Y / KCC-1 Mesoporous-Microporous Composite Molecular Sieve and Its Preparation, Hydrocracking Catalyst and Its Preparation and Application

Abstract

The present invention provides a Y / KCC-1 mesoporous / microporous composite molecular sieve and its preparation method, a hydrocracking catalyst and its preparation method and application. The Y / KCC-1 mesoporous / microporous composite molecular sieve has a core-shell structure, including a Y molecular sieve and a KCC-1 mesoporous material. The KCC-1 mesoporous material tightly wraps around the outside of the Y molecular sieve, and the surface morphology of the Y / KCC-1 mesoporous / microporous composite molecular sieve is fibrous. In the present invention, the microporous material Y molecular sieve and the mesoporous material KCC-1 are compounded, giving full play to the respective advantages of the microporous material and the mesoporous material, so that the composite molecular sieve has excellent diffusion performance, suitable acid properties and pore structure. The Y / KCC-1 composite hydrocracking catalyst prepared with this composite molecular sieve as the carrier is a novel catalyst material, which has relatively high catalytic activity and selectivity for the hydrocracking reaction of 1-methylnaphthalene, showing higher conversion rate, yield and product selectivity.

Description

Technical Field

[0001] The present invention relates to a Y / KCC-1 mesoporous / microporous composite molecular sieve and its preparation, a hydrocracking catalyst and its preparation and application, belonging to the technical field of petrochemical industry, especially the hydrocracking technology field. Background Art

[0002] Currently, the hydrocracking technology has become an important measure to optimize the structure of petroleum products and enhance the market adaptability. Developing hydrocracking catalysts with molecular sieve materials as carriers is the main direction of the research and development of the hydrocracking process. The properties of molecular sieves are crucial for the catalytic performance of the catalysts. Molecular sieve-based catalysts mostly use Y zeolite, Beta zeolite, ZSM-5 zeolite, etc. as carriers. These materials have suitable surface structures, pore size distributions, and acid properties. However, with the increasing heavy quality 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 large pore size, which is beneficial to the dispersion of active components. At the same time, it greatly reduces the restriction of the pore channels on the reactant and product molecules, and significantly enhances the diffusion and transmission capabilities. Hydrocracking catalysts need to have suitable hydrogenation performance and strong cracking performance, requiring the carrier material to have suitable acid properties. However, the acidity of mesoporous materials is weak and cannot be used alone as a carrier material. Combining mesoporous materials with microporous materials to prepare mesoporous / microporous composite materials can effectively improve the limitation of the relatively narrow pore size of microporous materials, and at the same time solve the problem of weak acidity of mesoporous materials, providing new ideas for the further development of hydrocracking catalysts.

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

[0004] Therefore, providing a novel Y / KCC-1 mesoporous / microporous composite molecular sieve and its preparation, a hydrocracking catalyst and its preparation and application has become an urgent technical problem to be solved in this field. Summary of the Invention

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

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

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

[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 fibrous pore structure, which can effectively improve the accessibility of active sites, enhance the diffusion performance of the catalyst, and at the same time has good thermal and hydrothermal stability.

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

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

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

[0012] Step (3): After mixing the first mixed solution and the second mixed solution thoroughly, add a co-surfactant and mix them evenly to obtain a Y / KCC-1 mesoporous and microporous composite molecular sieve precursor emulsion;

[0013] wherein the molar ratio of the surfactant, the hydrolyzing agent, water, the organic solvent, the co-surfactant and the organic silicon 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 the Y molecular sieve and the organic silicon source calculated as SiO2 is 0.10-2.50:1;

[0014] Step (4): Hydrothermally crystallize the Y / KCC-1 mesoporous and microporous composite molecular sieve precursor emulsion, perform centrifugation and washing after hydrothermal crystallization, and then obtain the Y / KCC-1 mesoporous and microporous composite molecular sieve through drying and calcination.

[0015] As a specific embodiment of the above-described preparation method of the present invention, in step (1), the surfactant includes one or a combination of cetyltrimethylammonium bromide, tetramethoxysilane, cetylpyridinium bromide, cetyltrimethylammonium chloride, decyltrimethylammonium chloride, etc.

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

[0017] In step (1) of the preparation method of the above-described Y / KCC-1 mesoporous and microporous composite molecular sieve of the present invention, the complete dissolution can be achieved by stirring. In some embodiments of the present invention, the stirring can be carried out at room temperature. As a specific embodiment of the above-described preparation method of the present invention, in step (2), the organic solvent includes one or a combination of cyclohexane, toluene, 1-octadecene, diethyl ether, octane, styrene, etc.

[0018] As a specific embodiment of the above-described preparation method of the present invention, in step (2), the organosilicon source includes one or a combination of tetraethyl orthosilicate, tetraethoxysilane, tetramethoxysilane, etc.

[0019] In step (2) of the preparation method of the above-described Y / KCC-1 mesoporous and microporous composite molecular sieve of the present invention, 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 conditions of this stirring in step (2), such as the stirring time, etc., and can be reasonably adjusted as needed. In some more preferred embodiments of the present invention, the stirring time can be, for example, 5 to 30 min.

[0020] As a specific embodiment of the above-described preparation method of the present invention, in step (2), the Y molecular sieve is a Y molecular sieve obtained by calcination or without calcination. Among them, when calcination is carried out, the calcination temperature can be 500 to 600 °C, and the calcination time can be 3 to 6 h. Preferably, the Y molecular sieve is preferably a Y molecular sieve obtained without calcination. In step (2) of the preparation method of the above-described Y / KCC-1 mesoporous and microporous composite molecular sieve of the present invention, the Y molecular sieve obtained without calcination can be prepared by a preparation method including the following steps:

[0021] Step 1): Add an alkali source and an aluminum source to water, then add a silicon source, stir to form a seed gel precursor, and prepare a seed gel of the microporous material Y molecular sieve through aging.

[0022] Step 2): Mix the alkali source, aluminum source and silicon source to form a reaction mixture. Add the seed gel obtained in Step 1) to the reaction mixture, stir, and then age to form a reactant gel.

[0023] Step 3): Perform hydrothermal crystallization treatment on the reactant gel. After treatment, centrifuge, wash, and then dry to obtain the microporous material Y zeolite.

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

[0025] Step 1): Add the alkali source and aluminum source to water, stir at room temperature until completely dissolved, add the silicon source under stirring, stir to form a seed gel precursor, and age without stirring to obtain the seed gel of the microporous material Y zeolite.

[0026] Step 2): Add the alkali source and aluminum source to water, stir at room temperature until completely dissolved, then add the silicon source while stirring rapidly until a homogeneous gel state is reached to obtain a reaction mixture. Add the seed gel prepared in Step 1) to the reaction mixture, stir, and age without stirring to form a reactant gel.

[0027] Step 3): Perform hydrothermal crystallization treatment on the reactant gel obtained in Step 2), centrifuge, wash, and then dry to obtain the microporous material Y zeolite.

[0028] In Step 1) of preparing the Y zeolite, the alkali source can be sodium hydroxide, sodium carbonate, etc., the aluminum source can be sodium aluminate, alumina, aluminum nitrate, aluminum chloride, etc., and the silicon source can be sodium silicate, silica sol, tetraethyl orthosilicate, nano-silica, etc.; the stirring time after adding the silicon source can be 5 - 30 min, the aging temperature can be 20 - 55 °C, and the aging time can be 10 - 36 h. Calculated as oxides, the molar ratio of each component in the seed gel of the microporous material Y zeolite is Na2O:Al2O3:SiO2:H2O = 10 - 20:1:5 - 27:200 - 450.

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

[0030] In step 3) of preparing the Y zeolite, the temperature of the hydrothermal crystallization treatment can be 90 - 140 °C, and the time of the hydrothermal crystallization treatment can be 5 - 24 h; the washing is to wash until the pH value is 8 - 10; the drying temperature can be 35 - 110 °C, and the drying time can be 5 - 12 h; calculated as oxides, the silica-alumina molar ratio SiO2 / Al2O3 of the Y zeolite can be 5 - 20:1.

[0031] As a specific embodiment of the above-mentioned preparation method of the present invention, in step (3), the co-surfactant includes one or a combination of several of n-pentanol, isopropanol, n-butanol, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, ethanol, etc.

[0032] In step (3) of the preparation method of the Y / KCC-1 mesoporous and microporous composite zeolite of the present invention above, the second mixed solution is added to the first mixed solution for thorough mixing. Among them, both the thorough mixing and the uniform mixing in step (3) can be achieved by stirring. The present invention does not make specific requirements on the conditions of the stirring for achieving thorough mixing and uniform mixing in step (3), such as the stirring time, etc., and can be reasonably adjusted as needed. In some more preferred embodiments of the present invention, the stirring times for the thorough mixing and the uniform mixing can be 5 - 20 min and 15 - 40 min respectively.

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

[0034] As a specific embodiment of the above-mentioned preparation method of the present invention, in step (4), the drying temperature is 25 - 90 °C, and the time is 4 - 12 h.

[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 time is 4-8 h.

[0036] In step (4) of the preparation method of the Y / KCC-1 micro-mesoporous composite molecular sieve described above of the present invention, the washing reagent used for washing can be reasonably selected as needed. For example, in some more preferred embodiments of the present invention, the washing reagent can be deionized water, acetone, ethanol, etc.

[0037] The Y / KCC-1 micro-mesoporous composite molecular sieve of the present invention is prepared by compositing the microporous material Y molecular sieve as a seed with the mesoporous material KCC-1 under hydrothermal conditions, and has excellent thermal and hydrothermal stabilities. In addition, the acidity of the Y / KCC-1 micro-mesoporous composite molecular sieve can be flexibly controlled by regulating the addition amount of the Y molecular sieve. The Y / KCC-1 micro-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 fibrous pore structure, which is beneficial to reducing the diffusion resistance of reactants and products, effectively enhancing the diffusion performance of the catalyst, increasing the reaction rate, and avoiding overreaction at the same time. During the preparation process, the particle size and pore structure properties of the Y / KCC-1 micro-mesoporous composite molecular sieve can also be regulated by adjusting the addition concentrations of the hydrolyzing agent and the surfactant, the time and temperature of hydrothermal crystallization, the addition ratio of the organic solvent to water, and the stirring time, etc., so that it has excellent diffusion performance, and further improves the catalytic performance of the catalyst using it as a carrier and the product quality.

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

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

[0040] As a specific embodiment of the H-type Y / KCC-1 micro-mesoporous composite molecular sieve described above 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 micro-mesoporous composite molecular sieve described above of the present invention, the mass ratio of the Y / KCC-1 micro-mesoporous composite molecular sieve to the ammonium salt solution is 1:5-20.

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

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

[0044] As a specific embodiment of the above-mentioned H-type Y / KCC-1 mesoporous / microporous composite molecular sieve of the present invention, the temperature of the drying is 60 to 100 °C, and the time is 7 to 12 h.

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

[0046] The above-mentioned H-type Y / KCC-1 mesoporous / microporous composite molecular sieve of the present invention can be prepared according to a preparation method including the following steps:

[0047] First, an ammonium salt is added to water and stirred to form an ammonium salt solution. Then, the Y / KCC-1 mesoporous / microporous composite molecular sieve is mixed with the ammonium salt solution for ion exchange. After cooling, it is suction filtered and washed to be close to neutral to complete one ion exchange. After multiple ion exchanges, finally, drying and calcination are carried out in sequence to obtain the H-type Y / KCC-1 mesoporous / microporous composite molecular sieve.

[0048] Among them, the pH value after suction filtration and washing in the preparation process is 7 to 9.

[0049] On the other hand, the present invention also provides a hydrocracking catalyst, which includes a carrier and a metal active component supported on the carrier. Among them, the carrier is the above-mentioned H-type Y / KCC-1 mesoporous / microporous composite molecular sieve, and the metal active component includes Group VIII metals and Group VIB metals; based on the total weight of the hydrocracking catalyst being 100%, the contents of the Group VIII metals and Group VIB metals in terms of oxides are 4 to 8 wt% and 10 to 20 wt%, respectively.

[0050] As a specific embodiment of the above-mentioned hydrocracking catalyst of the present invention, the Group VIII metals include nickel and / or cobalt, etc., and the Group VIB metals include molybdenum and / or tungsten, etc.

[0051] On the other hand, the present invention also provides a preparation method of the above-mentioned hydrocracking catalyst, and the preparation method includes:

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

[0053] As the preparation method of the hydrocracking catalyst described above in the present invention, among them, the precursor salts of Group VIII metals include nitrates of Group VIII metals, etc., and the precursor salts of Group VIB metals include ammonium acids or meta-acids of Group VIB metals, etc. For example, in some specific embodiments of the present invention, the nitrates of Group VIII metals can be nickel nitrate and / or cobalt nitrate, etc., and the ammonium acids or meta-acids of Group VIB metals can be ammonium molybdate and / or ammonium metatungstate, etc.

[0054] As the preparation method of the hydrocracking catalyst described above in the present invention, among them, the stirring is carried out at 50-100°C, and the stirring time is 0.5-2 h.

[0055] In the preparation method of the hydrocracking catalyst described above in the present invention, during the impregnation process, the impregnation solution can be dropped onto the H-type Y / KCC-1 mesoporous and microporous composite molecular sieve for equal-volume impregnation. In some more preferred embodiments of the present invention, the dropping is carried out in small amounts and multiple times.

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

[0057] As the preparation method of the hydrocracking catalyst described above in the present invention, among them, the drying temperature is 60-100°C, and the drying time is 5-12 h.

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

[0059] In the present invention, the stirring time involved in the preparation of Y molecular sieve, the preparation of KCC-1, and the preparation of the H-type Y / KCC-1 mesoporous and microporous composite molecular sieve can all be reasonably adjusted as needed. For example, in some more preferred embodiments of the present invention, the stirring speed can be 200-1000 r / s.

[0060] Finally, the present invention also provides the application of the above-mentioned hydrocracking catalyst (also denoted as the Y / KCC-1 composite hydrocracking catalyst) in the catalytic hydrocracking of 1-methylnaphthalene.

[0061] As a specific embodiment of the above-mentioned application of the present invention, among them, the application includes the following steps:

[0062] Step 1: Tablet and screen the hydrocracking catalyst, and then load it into a reactor;

[0063] Step 2: Presulfurize the hydrocracking catalyst before the hydrocracking reaction;

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

[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 pressure of the tableting is 20-30 MPa and the time is 10-20 min. In Step 1, the tableting can be carried out using a powder tableting machine.

[0067] As a specific embodiment of the above application of the present invention, in Step 1, the mesh number of the screening is 10-20 mesh or 20-40 mesh.

[0068] As a specific embodiment of the above application of the present invention, in Step 1, the loading amount of the hydrocracking catalyst is 0.5-1.5 g.

[0069] As a specific embodiment of the above application of the present invention, in Step 1, the reactor can be a high-pressure hydrocracking microreactor.

[0070] As a specific embodiment of the above application of the present invention, in Step 2, the presulfurization solution used for presulfurization is a cyclohexane mixed solution with a CS2 content of 1.5-5 wt%, the presulfurization pressure is 4-6 MPa, the hydrogen-oil volume ratio is 500-700:1, and the liquid hourly space velocity is 1-5 h -1 , the presulfurization temperature can be 200-350 °C, and the presulfurization time can be 2-12 h.

[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 , and the hydrogen-oil volume ratio can be 1000-1500:1.

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

[0073] The Y / KCC-1 micro-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. In the present invention, the microporous material Y molecular sieve and the mesoporous material KCC-1 are combined to obtain the Y / KCC-1 micro-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 micro-mesoporous composite molecular sieve has excellent diffusion performance, suitable acidic properties and pore structure. The Y / KCC-1 composite hydrocracking catalyst prepared with the Y / KCC-1 micro-mesoporous composite molecular sieve as the carrier is a new type of catalyst material, which has relatively high catalytic activity and selectivity for the hydrocracking reaction of 1-methylnaphthalene, showing higher conversion rate, yield and product selectivity, and has potential application value in the petrochemical field. Description of the Drawings

[0074] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

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

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

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

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

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

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

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

[0082] Figure 8Pore size distribution diagram of the Y zeolite prepared in Comparative Example 1 of the present invention, i.e., Yc.

[0083] Figure 9 Pore size distribution diagram of the KCC-1 zeolite prepared in Comparative Example 2 of the present invention, i.e., Kc.

[0084] Figure 10 Scanning electron microscope (SEM) spectrum of the Y / KCC-1 composite zeolite prepared in Example 1 of the present invention, i.e., YK1.

[0085] Figure 11 Scanning electron microscope (SEM) spectrum of the Y zeolite prepared in Comparative Example 1 of the present invention, i.e., Yc.

[0086] Figure 12 Scanning electron microscope (SEM) spectrum of the KCC-1 zeolite prepared in Comparative Example 2 of the present invention, i.e., Kc.

[0087] Figure 13 Transmission electron microscope (TEM) spectrum of the Y / KCC-1 composite zeolite prepared in Example 1 of the present invention, i.e., YK1.

[0088] Figure 14 Transmission electron microscope (TEM) spectrum of the KCC-1 zeolite prepared in Comparative Example 2 of the present invention, i.e., Kc.

[0089] Figure 15 ZLC diffusion curves and fitting curve spectra of the Y / KCC-1 composite zeolite prepared in Example 1 of the present invention, i.e., YK1, the Y zeolite prepared in Comparative Example 1, i.e., Yc, and the KCC-1 zeolite prepared in Comparative Example 2, i.e., Kc. Detailed implementation manners

[0090] It should be noted that the term "including" and any variations thereof in the specification, claims and above-mentioned drawings of the present invention are intended to cover non-exclusive inclusion. For example, a process, method, system, product or device that includes a series of steps or units does not necessarily limit to those clearly listed steps or units, but may include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0091] The "ranges" disclosed in the present invention are given in the form of a lower limit and an upper limit. There may 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, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 - 120 and 80 - 110 are listed for a specific parameter, ranges of 60 - 110 and 80 - 120 are also contemplated. Additionally, 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 are all contemplated: 1 - 3, 1 - 4, 1 - 5, 2 - 3, 2 - 4, and 2 - 5.

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

[0093] In the present invention, if there is no special indication, all the 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, if there is no special indication, all the 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, if there is no special indication, all the steps mentioned herein can be carried out in sequence or randomly, but preferably in sequence. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) carried out in sequence, or may also include steps (b) and (a) carried out in sequence. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or may also include steps (a), (c), and (b), or may also include steps (c), (a), and (b), etc.

[0096] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the attached tables, drawings and embodiments. The following described embodiments are some embodiments of the present invention, rather than all of them, and are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For the reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0097] Examples of Y / KCC-1 mesoporous-microporous composite molecular sieve

[0098] Example 1

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

[0100] Preparation of microporous material Y molecular sieve:

[0101] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them to 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of microporous material Y molecular sieve; in Step 1), in terms of oxides, the molar ratio of each component of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

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

[0103] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, and dry at 100 °C for 10 h to obtain the microporous material Y zeolite. Calculated as oxides, the silica-alumina molar ratio SiO₂ / Al₂O₃ of the microporous material Y zeolite is 8:1.

[0104] Preparation of Y / KCC-1 mesoporous-microporous composite zeolite:

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

[0106] Step (2): Add 1.5 g of the above-prepared microporous material Y zeolite into 90 ml of cyclohexane solvent, after ultrasonic treatment for 2 h, add 7.48 ml of tetraethyl orthosilicate, and stir at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

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

[0108] Step (4): Hydrothermally treat the Y / KCC-1 mesoporous-microporous composite zeolite precursor emulsion at 120 °C for 5 h, centrifuge and wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h to obtain the Y / KCC-1 mesoporous-microporous composite zeolite, denoted as YK1.

[0109] Example 2

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

[0111] Preparation of microporous material Y molecular sieve:

[0112] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them to 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of microporous material Y molecular sieve; in Step 1), in terms of oxides, the molar ratio of each component of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

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

[0114] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, and dry at 100 °C for 10 h to obtain the microporous material Y molecular sieve. In terms of oxides, the silica-alumina molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1.

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

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

[0117] Step (2): Add 1 g of the prepared microporous material Y zeolite into 90 ml of cyclohexane solvent. After ultrasonic treatment for 2 h, add 7.48 ml of tetraethyl orthosilicate, and stir at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

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

[0119] Step (4): Hydrothermally treat the Y / KCC-1 mesoporous / microporous composite molecular sieve precursor emulsion at 120 °C for 5 h, centrifuge, wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h to obtain the Y / KCC-1 mesoporous / microporous composite molecular sieve, denoted as YK2.

[0120] Example 3

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

[0122] Preparation of microporous material Y zeolite:

[0123] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them into 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s, stir for 5 min to form a seed gel precursor, and age statically at 25 °C for 20 h to prepare a seed gel of microporous material Y zeolite; In step 1), in terms of oxides, the molar ratio of each component of the seed gel of microporous material Y zeolite is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

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

[0125] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, and dry at 100 °C for 10 h to obtain microporous material Y zeolite. Calculated as oxides, the silica-alumina molar ratio SiO₂ / Al₂O₃ of the microporous material Y zeolite is 8:1.

[0126] Preparation of Y / KCC-1 mesoporous-microporous composite zeolite:

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

[0128] Step (2): Add 2 g of the above-prepared microporous material Y zeolite into 90 ml of cyclohexane solvent, after ultrasonic treatment for 2 h, add 7.48 ml of tetraethyl orthosilicate, and stir at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

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

[0130] Step (4): Hydrothermally treat the Y / KCC-1 mesoporous-microporous composite zeolite precursor emulsion at 120 °C for 5 h, centrifuge and wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h to obtain Y / KCC-1 mesoporous-microporous composite zeolite, denoted as YK3.

[0131] Example 4

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

[0133] Preparation of microporous material Y molecular sieve:

[0134] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them to 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of the microporous material Y molecular sieve; in Step 1), in terms of oxides, the molar ratio of each component of the seed gel of the microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

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

[0136] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, and dry at 100 °C for 10 h to obtain the microporous material Y molecular sieve. In terms of oxides, the silica-alumina molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1.

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

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

[0139] Step (2): Add 1.5 g of the above-prepared microporous material Y zeolite into 90 ml of cyclohexane solvent. After ultrasonic treatment for 2 h, add 7.48 ml of tetraethyl orthosilicate and stir at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

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

[0141] Step (4): Hydrothermally treat the Y / KCC-1 mesoporous / microporous composite molecular sieve precursor emulsion at 120 °C for 5 h, centrifuge, wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h to obtain the Y / KCC-1 mesoporous / microporous composite molecular sieve, denoted as YK4.

[0142] Example 5

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

[0144] Preparation of microporous material Y zeolite:

[0145] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them into 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of the microporous material Y zeolite; In Step 1), in terms of oxides, the molar ratio of each component of the seed gel of the microporous material Y zeolite is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

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

[0147] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, dry at 100 °C for 10 h to obtain the microporous material Y zeolite. Calculated as oxides, the silica-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y zeolite is 8:1.

[0148] Preparation of Y / KCC-1 mesoporous-microporous composite zeolite:

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

[0150] Step (2): Add 1.5 g of the microporous material Y zeolite prepared above into 90 ml of cyclohexane solvent, after ultrasonic treatment for 2 h, add 7.48 ml of tetraethyl orthosilicate, stir at a speed of 500 r / s for 15 min at room temperature to obtain a second mixed solution;

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

[0152] Step (4): Hydrothermally treat the Y / KCC-1 mesoporous-microporous composite zeolite precursor emulsion at 120 °C for 5 h, centrifuge and wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h to obtain the Y / KCC-1 mesoporous-microporous composite zeolite, denoted as YK5.

[0153] Example 6

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

[0155] Preparation of microporous material Y molecular sieve:

[0156] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them to 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of microporous material Y molecular sieve. In step 1), in terms of oxides, the molar ratio of each component of the seed gel of microporous material Y molecular sieve is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

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

[0158] Step 3): Hydrothermally crystallize the reactant gel obtained in step 2) at 110 °C for 12 h. Centrifuge and wash until the pH value = 9, and dry at 100 °C for 10 h to obtain the microporous material Y molecular sieve. In terms of oxides, the silicon-aluminum molar ratio SiO2 / Al2O3 of the microporous material Y molecular sieve is 8:1.

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

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

[0161] Step (2): Add 1.5 g of the above-prepared microporous material Y zeolite into 90 ml of cyclohexane solvent. After ultrasonic treatment for 2 h, add 7.48 ml of tetraethyl orthosilicate, and stir at a speed of 500 r / s at room temperature for 15 min to obtain a second mixed solution;

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

[0163] Step (4): Hydrothermally treat the Y / KCC-1 mesoporous-microporous composite zeolite precursor emulsion at 120 °C for 5 h, centrifuge, wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h to obtain a Y / KCC-1 mesoporous-microporous composite zeolite, denoted as YK6.

[0164] Example 7

[0165] This example provides a Y / KCC-1 mesoporous-microporous composite zeolite, which is prepared by a preparation method including the following specific steps:

[0166] Preparation of microporous material Y zeolite:

[0167] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them into 9.98 g of deionized water. Stir at a speed of 500 r / s at room temperature for 15 min until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO2) at a stirring speed of 700 r / s, and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain a seed gel of microporous material Y zeolite; In Step 1), in terms of oxides, the molar ratio of each component of the seed gel of microporous material Y zeolite is Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

[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 under the stirring speed of 500 r / s and stirred for 15 min to obtain a reaction mixture. Calculated on the basis of oxides, the molar ratio of each component of the reaction mixture was Na₂O:Al₂O₃:SiO₂:H₂O = 8.23:1:7.19:329.21; 7.32 g of the seed gel prepared in Step 1) was added to the reaction mixture and stirred at a stirring speed of 250 r / s for 15 min, and aged statically at 30 °C for 15 h to form a reactant gel; calculated on the basis of oxides, the molar ratio of each component of the reactant gel was Na₂O:Al₂O₃:SiO₂:H₂O = 2.33:1:8.37:382.38; the addition amount of the seed gel accounted for 4.9% of the total mass of the reactant gel.

[0169] Step 3): The reactant gel obtained in Step 2) was hydrothermally crystallized at 110 °C for 12 h, centrifuged and washed until the pH value = 9, and dried at 100 °C for 10 h to obtain microporous material Y zeolite. Calculated on the basis of oxides, the silica-alumina molar ratio SiO₂ / Al₂O₃ of the microporous material Y zeolite was 8:1.

[0170] Preparation of Y / KCC-1 mesoporous-microporous composite zeolite:

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

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

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

[0174] Step (4): The Y / KCC-1 mesoporous-microporous composite zeolite precursor emulsion was hydrothermally treated at 120 °C for 5 h, centrifuged, washed with deionized water, dried at 70 °C for 10 h, and calcined at 550 °C for 6 h to obtain Y / KCC-1 mesoporous-microporous composite zeolite, denoted as YK7.

[0175] Examples of Y / KCC-1 Composite Hydrocracking Catalyst

[0176] Example 1-1

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

[0178] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK1 as the carrier and mix YK1 with the ammonium chloride aqueous solution at a mass ratio of YK1: ammonium chloride aqueous solution = 1:10. Perform ion exchange at 80°C with a stirring speed of 350 r / s for 1.5 h. Filter and wash until the pH value = 8. After 3 times of ion exchange, dry at 80°C for 10 h and calcine at 550°C for 3 h to obtain H-type Y / KCC-1 mesoporous composite molecular sieve;

[0179] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. Stir at 60°C at a rotation speed of 400 r / s for 1 h until it is clear and transparent and make up the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution onto 1.5 g of H-type Y / KCC-1 mesoporous composite molecular sieve in an equal volume. Age at 25°C for 5 h, dry at 90°C for 10 h, and calcine at 550°C for 6 h to obtain NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT1.

[0180] Example 1-2

[0181] This example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method including the following specific steps:

[0182] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK2 as the carrier and mix YK2 with the ammonium chloride aqueous solution at a mass ratio of YK2: ammonium chloride aqueous solution = 1:10. Perform ion exchange at 80°C with a stirring speed of 350 r / s for 1.5 h. Filter and wash until the pH value = 8. After 3 times of ion exchange, dry at 80°C for 10 h and calcine at 550°C for 3 h to obtain H-type Y / KCC-1 mesoporous composite molecular sieve;

[0183] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. At 60 °C, stir at a speed of 400 r / s for 1 h until clear and transparent, and make up the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution in equal volume onto 1.5 g of H-type Y / KCC-1 mesoporous and microporous composite molecular sieve, age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h to obtain the NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT2.

[0184] Examples 1 - 3

[0185] This example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method including the following specific steps:

[0186] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK3 as the carrier and mix YK3 with the ammonium chloride aqueous solution at a mass ratio of YK3:ammonium chloride aqueous solution = 1:10. At 80 °C, carry out ion exchange at a stirring speed of 350 r / s for 1.5 h, filter with suction and wash until the pH value = 8. After carrying out ion exchange 3 times, dry at 80 °C for 10 h and calcine at 550 °C for 3 h to obtain the H-type Y / KCC-1 mesoporous and microporous composite molecular sieve;

[0187] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. At 60 °C, stir at a speed of 400 r / s for 1 h until clear and transparent, and make up the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution in equal volume onto 1.5 g of H-type Y / KCC-1 mesoporous and microporous composite molecular sieve, age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h to obtain the NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT3.

[0188] Examples 1 - 4

[0189] This example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method including the following specific steps:

[0190] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK4 as the carrier and mix YK4 with the ammonium chloride aqueous solution at a mass ratio of YK4:ammonium chloride aqueous solution = 1:10. At 80 °C, carry out ion exchange at a stirring speed of 350 r / s for 1.5 h, filter with suction and wash until the pH value = 8. After carrying out ion exchange 3 times, dry at 80 °C for 10 h and calcine at 550 °C for 3 h to obtain the H-type Y / KCC-1 mesoporous and microporous composite molecular sieve;

[0191] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. At 60 °C, stir at a speed of 400 r / s for 1 h until clear and transparent, and adjust the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution in equal volume onto 1.5 g of H-type Y / KCC-1 mesoporous composite molecular sieve, age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT4.

[0192] Examples 1 - 5

[0193] This example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method including the following specific steps:

[0194] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK5 as the carrier and mix YK5 with the ammonium chloride aqueous solution at a mass ratio of YK5:ammonium chloride aqueous solution = 1:10. At 80 °C, perform ion exchange at a stirring speed of 350 r / s for 1.5 h, filter and wash by suction until the pH value = 8. After performing ion exchange three times, dry at 80 °C for 10 h and calcine at 550 °C for 3 h to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0195] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. At 60 °C, stir at a speed of 400 r / s for 1 h until clear and transparent, and adjust the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution in equal volume onto 1.5 g of H-type Y / KCC-1 mesoporous composite molecular sieve, age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT5.

[0196] Examples 1 - 6

[0197] This example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method including the following specific steps:

[0198] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK6 as the carrier and mix YK6 with the ammonium chloride aqueous solution at a mass ratio of YK6:ammonium chloride aqueous solution = 1:10. At 80 °C, perform ion exchange at a stirring speed of 350 r / s for 1.5 h, filter and wash by suction until the pH value = 8. After performing ion exchange three times, dry at 80 °C for 10 h and calcine at 550 °C for 3 h to obtain an H-type Y / KCC-1 mesoporous composite molecular sieve;

[0199] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. At 60 °C, stir at a speed of 400 r / s for 1 h until it becomes clear and transparent, and then adjust the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution onto 1.5 g of H-type Y / KCC-1 mesoporous and microporous composite molecular sieve in equal volume. Age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT6.

[0200] Examples 1 - 7

[0201] This example provides a Y / KCC-1 composite hydrocracking catalyst, which is prepared by a preparation method including the following specific steps:

[0202] Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of YK7 as the carrier and mix YK7 with the ammonium chloride aqueous solution at a mass ratio of YK7:ammonium chloride aqueous solution = 1:10. At 80 °C, carry out ion exchange at a stirring speed of 350 r / s for 1.5 h, filter and wash by suction until the pH value = 8. After carrying out ion exchange three times, dry at 80 °C for 10 h and calcine at 550 °C for 3 h to obtain an H-type Y / KCC-1 mesoporous and microporous composite molecular sieve;

[0203] Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water. At 60 °C, stir at a speed of 400 r / s for 1 h until it becomes clear and transparent, and then adjust the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution onto 1.5 g of H-type Y / KCC-1 mesoporous and microporous composite molecular sieve in equal volume. Age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h to obtain a NiW / Y / KCC-1 composite hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier, denoted as CAT7.

[0204] Comparative Example 1

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

[0206] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them to 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO₂) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of microporous material Y zeolite. In Step 1), in terms of oxides, the molar ratio of each component of the seed gel of microporous material Y zeolite is Na₂O:Al₂O₃:SiO₂:H₂O = 15.96:1:6.74:316.48;

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

[0208] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, dry at 100 °C for 10 h, and calcine at 500 °C for 4 h to obtain the microporous material Y zeolite, denoted as Yc. In terms of oxides, the silica-alumina molar ratio SiO₂ / Al₂O₃ of the microporous material Y zeolite is 8:1.

[0209] Comparative Example 2

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

[0211] Add 3.06 g of cetyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water. Stir at a speed of 400 r / s for 15 min at room temperature until completely dissolved to obtain a first mixed solution;

[0212] Add 7.48 ml of tetraethyl orthosilicate to 90 ml of cyclohexane solvent. Stir at a speed of 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. Then, 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 the KCC-1 mesoporous molecular sieve precursor emulsion;

[0214] The KCC-1 mesoporous molecular sieve precursor emulsion was hydrothermally treated at 120 °C for 5 h, centrifuged, washed with deionized water, dried at 70 °C for 10 h, and calcined at 550 °C for 6 h to obtain the KCC-1 mesoporous molecular sieve, denoted as Kc.

[0215] Comparative Example 3

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

[0217] I. Preparation of microporous material Y zeolite:

[0218] Step 1): 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide were added to 9.98 g of deionized water, and the mixture was stirred at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Then, 10.24 g of sodium silicate solution (25 wt% SiO2) was added at a stirring speed of 700 r / s, and the mixture was stirred for 5 min to form a seed gel precursor, which was allowed to stand and age at 25 °C for 20 h to obtain the seed gel of microporous material Y zeolite. In Step 1), in terms of oxides, the molar ratio of the components of the seed gel of microporous material Y zeolite was Na2O:Al2O3:SiO2:H2O = 15.96:1:6.74:316.48;

[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 the mixture was stirred at a speed of 500 r / s for 10 min at room temperature until completely dissolved. Then, 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. In terms of oxides, the molar ratio of the components of the reaction mixture was Na2O:Al2O3:SiO2:H2O = 8.23:1:7.19:329.21; 7.32 g of the seed gel prepared in Step 1) was added to the reaction mixture and stirred at a stirring speed of 250 r / s for 15 min, and then allowed to stand and age at 30 °C for 15 h to form a reactant gel. In terms of oxides, the molar ratio of the components of the reactant gel was Na2O:Al2O3:SiO2:H2O = 2.33:1:8.37:382.38; the addition amount of the seed gel accounted for 4.9% of the total mass of the reactant gel;

[0220] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash it until the pH value = 9, dry it at 100 °C for 10 h, and calcine it at 500 °C for 4 h to obtain microporous material Y zeolite, denoted as Yc. In terms of oxides, the silica-alumina molar ratio SiO2 / Al2O3 of the microporous material Y zeolite is 8:1.

[0221] II. Preparation of H-type Y zeolite:

[0222] Step 4): Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 2 g of Yc as the 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 with a stirring speed of 350 r / s for 1.5 h, filter with suction and wash until the pH value = 8. After performing ion exchange three times, dry it at 80 °C for 10 h and calcine it at 550 °C for 3 h to obtain H-type Y zeolite, denoted as H-Yc.

[0223] III. Hydrothermal pickling treatment:

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

[0225] Step 6): Mix the hydrothermally treated Y zeolite with a 1.5 mol / L hydrochloric acid solution at a solid-liquid ratio (mass ratio) of 1:10, and treat it at 80 °C with a rotation speed of 400 r / s for 3 h. Filter with suction and wash until neutral, dry it at 70 °C for 10 h, and calcine it at 500 °C for 4 h to obtain the carrier, denoted as carrier a.

[0226] IV. Preparation of hydrocracking catalyst:

[0227] Step 7): Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water, stir at 60 °C with a rotation speed of 400 r / s for 1 h until it is clear and transparent, and make up the volume of the solution to 1.8 ml to obtain the impregnation solution. Impregnate the prepared impregnation solution onto carrier a in an equal volume, age it at 25 °C for 5 h, dry it at 90 °C for 10 h, and calcine it at 550 °C for 6 h to obtain the NiW / Y hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% 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 including the following specific steps:

[0230] I. Preparation of microporous material Y zeolite:

[0231] Step 1): Take 1.05 g of sodium aluminate and 2.04 g of sodium hydroxide and add them to 9.98 g of deionized water. Stir at a speed of 500 r / s for 15 min at room temperature until completely dissolved. Add 10.24 g of sodium silicate solution (25 wt% SiO₂) at a stirring speed of 700 r / s and stir for 5 min to form a seed gel precursor. Let it stand and age at 25 °C for 20 h to obtain the seed gel of microporous material Y zeolite. In Step 1), based on oxides, the molar ratio of each component of the seed gel of microporous material Y zeolite is Na₂O:Al₂O₃:SiO₂:H₂O = 15.96:1:6.74:316.48;

[0232] Step 2): Add 0.06 g of sodium hydroxide and 6.58 g of sodium aluminate to 64.27 g of deionized water. Stir at a speed of 500 r / s for 10 min at room temperature until completely dissolved. Add 68.44 g of sodium silicate solution (25 wt% SiO₂) at a stirring speed of 500 r / s and stir for 15 min to obtain a reaction mixture. Based on oxides, the molar ratio of each component of the reaction mixture is Na₂O:Al₂O₃:SiO₂:H₂O = 8.23:1:7.19:329.21; Add 7.32 g of the seed gel prepared in Step 1) to the reaction mixture and stir at a stirring speed of 250 r / s for 15 min. Let it stand and age at 30 °C for 15 h to form a reactant gel. Based on oxides, the molar ratio of each component of the reactant gel is Na₂O:Al₂O₃:SiO₂:H₂O = 2.33:1:8.37:382.38; The addition amount of the seed gel accounts for 4.9% of the total mass of the reactant gel;

[0233] Step 3): Hydrothermally crystallize the reactant gel obtained in Step 2) at 110 °C for 12 h, centrifuge and wash until the pH value = 9, dry at 100 °C for 10 h, and calcine at 500 °C for 4 h to obtain microporous material Y zeolite, denoted as Yc. Based on oxides, the silica-alumina molar ratio SiO₂ / Al₂O₃ of microporous material Y zeolite is 8:1.

[0234] II. Preparation of H-type Y zeolite:

[0235] Step 4): Prepare an ammonium chloride aqueous solution with a concentration of 1 mol / L. Take 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 at a stirring speed of 350 r / s for 1.5 h, filter with suction and wash until the pH value = 8. After performing ion exchange three times, dry at 80 °C for 10 h and calcine at 550 °C for 3 h to obtain H-type Y zeolite, denoted as H-Yc.

[0236] III. Hydrothermal alkali washing treatment:

[0237] Step 5): Hydrothermally treat the H-type Y zeolite, namely H-Yc, at 650 °C and 0.3 MPa for 2 h to obtain the hydrothermally treated Y zeolite;

[0238] Step 6): Mix the hydrothermally treated Y zeolite with a sodium hydroxide solution with a concentration of 0.5 mol / L at a solid-liquid ratio (weight ratio) of 1:10, and treat it at 70 °C with a rotation speed of 400 r / s for 2 h. After suction filtration and washing until neutral, dry it at 70 °C for 10 h and calcine it at 500 °C for 4 h to obtain the support, denoted as support b.

[0239] IV. Preparation of the hydrocracking catalyst:

[0240] Step 7): Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water, stir at 60 °C with a stirring speed of 400 r / s for 1 h until clear and transparent, and make up the volume of the solution to 1.8 ml to obtain the impregnation solution. Impregnate the prepared impregnation solution onto support b in an equal volume, age it at 25 °C for 5 h, dry it at 90 °C for 10 h, and calcine it at 550 °C for 6 h to obtain the NiW / Y hydrocracking catalyst. The catalyst composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% support, denoted as CATB.

[0241] Characterization test example

[0242] In this test example, the Y / KCC-1 micro-mesoporous composite zeolite prepared in Example 1 of the present invention, namely YK1, was analyzed by XRD, N2-adsorption desorption, scanning electron microscopy, transmission electron microscopy, diffusion performance, etc. The XRD results are as Figure 1 shown, the N2-adsorption desorption isotherm is as Figure 4 shown, the pore size distribution result is as Figure 7 shown, the scanning electron microscopy result is as Figure 10 shown, the transmission electron microscopy result is as Figure 13 shown, and the diffusion performance result is as Figure 15 shown.

[0243] In this test example, the Y zeolite prepared in Comparative Example 1, namely Yc, was also analyzed by XRD, N2-adsorption desorption, scanning electron microscopy, diffusion performance, etc. The XRD results are as Figure 2 shown, the N2-adsorption desorption isotherm is as Figure 5 shown, the pore size distribution result is as Figure 8 shown, the scanning electron microscopy result is as Figure 11 shown, and the diffusion performance result is as Figure 15 shown.

[0244] In this test example, the KCC-1 zeolite prepared in Comparative Example 2, namely Kc, was also analyzed by XRD, N2-adsorption desorption, scanning electron microscopy, transmission electron microscopy, diffusion performance, etc. The XRD results are as Figure 3As shown, the N2-adsorption / desorption isotherm is as Figure 6 shown, and the pore size distribution results are as Figure 9 shown. The scanning electron microscopy results are as Figure 12 shown, and the transmission electron microscopy results are as Figure 14 shown, and the diffusion performance results are as Figure 15 shown.

[0245] As can be seen from the above results, the Y / KCC-1 micro-mesoporous composite molecular sieve provided in Example 1 of the present invention has a core-shell structure, including Y molecular sieve and KCC-1 mesoporous material. The KCC-1 mesoporous material tightly wraps outside the Y molecular sieve, and the surface morphology of the Y / KCC-1 micro-mesoporous composite molecular sieve is fibrous. The present invention successfully composites the Y molecular sieve with the KCC-1 mesoporous material, and the obtained Y / KCC-1 micro-mesoporous composite molecular sieve has a phase structure similar to that of the microporous Y molecular sieve; the surface morphologies of the KCC-1 mesoporous material and the Y / KCC-1 micro-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 sieves provided in Examples 1-7, the Y molecular sieve provided in Comparative Example 1, the KCC-1 molecular sieve provided in Comparative Example 2, the hydrothermally acid-treated Y molecular sieve provided in Comparative Example 3, i.e., carrier a, and the hydrothermally 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] As can be seen from Table 1 above, compared with the microporous Y molecular sieve, the specific surface area, pore volume and pore size of the Y / KCC-1 micro-mesoporous composite molecular sieve prepared in the examples of the present invention are all increased. This indicates that the present invention composites the microporous Y molecular sieve with the KCC-1 mesoporous material, which can effectively improve the pore structure properties of the material, and at the same time can accurately control the particle size of the micro-mesoporous 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] Item Effective Diffusion Coefficient Example 1 1.01E-03 Comparative Example 1 6.05E-04 Comparative Example 2 2.30E-03

[0253] Combined with Figure 15As can be seen from Table 2, the relationship of the effective diffusion coefficients is: Comparative Example 2 > Example 1 > Comparative Example 1, indicating that when the mesoporous and microporous composite molecular sieve provided in the examples of the present invention is used as the hydrocracking catalyst carrier, compared with the traditional microporous material carrier, the mesoporous and microporous composite molecular sieve provided in the examples of the present invention can effectively improve the diffusion ability of reactant molecules in the pores.

[0254] Performance test example

[0255] In this test example, the hydrocracking reactions of 1-methylnaphthalene catalyzed by CAT1 - CAT7 provided in Examples 1-1 to 1-7 of the present invention, CATA and CATB provided in Comparative Examples 3-4 were evaluated respectively. The evaluation was carried out on a fixed-bed micro-reactor. During the evaluation process, the conversion rate, yield and selectivity of the hydrocracking of the catalyst were 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 - 7 and Comparative Examples 3 - 4 were respectively tableted for 10 min under a pressure of 25 MPa, screened to 20 - 40 mesh, and 1 g was taken and loaded into the reactor.

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

[0258] Step 3: The hydrocracking reaction of 1-methylnaphthalene was carried out in a high-pressure hydrogenation micro-reactor, that is, a fixed-bed micro-reactor. Among them, the reaction temperature was 480 °C, the reaction pressure was 6 MPa, the liquid hourly space velocity was 2 h -1 , and the hydrogen-oil volume ratio was 1200:1;

[0259] Step 4: The contents of each component in the liquid product obtained from the hydrocracking reaction were measured by gas chromatography - mass spectrometry (GC-MS).

[0260] Table 3

[0261]

[0262]

[0263] The catalytic reaction results of the hydrogenation cracking of 1-methylnaphthalene over the catalysts shown in Table 3 above indicate that the conversion rate, alkylbenzene yield, and alkylbenzene selectivity of 1-methylnaphthalene over the Y / KCC-1 composite hydrocracking catalyst provided in the embodiments of the present invention are significantly higher than those of the hydrocracking catalyst prepared with a conventional modified Y zeolite as the carrier. Therefore, the novel composite hydrocracking catalyst provided in the embodiments of the present invention has great potential industrial application value.

[0264] In summary, the Y / KCC-1 micro-mesoporous composite molecular sieve provided in the embodiments of the present invention has a core-shell structure, including a Y zeolite and a KCC-1 mesoporous material tightly wrapped outside the Y zeolite. In the embodiments of the present invention, the microporous material Y zeolite and the mesoporous material KCC-1 are combined to obtain the Y / KCC-1 micro-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 micro-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 micro-mesoporous composite molecular sieve as the carrier is a novel catalyst material, which has high catalytic activity and selectivity for the hydrogenation cracking reaction of 1-methylnaphthalene, showing higher conversion rate, yield, and product selectivity, and has potential application value in the petrochemical field.

[0265] As described above, the above are only specific embodiments of the present invention, and the scope of the invention implementation cannot be limited by them. Therefore, the replacement of equivalent components, or equivalent changes and modifications made according to the scope of the present invention patent protection, should still fall within the scope covered by this patent. In addition, the technical features in the present invention can be freely combined and used among the technical features, between the technical features and the technical invention, and between the technical inventions.

Claims

1. A hydrocracking catalyst, comprising a carrier and a metal active component supported on the carrier, characterized in that, The carrier is an H-type Y / KCC-1 mesoporous and microporous composite molecular sieve, which is obtained by first mixing 2 g of Y / KCC-1 mesoporous and microporous composite molecular sieve with 20 g of ammonium chloride aqueous solution with a concentration of 1 mol / L, performing ion exchange at 80 °C with a stirring speed of 350 r / s for 1.5 h, filtering and washing until the pH value = 8, performing ion exchange three times, drying at 80 °C for 10 h, and calcining at 550 °C for 3 h; Among them, the specific surface area of the Y / KCC-1 mesoporous composite molecular sieve is 651.22 m 2 ·g -1 , the pore diameter is 9.25 nm, the pore volume is 0.68 cm 3 ·g -1 and the average particle size is 430 nm, and it is prepared by the following steps: Add 4.59 g of cetyltrimethylammonium bromide and 1.78 g of urea to 90 ml of deionized water, and stir at a rotation speed of 400 r / s at room temperature for 20 min until completely dissolved to obtain a first mixed solution; Add 1.5 g of microporous material Y molecular sieve to 90 ml of cyclohexane solvent, ultrasonicate for 2 h, then add 7.48 ml of tetraethyl orthosilicate, and stir at a rotation speed of 500 r / s at room temperature for 15 min to obtain a second mixed solution; and the microporous material Y molecular sieve is a microporous material Y molecular sieve that has not been calcined and amine-exchanged; Add the second mixed solution to the first mixed solution, stir at a rotation speed of 700 r / s at room temperature for 15 min, add 5 ml of n-pentanol, and stir at a rotation speed of 400 r / s at room temperature for 30 min to obtain an emulsion; Hydrothermally treat the emulsion at 120 °C for 5 h, centrifuge, wash with deionized water, dry at 70 °C for 10 h, and calcine at 550 °C for 6 h; Based on the total weight of the hydrocracking catalyst being 100%, its composition is 10 wt% WO3, 5 wt% NiO, and 85 wt% carrier.

2. The preparation method of the hydrocracking catalyst according to claim 1, characterized in that, The preparation method includes: Dissolve 0.21 g of ammonium metatungstate and 0.39 g of nickel nitrate in deionized water, stir at a rotation speed of 400 r / s at 60 °C for 1 h until clear and transparent, and make up the volume of the solution to 1.8 ml to obtain an impregnation solution. Impregnate the prepared impregnation solution onto 1.5 g of H-type Y / KCC-1 mesoporous and microporous composite molecular sieve in an equal volume manner, age at 25 °C for 5 h, dry at 90 °C for 10 h, and calcine at 550 °C for 6 h.

3. Use of the hydrocracking catalyst according to claim 1 in the hydrocracking of 1-methylnaphthalene, characterized in that, The application includes the following specific steps: Step 1: Press the hydrocracking catalyst at a pressure of 25 MPa for 10 min, screen it to 20 - 40 mesh, and take 1 g to fill it into the reactor; Step 2: Before the hydrogenation reaction, the above catalysts are pre-sulfurized respectively. The pre-sulfurization solution used for pre-sulfurization is a cyclohexane mixed solution with a CS2 content of 1.5 wt%. The pre-sulfurization conditions include: hydrogen pressure of 6 MPa, hydrogen-oil volume ratio of 600:1, liquid hourly space velocity of 2.5 h -1 , maintaining at 230 °C for 2 h and at 320 °C for 3 h; Step 3: Carry out hydrocracking reaction of 1-methylnaphthalene in a high-pressure hydrogenation micro-reactor, namely a fixed-bed micro-reactor, where the reaction temperature is 480 °C, the reaction pressure is 6 MPa, the liquid hourly space velocity is 2 h -1 , and the hydrogen-oil volume ratio is 1200:1; Step 4: Use gas chromatography - mass spectrometry (GC-MS) to measure the content of each component in the liquid product obtained from the hydrocracking reaction.

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