according to the normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0097] Y / KCC-1 mesoporous composite molecular sieve embodiment

[0098] Example 1

[0099] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0100] Preparation of microporous material Y molecular sieve:

[0101] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0102] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0103] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0104] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0105] Step (1): adding 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 r / s for 15 min until completely dissolved, to obtain a first mixed solution;

[0106] Step (2): 1.5 g of the microporous material Y molecular sieve 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 the mixture was stirred at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0107] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0108] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK1.

[0109] Example 2

[0110] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0111] Preparation of microporous material Y molecular sieve:

[0112] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0113] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0114] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0115] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0116] Step (1): adding 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 r / s for 15 min until completely dissolved, to obtain a first mixed solution;

[0117] Step (2): add 1 g of the microporous material Y molecular sieve prepared above to 90 ml of cyclohexane solvent, ultrasonicate for 2 h, add 7.48 ml of tetraethyl silicate, and stir at room temperature at a speed of 500 r / s for 15 min to obtain a second mixed solution;

[0118] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0119] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK2.

[0120] Example 3

[0121] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0122] Preparation of microporous material Y molecular sieve:

[0123] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0124] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0125] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0126] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0127] Step (1): adding 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 / s for 15 min until completely dissolved, to obtain a first mixed solution;

[0128] Step (2): adding 2 g of the microporous material Y molecular sieve prepared above to 90 ml of cyclohexane solvent, ultrasonicating for 2 h, adding 7.48 ml of tetraethyl silicate, and stirring at 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0129] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0130] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK3.

[0131] Example 4

[0132] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0133] Preparation of microporous material Y molecular sieve:

[0134] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0135] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0136] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0137] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0138] Step (1): adding 3.06 g of hexadecyltrimethylammonium bromide and 2.67 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 r / s for 20 min until completely dissolved, to obtain a first mixed solution;

[0139] Step (2): 1.5 g of the microporous material Y molecular sieve 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 the mixture was stirred at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0140] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0141] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK4.

[0142] Example 5

[0143] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0144] Preparation of microporous material Y molecular sieve:

[0145] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0146] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0147] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0148] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0149] Step (1): adding 3.06 g of hexadecyltrimethylammonium bromide and 3.14 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 r / s for 25 min until completely dissolved, to obtain a first mixed solution;

[0150] Step (2): 1.5 g of the microporous material Y molecular sieve 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 the mixture was stirred at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0151] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0152] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK5.

[0153] Example 6

[0154] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0155] Preparation of microporous material Y molecular sieve:

[0156] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0157] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0158] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0159] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0160] Step (1): adding 4.59 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 / s for 20 min until completely dissolved, to obtain a first mixed solution;

[0161] Step (2): 1.5 g of the microporous material Y molecular sieve 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 the mixture was stirred at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0162] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0163] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK6.

[0164] Example 7

[0165] This embodiment provides a Y / KCC-1 mesoporous composite molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0166] Preparation of microporous material Y molecular sieve:

[0167] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0168] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0169] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, and dried at 100°C for 10 hours to obtain microporous material Y molecular sieve. The silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1, calculated as oxide.

[0170] Preparation of Y / KCC-1 mesoporous composite molecular sieve:

[0171] Step (1): adding 5.37 g of hexadecyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water, stirring at room temperature at a speed of 400 r / s for 25 min until completely dissolved, to obtain a first mixed solution;

[0172] Step (2): 1.5 g of the microporous material Y molecular sieve prepared above was added to 90 ml of cyclohexane solvent, and after ultrasonication for 2 h, 7.48 ml of tetraethyl silicate (density 0.94 g / cm 3 ), stirring at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0173] Step (3): adding the second mixed solution to the first mixed solution, stirring at a speed of 700 r / s for 15 min at room temperature, adding 5 ml of n-pentanol, stirring at a speed of 400 r / s for 30 min at room temperature, to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion;

[0174] Step (4): The Y / KCC-1 mesoporous composite molecular sieve precursor emulsion is 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 a Y / KCC-1 mesoporous composite molecular sieve, denoted as YK7.

[0175] Y / KCC-1 Composite Hydrocracking Catalyst Example

[0176] Example 1-1

[0177] This embodiment provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0178] An ammonium chloride aqueous solution with a concentration of 1 mol / L was prepared, 2 g of YK1 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK1:ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, filtered and washed until the pH value was 8, and after ion exchange for 3 times, dried at 80°C for 10 h, and calcined at 550°C for 3 h, to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0179] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated on 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition of which was 10wt% WO3, 5wt% NiO and 85wt% carrier, recorded as CAT1.

[0180] Example 1-2

[0181] This embodiment provides a Y / 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 YK2 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK2:ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, filtered and washed until the pH value was 8, and after ion exchange for 3 times, dried at 80°C for 10 h, and calcined at 550°C for 3 h, to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0183] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated on 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition of which was 10wt% WO3, 5wt% NiO and 85wt% carrier, recorded as CAT2.

[0184] Examples 1-3

[0185] This embodiment provides a Y / 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 YK3 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK3:ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, and the solution was filtered and washed until the pH value was 8. After ion exchange was performed three times, the solution was dried at 80°C for 10 h, and calcined at 550°C for 3 h to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0187] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition of which was 10wt% WO3, 5wt% NiO and 85wt% carrier, recorded as CAT3.

[0188] Examples 1-4

[0189] This embodiment provides a Y / 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 YK4 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK4: ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, and the solution was filtered and washed until the pH value was 8. After ion exchange was performed three times, the solution was dried at 80°C for 10 h, and calcined at 550°C for 3 h to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0191] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition of which was 10wt% WO3, 5wt% NiO and 85wt% carrier, recorded as CAT4.

[0192] Examples 1-5

[0193] This embodiment provides a Y / 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 YK5 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK5: ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, and the mixture was filtered and washed until the pH value was 8. After ion exchange was performed three times, the mixture was dried at 80°C for 10 h, and calcined at 550°C for 3 h to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0195] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition being 10wt% WO3, 5wt% NiO and 85wt% carrier, denoted as CAT5.

[0196] Examples 1-6

[0197] This embodiment provides a Y / 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 YK6 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK6: ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, and the mixture was filtered and washed until the pH value was 8. After ion exchange was performed three times, the mixture was dried at 80°C for 10 h, and calcined at 550°C for 3 h to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0199] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated into 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition being 10wt% WO3, 5wt% NiO and 85wt% carrier, denoted as CAT6.

[0200] Examples 1-7

[0201] This embodiment provides a Y / 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 YK7 was used as a carrier and mixed with the ammonium chloride aqueous solution at a mass ratio of YK7:ammonium chloride aqueous solution = 1:10, ion exchange was performed at 80°C and a stirring speed of 350 r / s for 1.5 h, filtered and washed until the pH value was 8, and after ion exchange for 3 times, dried at 80°C for 10 h, and calcined at 550°C for 3 h, to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0203] 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution. An equal volume of the prepared impregnation solution was impregnated on 1.5g of H-type Y / KCC-1 mesoporous composite molecular sieve, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst, the catalyst composition of which was 10wt% WO3, 5wt% NiO and 85wt% carrier, and was recorded as CAT7.

[0204] Comparative Example 1

[0205] This comparative example provides a microporous material Y molecular sieve, which is prepared by a preparation method comprising the following specific steps:

[0206] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0207] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0208] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, dried at 100°C for 10 hours, and calcined at 500°C for 4 hours to obtain microporous material Y molecular sieve, denoted as Yc. Calculated as oxide, the silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1.

[0209] Comparative Example 2

[0210] This comparative example provides a mesoporous material KCC-1, which is prepared by a preparation method comprising the following specific steps:

[0211] 3.06 g of hexadecyltrimethylammonium bromide and 1.78 g of urea were added to 90 ml of deionized water, and stirred at 400 r / s for 15 min at room temperature until completely dissolved to obtain a first mixed solution;

[0212] 7.48 ml of tetraethyl silicate was added to 90 ml of cyclohexane solvent, and stirred at 500 r / s for 15 min at room temperature to obtain a second mixed solution;

[0213] The second mixed solution was added to the first mixed solution, and the mixture was stirred at a speed of 700 r / s for 15 min at room temperature. 5 ml of n-pentanol was added, and the mixture was stirred at a speed of 400 r / s for 30 min at room temperature to obtain a KCC-1 mesoporous molecular sieve precursor emulsion.

[0214] 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 KCC-1 mesoporous molecular sieve, which was recorded as Kc.

[0215] Comparative Example 3

[0216] This comparative example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0217] 1. Preparation of microporous material Y molecular sieve:

[0218] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0219] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0220] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, dried at 100°C for 10 hours, and calcined at 500°C for 4 hours to obtain microporous material Y molecular sieve, denoted as Yc. Calculated as oxide, the silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1.

[0221] 2. Preparation of H-type Y molecular sieve:

[0222] Step 4): prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L, use 2 g of Yc as a carrier and mix Yc with the ammonium chloride aqueous solution at a mass ratio of Yc: ammonium chloride aqueous solution = 1:10, perform ion exchange at 80°C and a stirring speed of 350 r / s for 1.5 hours, filter and wash until the pH value is 8, perform ion exchange three times, dry at 80°C for 10 hours, and calcine at 550°C for 3 hours to obtain an H-type Y molecular sieve, recorded as H-Yc.

[0223] 3. Hydrothermal pickling treatment:

[0224] Step 5): hydrothermally treating the H-type Y molecular sieve, i.e., H-Yc, at 650° C. and 0.3 MPa for 2 h to obtain the hydrothermally treated Y molecular sieve;

[0225] Step 6): The Y molecular sieve after hydrothermal treatment is mixed with a 1.5 mol / L hydrochloric acid solution at a solid-liquid ratio (mass ratio) of 1:10, and treated at 80°C and a speed of 400 r / s for 3 hours, filtered and washed until neutral, dried at 70°C for 10 hours, and calcined at 500°C for 4 hours to obtain a carrier, recorded as carrier a.

[0226] 4. Preparation of hydrocracking catalyst:

[0227] Step 7): 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution, and an equal volume of the prepared impregnation solution was impregnated onto a carrier a, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y hydrocracking catalyst, wherein the catalyst composition was 10wt% WO3, 5wt% NiO and 85wt% carrier, denoted as CATA.

[0228] Comparative Example 4

[0229] This comparative example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method comprising the following specific steps:

[0230] 1. Preparation of microporous material Y molecular sieve:

[0231] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide are added to 9.98 g of deionized water, stirred at 500 r / s for 15 min at room temperature until completely dissolved, 10.24 g of sodium silicate solution (25 wt% SiO2) is added at a stirring speed of 700 r / s, stirred for 5 min to form a seed gel precursor, and aged at 25° C. for 20 h to obtain a seed gel of microporous material Y molecular sieve; in step 1), the molar ratio of the components of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O=15.96:1:6.74:316.48, calculated as oxide;

[0232] Step 2): 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate were added to 64.27 g of deionized water, and stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. 68.44 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. The molar ratio of the components of the reaction mixture, calculated as oxides, was Na2O:Al2O3:SiO2:H2O=8.23 :1:7.19:329.21;7.32g of the seed gel prepared in step 1) is added to the reaction mixture and stirred at a stirring speed of 250r / s for 15min, and aged at 30°C for 15h to form a reactant gel;the molar ratio of the components of the reactant gel is Na2O:Al2O3:SiO2:H2O=2.33:1:8.37:382.38 in terms of oxides;the amount of the seed gel added accounts for 4.9% of the total mass of the reactant gel;

[0233] Step 3): The reactant gel obtained in step 2) is hydrothermally crystallized at 110°C for 12 hours, centrifuged, washed to a pH value of 9, dried at 100°C for 10 hours, and calcined at 500°C for 4 hours to obtain microporous material Y molecular sieve, denoted as Yc. Calculated as oxide, the silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1.

[0234] 2. Preparation of H-type Y molecular sieve:

[0235] Step 4): prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L, use 2 g of Yc as a carrier and mix Yc with the ammonium chloride aqueous solution at a mass ratio of Yc: ammonium chloride aqueous solution = 1:10, perform ion exchange at 80°C and a stirring speed of 350 r / s for 1.5 hours, filter and wash until the pH value is 8, perform ion exchange three times, dry at 80°C for 10 hours, and calcine at 550°C for 3 hours to obtain an H-type Y molecular sieve, recorded as H-Yc.

[0236] 3. Hydrothermal alkali washing treatment:

[0237] Step 5): hydrothermally treating the H-type Y molecular sieve, i.e., H-Yc, at 650° C. and 0.3 MPa for 2 h to obtain the hydrothermally treated Y molecular sieve;

[0238] Step 6): The Y molecular sieve after hydrothermal treatment is mixed with a sodium hydroxide solution with a concentration of 0.5 mol / L at a solid-liquid ratio (weight ratio) of 1:10, and treated at 70°C and a speed of 400r / s for 2h, filtered and washed until neutral, dried at 70°C for 10h, and calcined at 500°C for 4h to obtain a carrier, recorded as carrier b.

[0239] 4. Preparation of hydrocracking catalyst:

[0240] Step 7): 0.21g of ammonium metatungstate and 0.39g of nickel nitrate were dissolved in deionized water, stirred at 60°C and 400r / s for 1h until the solution became clear and transparent, and the volume of the solution was fixed to 1.8ml to obtain an impregnation solution, and an equal volume of the prepared impregnation solution was impregnated onto a carrier b, aged at 25°C for 5h, dried at 90°C for 10h, and calcined at 550°C for 6h to obtain a NiW / Y hydrocracking catalyst, wherein the catalyst composition was 10wt% WO3, 5wt% NiO and 85wt% carrier, denoted as CATB.

[0241] Characterization Test Case

[0242] In this test example, the Y / KCC-1 micro-mesoporous composite molecular sieve, i.e., YK1, 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 Fig.10 The transmission electron microscopy results are shown in Fig.13 The diffusion performance results are shown in Fig.15 shown.

[0243] In this test example, the Y molecular sieve, i.e., Yc, prepared in Comparative Example 1 was analyzed by XRD, N2- adsorption and desorption, scanning electron microscopy, and diffusion performance. The XRD results are as follows: 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 Fig.11 The diffusion performance results are shown in Fig.15 shown.

[0244] In this test example, the KCC-1 molecular sieve prepared in comparative example 2, i.e., Kc, was analyzed by XRD, N2- adsorption and desorption, scanning electron microscopy, transmission electron microscopy, diffusion performance, etc. The XRD results are as follows: Figure 3As shown, the N2- adsorption-desorption isotherm is as follows Figure 6 The pore size distribution results are shown in Fig. 9 The scanning electron microscopy results are shown in Fig.12 The transmission electron microscopy results are shown in Fig.14 The diffusion performance results are shown in Fig.15 shown.

[0245] From the above results, it can be seen that the Y / KCC-1 mesoporous composite molecular sieve provided in Example 1 of the present invention has a core-shell structure, including a Y molecular sieve and a KCC-1 mesoporous material, the KCC-1 mesoporous material is tightly wrapped outside the Y molecular sieve, and the surface morphology of the Y / KCC-1 mesoporous composite molecular sieve is fibrous. The present invention successfully composites the Y molecular sieve with the KCC-1 mesoporous material, and the resulting Y / KCC-1 mesoporous composite molecular sieve has a physical structure similar to that of the microporous Y molecular sieve; the surface morphologies of the KCC-1 mesoporous material and the Y / KCC-1 mesoporous composite molecular sieve are both fibrous, indicating that their unique morphologies are retained before and after the composite.

[0246] This test example also measured the average particle size, specific surface area, pore size and pore volume data of the Y / KCC-1 micro-mesoporous composite molecular sieve provided in Examples 1 to 7, the Y molecular sieve provided in Comparative Example 1, the KCC-1 molecular sieve provided in Comparative Example 2, the hydrothermal acid-treated Y molecular sieve provided in Comparative Example 3, i.e., carrier a, and the hydrothermal alkali-treated Y molecular sieve provided in Comparative Example 4, i.e., carrier b. The results are shown in Table 1 below.

[0247] Table 1

[0248]

[0249] It can be seen from Table 1 above that the Y / KCC-1 mesoporous and microporous composite molecular sieve prepared in the embodiment of the present invention has a larger specific surface area, pore volume and pore size than the microporous Y molecular sieve, which indicates that the present invention can effectively improve the pore structure properties of the material by compounding the microporous Y molecular sieve and the KCC-1 mesoporous material, and can also accurately control the particle size of the mesoporous and microporous composite molecular sieve.

[0250] This test example also measured the effective diffusion coefficient data of the Y / KCC-1 composite molecular sieve provided in Example 1, i.e., YK1, the Y molecular sieve provided in Comparative Example 1, i.e., Yc, and the KCC-1 molecular sieve provided in Comparative Example 2, i.e., Kc. The results are shown in Table 2 below.

[0251] Table 2

[0252] project Effective diffusion coefficient Example 1 1.01E-03 Comparative Example 1 6.05E-04 Comparative Example 2 2.30E-03

[0253] Combination Fig.15As can be seen from Table 2, the relationship between the effective diffusion coefficients is: Comparative Example 2>Example 1>Comparative Example 1, which means 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 capacity of the reactant molecules in the pores.

[0254] Performance test case

[0255] This test example evaluates the 1-methylnaphthalene hydrocracking reaction catalyzed by CAT1-CAT7 provided in Examples 1-1 to 1-7 of the present invention, and CATA and CATB provided in Comparative Examples 3-4. The evaluation is carried out on a fixed bed microreactor. During the evaluation, the conversion rate, yield and selectivity of the hydrocracking of the catalyst are investigated. The experimental data obtained are shown in Table 3 below. The specific steps are as follows:

[0256] Step 1: The catalysts provided in Examples 1 to 7 and Comparative Examples 3 to 4 were tableted at a pressure of 25 MPa for 10 min, sieved into 20-40 meshes, and 1 g was loaded into a reactor;

[0257] Step 2: The above catalysts were pre-sulfurized before the hydrogenation reaction, wherein the pre-sulfurization liquid used for pre-sulfurization was a cyclohexane mixed solution with a CS2 content of 1.5 wt%, and the pre-sulfurization conditions included: hydrogen pressure 6 MPa, hydrogen-oil volume ratio 600:1, liquid hourly space velocity 2.5 h -1 , 230℃ for 2h, 320℃ for 3h;

[0258] Step 3: 1-methylnaphthalene is subjected to a hydrocracking reaction in a high-pressure hydrogenation microreactor, i.e., a fixed-bed microreactor, wherein the reaction temperature is 480°C, the reaction pressure is 6 MPa, and the liquid hourly space velocity is 2 h -1 , the volume ratio of hydrogen to oil is 1200:1;

[0259] Step 4: Using gas chromatography-mass spectrometry (GC-MS) to measure the content of each component in the liquid product obtained from the hydrocracking reaction.

[0260] Table 3

[0261]

[0262]

[0263] The results of the hydrocracking catalytic reaction of 1-methylnaphthalene by each catalyst shown in Table 3 above show that the conversion rate, alkylbenzene yield and alkylbenzene selectivity of 1-methylnaphthalene in the Y / KCC-1 composite hydrocracking catalyst provided in the embodiment of the present invention are significantly higher than those of the hydrocracking catalyst prepared with the conventional modified Y molecular sieve as the carrier. Therefore, this novel composite hydrocracking catalyst provided in the embodiment of the present invention has great potential industrial application value.

[0264] In summary, the Y / KCC-1 mesoporous composite molecular sieve provided in the embodiment of the present invention has a core-shell structure, including a Y molecular sieve and a KCC-1 mesoporous material tightly wrapped outside the Y molecular sieve. In the embodiment of the present invention, the microporous material Y molecular sieve and the mesoporous material KCC-1 are compounded to obtain the Y / KCC-1 mesoporous composite molecular sieve, which gives full play to the respective advantages of the microporous material and the mesoporous material, so that the Y / KCC-1 mesoporous composite molecular sieve has excellent diffusion performance, suitable acid properties, and pore structure. The Y / KCC-1 composite hydrocracking catalyst prepared with the Y / KCC-1 mesoporous composite molecular sieve as a carrier is a new catalyst material, which has high catalytic activity and selectivity for the hydrocracking reaction of 1-methylnaphthalene, and shows higher conversion rate, yield and product selectivity, and has potential application value in the field of petrochemical industry.

[0265] The above is only a specific embodiment of the present invention, and cannot be used to limit the scope of the invention. Therefore, the replacement of equivalent components, or equivalent changes and modifications made according to the protection scope of the patent of the present invention, should still fall within the scope of this patent. In addition, the technical features of the present invention can be freely combined with each other, with each other and with each other, and with each other.

Claims

1. A Y / KCC-1 mesoporous composite molecular sieve, characterized in that: The Y / KCC-1 mesoporous composite molecular sieve has a core-shell structure, including a Y molecular sieve and a KCC-1 mesoporous material, wherein the KCC-1 mesoporous material is tightly wrapped outside the Y molecular sieve, and the surface morphology of the Y / KCC-1 mesoporous composite molecular sieve is fibrous.

2. The Y / KCC-1 mesoporous composite molecular sieve according to claim 1, characterized in that: The specific surface area of ​​the Y / KCC-1 mesoporous composite molecular sieve is 590 to 800 m 2 ·g -1 , pore diameter is 7.4~10nm, pore volume is 0.4~1.0cm 3 ·g -1 And the average particle size is 150 to 750 nm.

3. The method for preparing the Y / KCC-1 mesoporous composite molecular sieve according to claim 1 or 2, characterized in that: The preparation method comprises: Step (1): adding a surfactant and a hydrolyzing agent into water and dissolving them completely to obtain a first mixed solution; Step (2): adding the Y molecular sieve obtained by calcination or without calcination into an organic solvent to dissolve it, and then adding an organic silicon source and mixing them uniformly to obtain a second mixed solution; Step (3): after the first mixed solution and the second mixed solution are fully mixed, a co-surfactant is added and mixed evenly to obtain a Y / KCC-1 mesoporous composite molecular sieve precursor emulsion; 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 Y molecular sieve and organosilicon source calculated as SiO2 is 0.10-2.50:1; Step (4): subjecting the Y / KCC-1 mesoporous composite molecular sieve precursor emulsion to hydrothermal crystallization treatment, centrifuging and washing after the hydrothermal crystallization treatment, and then drying and calcining to obtain the Y / KCC-1 mesoporous composite molecular sieve.

4. The preparation method according to claim 3, characterized in that: In step (1), the surfactant includes one or a combination of cetyltrimethylammonium bromide, tetramethoxysilane, cetylpyridinium bromide, cetyltrimethylammonium chloride and dodecyltrimethylammonium chloride; Preferably, the hydrolyzing agent includes one or a combination of urea, organic amine, triethanolamine and ammonia water; Also preferably, in step (2), the organic solvent comprises one or a combination of cyclohexane, toluene, 1-octadecene, diethyl ether, octane and styrene; Also preferably, the organic silicon source includes one or a combination of tetraethyl silicate, tetraethoxysilane and tetramethoxysilane; Also preferably, in step (3), the co-surfactant comprises one or a combination of n-pentanol, isopropanol, n-butanol, 1-butyl-3-methylimidazolium trifluoromethanesulfonate and ethanol; Also preferably, in step (4), the temperature of the hydrothermal crystallization treatment is 60 to 120° C., and the time is 2 to 20 hours; Also preferably, the drying temperature is 25 to 90° C. and the drying time is 4 to 12 hours; Also preferably, the calcination temperature is 450-650° C. and the calcination time is 4-8 hours.

5. An H-type Y / KCC-1 mesoporous composite molecular sieve, which is obtained by subjecting the Y / KCC-1 mesoporous composite molecular sieve according to claim 1 or 2 to ion exchange with an ammonium salt solution, and then drying and calcining the product; preferably, the ammonium salt comprises one or a combination of ammonium nitrate, ammonium chloride and ammonium sulfate; Also preferably, the concentration of the ammonium salt solution is 1 to 4 mol / L; Also preferably, the mass ratio of the Y / KCC-1 mesoporous composite molecular sieve to the ammonium salt solution is 1:5-20; Also preferably, the ion exchange temperature is 55 to 95° C. and the time is 0.5 to 5 h; Also preferably, the number of ion exchanges is 2 to 4 times; Also preferably, the drying temperature is 60-100°C and the drying time is 7-12h; Also preferably, the calcination temperature is 450-650° C. and the calcination time is 1-6 hours.

6. A hydrocracking catalyst comprising a carrier and a metal active component supported on the carrier, characterized in that: The carrier is the H-type Y / KCC-1 mesoporous composite molecular sieve as described in claim 5, and the metal active components include Group VIII metals and Group VIB metals; based on the total weight of the hydrocracking catalyst as 100%, the contents of Group VIII metals and Group VIB metals in terms of oxides are 4-8wt% and 10-20wt%, respectively.

7. The method for preparing the hydrocracking catalyst according to claim 6, characterized in that: The preparation method comprises: The precursor salt of the VIII group metal and the precursor salt of the VIB group metal are added to deionized water and stirred until clear and transparent to obtain an impregnation solution, and then the H-type Y / KCC-1 mesoporous composite molecular sieve is impregnated in the impregnation solution for equal volume impregnation, followed by aging, drying and calcination to obtain the hydrocracking catalyst.

8. The preparation method according to claim 7, characterized in that: The precursor salt of the Group VIII metal includes the nitrate of the Group VIII metal, and the precursor salt of the Group VIB metal includes the ammonium acid or ammonium metaacid of the Group VIB metal; Preferably, the stirring is carried out at 50-100° C. and the stirring time is 0.5-2 h; Also preferably, the aging temperature is 20 to 35° C., and the aging time is 2 to 10 hours; Also preferably, the drying temperature is 60 to 100° C. and the drying time is 5 to 12 hours; Also preferably, the calcination temperature is 450-650° C., and the calcination time is 4-8 hours.

9. Use of the hydrocracking catalyst according to claim 6 in catalyzing the hydrocracking of 1-methylnaphthalene.

10. The use according to claim 9, characterized in that: The application comprises the following steps: Step 1: tableting and screening the hydrocracking catalyst, and then loading it into a reactor; Preferably, in step 1, the tabletting pressure is 20-30 MPa, and the time is 10-20 min; preferably, the sieving mesh size is 10-20 mesh or 20-40 mesh; preferably, the loading amount of the hydrocracking catalyst is 0.5-1.5 g; Step 2: pre-sulfiding the hydrocracking catalyst before the hydrocracking reaction; Preferably, in step 2, the presulfiding liquid used for presulfiding is a cyclohexane mixed solution with a CS2 content of 1.5 to 5 wt%, the presulfiding 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 2-12h; Step 3: using the presulfurized hydrocracking catalyst to catalyze 1-methylnaphthalene for hydrocracking reaction; Preferably, in step 3, the temperature of the hydrocracking reaction is 380-480°C, the pressure is 6-8 MPa, and the liquid hourly space velocity is 0.5-10 h -1 , the volume ratio of hydrogen to oil can be 1000-1500:1; Step 4: Determine the content of each component in the liquid product obtained after the hydrocracking reaction by gas chromatography-mass spectrometry.

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