CN111085244A - Preparation method of hierarchical pore composite material - Google Patents
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Abstract
A preparation method of a hierarchical pore composite material is characterized by comprising the steps of carrying out double-cross double baking on a silicon-aluminum material, wherein the silicon-aluminum material simultaneously contains a Y-shaped molecular sieve and a mesoporous alumina layer with a pseudo-boehmite structure, the mesoporous alumina layer grows on the surface of crystal grains of the Y-shaped molecular sieve and uniformly coats the crystal grains of the molecular sieve, the disordered structure of the mesoporous alumina layer extends and grows from the edge of ordered diffraction stripes of an FAU crystal phase structure of the Y-shaped molecular sieve, and the two structures are built together; the chemical composition of the silicon-aluminum material is (4-12) Na based on the weight of oxide2O·(20～60)SiO2·(30～75)Al2O3(ii) a The grain size parameter D (V, 0.5) of the silicon-aluminum material is 1.8-2.5, and the grain size parameter D (V, 0.9) is 4.0-8.0. The hierarchical porous composite material obtained by the method has high accessibility of the active center and more excellent reaction performance.
Description
Technical Field
The invention relates to a preparation method of a hierarchical pore composite material, in particular to a preparation method of a hierarchical pore composite material with an alumina mesoporous layer coated on the surface of a molecular sieve.
Background
Catalytic cracking is an important process in petroleum refining, is widely applied to the petroleum processing industry, and plays a significant role in oil refineries. In the catalytic cracking process, heavy fractions such as vacuum distillates or heavier residues are reacted in the presence of a catalyst to convert into gasoline, distillates and other liquid cracked products, and lighter gaseous cracked products of four carbons or less. The catalytic cracking reaction process follows a carbonium ion reaction mechanism, and therefore, an acidic catalytic material, particularly a catalytic material having a strong B acid center, needs to be used. Amorphous alumino-silicate material is an acidic catalytic material, which has both B and L acid centers, is the main active component in early catalytic cracking catalysts, but is gradually replaced by crystalline molecular sieves due to its lower cracking activity and higher required reaction temperature. The crystalline molecular sieve is a porous material with the pore diameter less than 2nm and a special crystalline phase structure, and the material with the pore diameter less than 2nm is named as a microporous material according to the definition of IUPAC, so that the crystalline molecular sieve or zeolite generally belongs to the microporous material, and the microporous molecular sieve material has stronger acidity and higher structural stability due to the complete crystal structure and the special framework structure, shows higher catalytic activity in a catalytic reaction, and is widely applied to petroleum processing and other catalytic industries.
The Y-type molecular sieve is used as a typical microporous molecular sieve material, and is applied in the fields of catalytic cracking, hydrocracking and the like on a large scale due to the regular pore channel structure, good stability and strong acidity. When the modified Y-type molecular sieve is used in a catalytic cracking catalyst, certain modification treatment is usually required to be carried out on the Y-type molecular sieve, such as skeleton dealumination inhibition through rare earth modification, the structural stability of the molecular sieve is improved, the retention degree of acid centers is increased, and the cracking activity is further improved; or the framework silicon-aluminum ratio is improved through ultra-stabilization treatment, so that the stability of the molecular sieve is improved.
With the increasing exhaustion of petroleum resources, the trend of crude oil heaving and deterioration is obvious, the proportion of blending slag is continuously improved, and the demand of the market for light oil products is not reduced, so that in recent years, the deep processing of heavy oil and residual oil is more and more emphasized in the petroleum processing industry, many refineries begin to blend vacuum residual oil, even directly use atmospheric residual oil as a cracking raw material, the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefit of oil refining enterprises, and the macromolecular cracking capability of the catalyst is a focus of attention. The Y-type molecular sieve is the most main cracking active component in the conventional cracking catalyst, but due to the smaller pore channel structure, the Y-type molecular sieve shows a relatively obvious pore channel limiting effect in large molecular reaction, and also shows a certain inhibiting effect on large molecular cracking reactions such as heavy oil or residual oil and the like. Therefore, for catalytic cracking of heavy oil, it is necessary to use a material having a large pore diameter, no diffusion limitation to reactant molecules, and a high cracking activity.
According to the IUPAC definition, a material with the pore diameter of 2-50 nm is a mesoporous (mesoporous) material, and the size range of macromolecules such as heavy oil or residual oil is in the pore diameter range, so that the research of mesoporous materials, particularly mesoporous silicon-aluminum materials, has attracted great interest to researchers in the field of catalysis. Mesoporous materials appeared in 1992 for the first time, and were first developed successfully by the American Mobil company (Beck J S, Vartuli J Z, Roth W J et al, J.Am.Chem.Comm.Soc., 1992, 114, 10834-containing 10843), named as M41S series mesoporous molecular sieves, including MCM-41(Mobil Corporation Material-41) and MCM-48, etc., the pore size of the molecular sieves can reach 1.6-10 nm, and the mesoporous materials are uniform and adjustable, have concentrated pore size distribution, large specific surface area and pore volume, and strong adsorption capacity; however, the pore wall structure of the molecular sieve is an amorphous structure, so that the molecular sieve has poor hydrothermal stability and weak acidity, cannot meet the operation conditions of catalytic cracking, and is greatly limited in industrial application.
In order to solve the problem of poor hydrothermal stability of mesoporous molecular sieves, part of research work focuses on increasing the wall thickness of molecular sieves, and if a neutral template agent is adopted, a molecular sieve with a thicker pore wall can be obtained, but the defect of weaker acidity still exists. In CN1349929A, a novel mesoporous molecular sieve is disclosed, which introduces primary and secondary structural units of zeolite into the pore wall of the molecular sieve to make it have the basic structure of conventional zeolite molecular sieve, and the mesoporous molecular sieve has strong acidity and ultrahigh hydrothermal stability. However, the molecular sieve has the defects that a template agent with high price is required to be used, the aperture is only about 2.7nm, the molecular sieve still has large steric hindrance effect on macromolecular cracking reaction, the structure is easy to collapse under the high-temperature hydrothermal condition, and the cracking activity is poor.
In the field of catalytic cracking, silicon-aluminum materials are widely used due to their strong acid centers and good cracking properties. The proposal of the mesoporous concept provides possibility for the preparation of a novel catalyst, and the current research results mostly focus on the use of expensive organic template agents and organic silicon sources and mostly need to be subjected to a high-temperature hydrothermal post-treatment process. In order to reduce the preparation cost and obtain porous materials in the mesoporous range, more research efforts have been focused on the development of disordered mesoporous materials. US5,051,385 discloses a monodisperse mesoporous silicon-aluminum composite material, which is prepared by mixing acidic inorganic aluminum salt and silica sol and then adding alkali for reaction, wherein the aluminum content is 5-40 wt%, the aperture is 20-50 nm, and the specific surface area is 50-100 m2(ii) in terms of/g. US4,708,945 discloses a catalyst prepared by loading silica particles or hydrated silica on porous boehmite and hydrothermally treating the obtained composite at a temperature of more than 600 ℃ for a certain time to obtain a catalyst prepared by loading silica on the surface of the boehmite, wherein the silica is combined with hydroxyl of the transition boehmite and the surface area reaches 100-200 m2(iv) g, average pore diameter of 7 to 7.5 nm. A series of acidic cracking catalysts are disclosed in US4,440,872, some of which are supported on gamma-Al2O3Impregnating silane, and then roasting at 500 ℃ or treating with water vapor. In CN1353008A, inorganic aluminum salt and water glass are used as raw materials, stable and clear silicon-aluminum sol is formed through the processes of precipitation, washing, dispergation and the like, white gel is obtained through drying, and then the silicon-aluminum catalytic material is obtained through roasting for 1-20 hours at 350-650 ℃. CN1565733A discloses a mesoporous silicon-aluminum material which has a pseudo-boehmite structure, concentrated pore size distribution and a specific surface area of about 200-400 m2The mesoporous silicon-aluminum material has the advantages that the pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, the most probable pore diameter is 5-15 nm, an organic template agent is not needed in the preparation of the mesoporous silicon-aluminum material, the synthesis cost is low, the obtained silicon-aluminum material has high cracking activity and hydrothermal stability, and good macromolecular cracking performance is shown in a catalytic cracking reaction.
Disclosure of Invention
The Y-type molecular sieve has the advantages of complete crystal structure, strong acidity, excellent structural stability and cracking performance, the mesoporous alumina material has a typical mesoporous structure, a mesoporous layer of alumina is coated on the surface of the Y-type molecular sieve, and the two structures are built together to form an effective pore channel and an acidity gradient, so that the respective advantages can be enhanced. Based on this, the present invention was made.
The invention aims to provide a preparation method of a hierarchical pore composite material simultaneously containing a Y-shaped molecular sieve and an alumina layer.
The preparation method of the hierarchical pore composite material provided by the invention comprises the following preparation steps: according to the weight ratio of 1 (0.2-1.2), carrying out first exchange treatment on a silicon-aluminum material and ammonium salt at the temperature of 40-90 ℃ for 0.5-3 hours, filtering, washing and drying; carrying out primary hydrothermal roasting treatment on the sample for 1-4 hours at 500-700 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium salt at the temperature of 40-90 ℃ according to the weight ratio of 1 (0.2-0.8), filtering, washing with water, and drying; and carrying out second hydrothermal roasting treatment on the sample for 1-4 hours at the temperature of 500-700 ℃ under the condition of 100% steam.
The hierarchical pore composite material prepared by the method is characterized by simultaneously containing a layer of alumina mesoporous layer and a Y-shaped molecular sieve, wherein the alumina layer is coated on the surface of the molecular sieve, and the two structures are connected together; the chemical composition of the hierarchical porous composite material is (0.3-1.0) Na based on the weight of oxides2O·(25～65)SiO2·(30～75)Al2O3(ii) a The unit cell constant is 2.440-2.455 nm, preferably 2.442-2.453 nm, the relative crystallinity is 20-60%, preferably 25-55%, and the total specific surface area is 350-550 m2(ii) a total pore volume of 0.25 to 0.40cm3And g, the ratio of the amount of the B acid to the amount of the L acid at 350 ℃, namely B/L is 0.20-0.50.
Preparation method of the inventionThe method comprises the steps that the silicon-aluminum material simultaneously contains a Y-type molecular sieve and a pseudo-boehmite structure mesoporous alumina layer, the mesoporous alumina layer grows on the surface of a Y-type molecular sieve crystal grain and uniformly coats the molecular sieve crystal grain, the disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together; the chemical composition of the silicon-aluminum material is (4-12) Na calculated by the weight of the oxide2O·(20～60)SiO2·(30～75)Al2O3(ii) a The total specific surface area is 380-700 m2(ii) a total pore volume of 0.32 to 0.48cm3The BJH pore size distribution curve shows that two or more pore distributions appear at 3-4 nm and 6-9 nm respectively. The grain size parameter D (V, 0.5) of the silicon-aluminum material is 1.8-2.5, and the grain size parameter D (V, 0.9) is 4.0-8.0. The XRD spectrum has characteristic diffraction peaks at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 28 degrees, 31.4 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively, wherein the characteristic diffraction peaks at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees and 31.4 degrees correspond to the FAU crystal phase structure of the Y-type molecular sieve, and the characteristic diffraction peaks at 28 degrees, 38.5 degrees, 49 degrees and 65 degrees correspond to the pseudo-boehmite structure of the mesoporous layer. The Transmission Electron Microscope (TEM) picture shows that the pseudo-boehmite disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together. A Scanning Electron Microscope (SEM) shows that a corrugated structure is coated on the surface of the molecular sieve crystal grains, and the molecular sieve crystal grains are uniformly coated in the corrugated structure.
According to the preparation method, the silicon-aluminum material can be prepared through the following processes: (1) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then carrying out static crystallization at the temperature of 95-105 ℃; (2) filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; (3) mixing the NaY molecular sieve filter cake obtained in the step (2) with deionized water, pulping and homogenizing, adding an aluminum source and an alkali solution into the mixture simultaneously in a parallel flow mode under the conditions that the temperature is between room temperature and 85 ℃ and violent stirring, and controlling the pH value of a slurry system to be 9-11 in the mixing process; (4) and then the mixture is processed for 1 to 10 hours at the constant temperature ranging from room temperature to 90 ℃ and the product is recovered, or the mixture is processed for 1 to 4 hours at the constant temperature ranging from room temperature to 90 ℃, and then the slurry is placed in a closed crystallization kettle and is subjected to hydrothermal crystallization for 3 to 30 hours at the temperature ranging from 95 ℃ to 105 ℃ and the product is recovered.
Wherein, the raw materials for synthesizing the NaY molecular sieve in the step (1) generally refer to guiding agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water, and the adding proportion of the raw materials can be the charging proportion of the conventional NaY molecular sieve, such as Na2O：Al2O3：SiO2：H2O is 1.5-8: 1: 5-18: 100 to 500, the charge ratio of NaY molecular sieve for preparing special performance, for example, the charge ratio of NaY molecular sieve for preparing large or small crystal grains, is not particularly limited as long as NaY molecular sieve having FAU crystal phase structure can be obtained. The guiding agent can be prepared according to the prior art (US3639099 and US3671191), and the guiding agent is prepared by mixing a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na2O:Al2O3: (15～17)SiO2:(280～380)H2Mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at room temperature to 70 ℃. In the feeding proportion of the NaY molecular sieve, Al in the guiding agent2O3The content of (A) is based on the total charge Al2O33 to 15%, preferably 5 to 10% of the total amount. The static crystallization in the step (1) is carried out for 8-50 hours, preferably 10-40 hours, and more preferably 15-35 hours.
Wherein, the aluminum source in the step (3) is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate, and when the sodium metaaluminate is taken as the alkali solution, the alumina content of the alkali solution is counted in the total alumina content. The sodium metaaluminate can be sodium metaaluminate with different causticity ratios and different concentrations. The caustic ratio is preferably 1.5 to 11.5, more preferably 1.65 to 2.55, and the concentration is preferably 40 to 200gAl2O3a/L, more preferably 41 to 190 gAl2O3/L。
The concept of the concurrent flow mode of adding the aluminum source and the alkali solution simultaneously in the step (3) refers to an operation mode of adding n +1(n is more than or equal to 1) materials (such as the aluminum source and the alkali solution in the invention) into the container simultaneously for mixing, so that each material is added at a constant speed, and the n +1 materials are added in the same time. For example, a peristaltic pump may be used in a specific operation, the flow parameters per unit time of the peristaltic pumps for delivering the aluminum source and the alkaline solution are controlled and performed at a constant speed to ensure that the aluminum source and the alkaline solution are added in the same time. The temperature of the mixing process in the step (3) is between room temperature and 85 ℃, and preferably between 30 and 70 ℃.
In the preparation method of the present invention, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, and ammonium bicarbonate.
In the preparation method, the proportion of the first exchange treatment of the silicon-aluminum material and the ammonium salt is 1 (0.2-1.2), preferably 1 (0.4-1.0), in terms of weight ratio, and the exchange treatment temperature is 40-90 ℃, preferably 50-80 ℃.
In the preparation method of the invention, the first hydrothermal roasting treatment and the second hydrothermal roasting treatment are carried out for 1-4 hours at the temperature of 500-700 ℃, preferably 550-650 ℃.
In the preparation method, the weight ratio of the second exchange treatment to ammonium salt is 1 (0.2-0.8), preferably 1 (0.3-0.6), and the exchange treatment temperature is 40-90 ℃, preferably 50-80 ℃.
The hierarchical pore composite material prepared by the method has the advantages that the microporous structure of the Y-type molecular sieve and the mesoporous structure of the gamma-alumina exist at the same time, and the two pore structures are organically combined and communicated with each other, so that the accessibility of an active center is improved, the reaction performance is improved, and the hierarchical pore composite material has better reaction activity compared with a simple mechanical mixed sample. After aging treatment for 8 hours at 800 ℃ and 100% of water vapor, the micro-anti-activity index MA can reach 51-62.
Drawings
FIG. 1 is an X-ray diffraction spectrum of a hierarchical pore composite PL-1 prepared in example 1.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The SEM adopts a Hitachi S4800 type Hitachi field emission SEM in Japan, the accelerating voltage is 5kV, and the energy spectrum is collected and processed by Horiba 350 software.
Transmission electron microscopy TEM test Using a transmission electron microscope model of FEI Tecnai F20G2S-TWIN, operating at 200 kV.
The phase, unit cell constant, crystallinity, and the like were measured by X-ray diffraction. Wherein, the crystallinity is determined according to the industry standards SH/T0340-92 and SH/T0339-92 of China general petrochemical company, and the NaY molecular sieve crystallinity standard sample is determined: NaY molecular sieve (GS BG 75004-.
The data of specific surface, pore volume, pore size distribution and the like are measured by a low-temperature nitrogen adsorption-desorption method.
The particle size distribution test is carried out by mixing micro porous material with deionized water, adding a small amount of slurry into the laser particle size analyzer, recording a plurality of analysis data after stable analysis, and carrying out average treatment to obtain corresponding particle size distribution data.
Chemical compositions were measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP laboratory), eds" Yangcui et al, published by scientific publishers, 1990).
The determination of B acid and L acid amount adopts infrared pyridine adsorption in-situ measurement method FT-IR, and NICOLET750 infrared instrument with DTGS KBr as detector and 4cm resolution-1。
Example 1
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
Mixing water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water according to 8.5SiO2：Al2O3： 2.65Na2O：210H2Mixing at a molar ratio of O, whereinThe mass ratio of the guiding agent is 5 percent, the guiding agent is vigorously stirred to form NaY molecular sieve gel, the gel is placed in a crystallization kettle to be statically crystallized for 18 hours at the temperature of 100 ℃, and after crystallization is finished, cooling is carried out, and crystallized slurry is filtered and washed to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 50 ℃, and simultaneously carrying out AlCl in a parallel flow mode under the condition of vigorous stirring3Solution (concentration 60 gAl)2O3and/L) and NaOH solution (with the concentration of 1M) are added into the mixture, the pH value of a slurry system is controlled to be 9.4 in the mixing process, after the mixture is mixed for a certain time, the mixture is treated at the constant temperature of 70 ℃ for 6 hours, and then the filtration, the washing and the drying are carried out, so that the silicon-aluminum material AFCY-2 is obtained.
The SEM picture of AFCY-2 shows that the molecular sieve crystal grain surface is coated with a wrinkle-like structure. A Transmission Electron Microscope (TEM) picture shows that a regular and ordered diffraction stripe and a disordered structure without fixed crystal face trend can be seen, wherein the ordered diffraction stripe represents an FAU crystal structure, the disordered structure is a pseudo-boehmite structure, the disordered structure is derived from the edge of the ordered diffraction stripe, and the two structures are built together. The XRD spectrum shows that diffraction peaks appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 28 degrees, 31.4 degrees, 38.5 degrees, 49 degrees and 65 degrees, and the FAU crystal phase structure of the Y-type molecular sieve and the pseudo-boehmite structure of the mesoporous layer correspond to the structure of the FAU crystal phase of the Y-type molecular sieve. The chemical composition of the oxide-doped sodium titanate is 11.7Na by weight2O·57.6SiO2·30.1Al2O3(ii) a The total specific surface area is 651m2(ii)/g, total pore volume 0.350 cm3(ii)/g; the BJH pore size distribution curve shows that the two-peak distribution is respectively about 3.8nm and 6.6 nm; the laser particle size analyzer measured D (V, 0.5) ═ 1.97 and D (V, 0.9) ═ 4.11.
According to the weight ratio of 1:0.8, performing first exchange treatment on AFCY-2 and ammonium chloride at 80 ℃ for 1 hour, filtering, washing with water, and drying; carrying out first hydrothermal roasting treatment on the sample for 4 hours at 550 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium chloride at the temperature of 80 ℃ according to the weight ratio of 1:0.3, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at the temperature of 550 ℃ and under the condition of 100 percent of water vapor to obtain the hierarchical porous composite material, which is marked as PL-1.
An XRD diffraction pattern of PL-1 is shown in FIG. 1, in which diffraction peaks marked by x at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 ° and 31.4 ° are characteristic diffraction peaks of the Y-type molecular sieve, and diffraction peaks marked by braces between 20 ° and 30 ° and around 66 ° are characteristic diffraction peaks of the alumina layer. The chemical composition of PL-1 is 0.9Na based on the weight of oxide2O·63.6SiO2·34.8Al2O3(ii) a The unit cell constant is 2.450nm, the relative crystallinity is 54 percent, and the total specific surface area is 529m2In terms of/g, total pore volume 0.307cm3And/g, the ratio of the amount of the B acid to the amount of the L acid at 350 ℃, namely B/L is 0.48.
Example 2
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
Preparing NaY molecular sieve gel according to the molar ratio in the example 1, statically crystallizing at 100 ℃ for 26 hours, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 45 ℃, and simultaneously carrying out concurrent flow on Al under vigorous stirring2(SO4)3Solution (concentration 90 gAl)2O3adding/L) and ammonia water (mass fraction is 8%) into the mixture, controlling the pH value of a slurry system to be 9.8 in the mixing process, mixing for a certain time, then carrying out constant-temperature treatment at 55 ℃ for 8 hours, filtering, washing and drying to obtain the silicon-aluminum material AFCY-4.
The SEM picture of AFCY-4 shows that the molecular sieve crystal grain surface is coated with a wrinkled structure. The transmission electron microscope photo shows regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together. An XRD spectrogram shows that an FAU crystal phase structure and a pseudo-boehmite structure exist at the same time; the chemical composition of the oxide-based nano-particles is 5.8Na by weight2O·31.4SiO2·62.3Al2O3(ii) a The total specific surface area is 498m2(ii)/g, total pore volume 0.432cm3(ii)/g; the BJH pore size distribution curve shows bimodal distribution around 3.8nm and 7.4nm respectively; the laser particle size analyzer measured D (V, 0.5) to 2.34 and D (V, 0.9) to 6.72.
According to the weight ratio of 1:0.5, performing first exchange treatment on AFCY-4 and ammonium nitrate at the temperature of 60 ℃ for 1 hour, filtering, washing with water and drying; carrying out first hydrothermal roasting treatment on a sample for 2 hours at the temperature of 600 ℃ and under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium chloride at the temperature of 60 ℃ according to the weight ratio of 1:0.3, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at the temperature of 600 ℃ and under the condition of 100% water vapor to obtain the hierarchical porous composite material, which is marked as PL-2.
The XRD diffraction pattern of PL-2 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-2 is 0.5Na based on the weight of oxide2O·32.5SiO2·66.8Al2O3(ii) a The unit cell constant is 2.447nm, the relative crystallinity is 35 percent, and the total specific surface area is 450m2G, total pore volume 0.4cm3And/g, the ratio of the amount of the B acid to the amount of the L acid at 350 ℃, namely B/L is 0.30.
Example 3
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
According to 7.5SiO2：Al2O3：2.15Na2O：190H2Preparing NaY molecular sieve gel according to the molar ratio of O, statically crystallizing for 40 hours at the temperature of 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 55 ℃, and simultaneously carrying out Al parallel flow under vigorous stirring2(SO4)3Solution (concentration 90 gAl)2O3/L) and NaAlO2Solution (concentration 1)02gAl2O3and/L) adding the silicon-aluminum material into the slurry, controlling the pH value of a slurry system to be 9.0 in the mixing process, mixing for a certain time, then carrying out constant-temperature treatment at 60 ℃ for 2 hours, filtering, washing and drying to obtain the silicon-aluminum material AFCY-5.
The SEM picture of AFCY-5 shows that the molecular sieve crystal grain surface is coated with a wrinkled structure. The transmission electron microscope photo shows regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together. An XRD spectrogram shows that an FAU crystal phase structure and a pseudo-boehmite structure exist at the same time; the chemical composition of the oxide-doped sodium titanate is 10.8Na in terms of weight of oxide2O·53.8SiO2·35.0Al2O3(ii) a The total specific surface area of the powder is 647m2(iv)/g, total pore volume 0.377cm3(ii)/g; the BJH pore size distribution curve shows bimodal distribution around 3.8nm and 9.0nm respectively; d (V, 0.5) ═ 2.13 and D (V, 0.9) ═ 5.02 measured by a laser particle sizer.
According to the weight ratio of 1:0.5, carrying out first exchange treatment on AFCY-5 and ammonium sulfate at 70 ℃, wherein the treatment time is 2 hours, filtering, washing and drying; carrying out first hydrothermal roasting treatment on the sample for 2 hours at 650 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium sulfate at 70 ℃ according to the weight ratio of 1:0.4, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at 650 ℃ under the condition of 100% water vapor to obtain the hierarchical porous composite material, which is marked as PL-3.
The XRD diffraction pattern of PL-3 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-3 is 0.95Na based on the weight of oxide2O·58.9SiO2·38.9Al2O3(ii) a The unit cell constant is 2.444nm, the relative crystallinity is 46 percent, and the total specific surface area is 508m2(ii)/g, total pore volume 0.311cm3And/g, the ratio of the amount of B acid to the amount of L acid at 350 ℃, namely B/L is 0.44.
Example 4
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 3, statically crystallizing for 32 hours at 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 40 ℃, and simultaneously carrying out Al parallel flow under vigorous stirring2(SO4)3Solution (concentration 90 gAl)2O3and/L) and NaOH solution (with the concentration of 1M) are added into the mixture, the pH value of a slurry system is controlled to be 10.5 in the mixing process, after the mixture is mixed for a certain time, the mixture is treated at the constant temperature of 75 ℃ for 3 hours, and then the filtration, the washing and the drying are carried out, so that the silicon-aluminum material AFCY-6 is obtained.
The SEM picture of AFCY-6 shows that the molecular sieve crystal grain surface is coated with a wrinkled structure. The transmission electron microscope photo shows regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together. An XRD spectrogram shows that an FAU crystal phase structure and a pseudo-boehmite structure exist at the same time; the chemical composition of the oxide-doped sodium titanate is 10.5Na in terms of weight of oxide2O·58.4SiO2·30.4Al2O3(ii) a The total specific surface area is 670m2(ii)/g, total pore volume 0.334cm3(ii)/g; the BJH pore size distribution curve shows bimodal distribution around 3.8nm and 6.6nm respectively; the laser particle size analyzer measured D (V, 0.5) ═ 1.92 and D (V, 0.9) ═ 4.01.
According to the weight ratio of 1:1, performing first exchange treatment on AFCY-6 and ammonium chloride at 75 ℃ for 1 hour, filtering, washing with water, and drying; carrying out first hydrothermal roasting treatment on the sample for 3 hours at 580 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium chloride at 75 ℃ according to the weight ratio of 1:0.4, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at 580 ℃ under the condition of 100% water vapor to obtain the hierarchical porous composite material, which is marked as PL-4.
The XRD diffraction pattern of PL-4 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-4 is 0.48Na based on the weight of oxide2O·64.1SiO2·35.1Al2O3(ii) a The unit cell constant is 2.446nm, the relative crystallinity is 58 percent, and the total specific surface area is 532m2In terms of/g, total pore volume 0.288cm3And/g, the ratio of the amount of the acid B to the amount of the acid L at 350 ℃, namely B/L is 0.50.
Example 5
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
According to 7.5SiO2：Al2O3：2.15Na2O：190H2In the molar ratio of O, water glass, aluminum sulfate, sodium metaaluminate, a directing agent and deionized water are violently mixed to form NaY molecular sieve gel, the mass ratio of the directing agent is 5%, the gel is statically crystallized for 42 hours at the temperature of 100 ℃, and a NaY molecular sieve filter cake is obtained after cooling, filtering and washing; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 55 ℃, and simultaneously carrying out AlCl in a parallel flow mode at the temperature3Solution (concentration 60 gAl)2O3/L) and sodium metaaluminate solution (concentration 180 gAl)2O3and/L) adding the silicon-aluminum material AFYH-2, controlling the pH value of the slurry to be 9.0, mixing for a certain time, stirring at the constant temperature of 75 ℃ for 1 hour, then transferring the slurry into a stainless steel crystallization kettle, performing hydrothermal crystallization at the temperature of 100 ℃ for 20 hours, filtering, washing and drying to obtain the silicon-aluminum material AFYH-2.
An XRD spectrum of AFYH-2 shows that diffraction peaks appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 28 degrees, 31.4 degrees, 38.5 degrees, 49 degrees and 65 degrees, which respectively shows that the silicon aluminum material simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure of a Y-type molecular sieve; scanning electron microscope SEM pictures show that the wrinkled structure is coated on the surface of the molecular sieve crystal grains; the transmission electron microscope photo shows regular and ordered diffraction stripes and a disordered structure without fixed crystal face trend, and the disordered structure is derived from the edges of the ordered diffraction stripes for growth, two kinds of diffraction stripes are adoptedThe structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 2.30 and D (V, 0.9) ═ 5.88. The anhydrous chemical expression of AFYH-2 is 9.1Na based on the weight of oxide2O·43.5SiO2·47.0Al2O3(ii) a The total specific surface area is 601m2(iv)/g, total pore volume of 0.440 cm3(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.
According to the weight ratio of 1:0.6, carrying out primary exchange treatment on AFYH-2 and ammonium chloride at 65 ℃ for 1 hour, filtering, washing with water, and drying; carrying out first hydrothermal roasting treatment on the sample for 4 hours at 530 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium chloride at 65 ℃ according to the weight ratio of 1:0.6, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at 530 ℃ and under the condition of 100% water vapor to obtain the hierarchical porous composite material, which is marked as PL-5.
The XRD diffraction pattern of PL-5 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-5 is 0.67Na based on the weight of oxide2O·47.7SiO2·51.2Al2O3(ii) a The unit cell constant is 2.451nm, the relative crystallinity is 44 percent, and the total specific surface area is 485m2(ii)/g, total pore volume 0.389cm3And/g, the ratio of the amount of the B acid to the amount of the L acid at 350 ℃, namely B/L is 0.38.
Example 6
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
According to 8.5SiO2：Al2O3：2.65Na2O：210H2Preparing NaY molecular sieve gel according to the molar ratio of O, statically crystallizing for 20 hours at the temperature of 100 ℃, and cooling, filtering and washing to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 45 ℃, and simultaneously carrying out Al parallel flow at the temperature2(SO4)3Solution (concentration 90 gAl)2O3adding/L) and ammonia water (mass fraction is 8%) into the solution, controlling the pH value of the slurry to be 10.0, mixing for a certain time, stirring at the constant temperature of 70 ℃ for 4 hours, then transferring the slurry into a stainless steel crystallization kettle, carrying out hydrothermal crystallization at the temperature of 100 ℃ for 28 hours, filtering, washing and drying to obtain the silicon-aluminum material AFYH-7.
An XRD spectrum of AFYH-7 shows that the FAU crystal phase structure and the pseudo boehmite structure simultaneously contain the Y-type molecular sieve; scanning electron microscope SEM pictures show that the wrinkled structure is coated on the surface of the molecular sieve crystal grains; the transmission electron microscope photo shows regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 2.41 and D (V, 0.9) ═ 7.09. The anhydrous chemical expression of AFYH-7 is 5.9Na based on the weight of oxide2O·25.4SiO2·68.1Al2O3(ii) a The total specific surface area is 465 m2(ii)/g, total pore volume 0.458cm3(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.
Performing first exchange treatment on AFYH-7 and ammonium sulfate at 55 ℃ according to the weight ratio of 1:0.4, wherein the treatment time is 1 hour, filtering, washing with water, and drying; carrying out first hydrothermal roasting treatment on the sample for 1 hour at 680 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium sulfate at the temperature of 55 ℃ according to the weight ratio of 1:0.2, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at 680 ℃ and 100% steam to obtain the hierarchical porous composite material, which is marked as PL-6.
The XRD diffraction pattern of PL-6 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-6 is 0.81Na based on the weight of oxide2O·27.5SiO2·71.4Al2O3(ii) a The unit cell constant is 2.443nm, the relative crystallinity is 39 percent, and the total specific surface area is 360m2In g, total pore volume 0.392cm3The ratio of the amount of B acid to the amount of L acid at 350 ℃,namely, B/L is 0.30.
Example 7
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 6, statically crystallizing at 100 ℃ for 40 hours, and cooling, filtering and washing to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, and simultaneously carrying out AlCl in a parallel flow mode at room temperature3Solution (concentration 60 gAl)2O3/L) and sodium metaaluminate solution (concentration 102 gAl)2O3and/L) adding the silicon-aluminum material AFYH-8, controlling the pH value of the slurry to be 11.0, mixing for a certain time, stirring at the constant temperature of 60 ℃ for 2 hours, then transferring the slurry into a stainless steel crystallization kettle, performing hydrothermal crystallization at the temperature of 100 ℃ for 12 hours, filtering, washing and drying to obtain the silicon-aluminum material AFYH-8.
An XRD spectrum of AFYH-8 shows that the FAU crystal phase structure and the pseudo boehmite structure simultaneously contain the Y-type molecular sieve; scanning electron microscope SEM pictures show that the wrinkled structure is coated on the surface of the molecular sieve crystal grains; the transmission electron microscope photo shows regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 2.48 and D (V, 0.9) ═ 7.63. The anhydrous chemical expression of AFYH-8 is 6.8Na based on the weight of oxide2O·21.5SiO2·71.2Al2O3(ii) a The total specific surface area is 426 m2Per g, total pore volume of 0.468cm3(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.
According to the weight ratio of 1:0.8, carrying out primary exchange treatment on AFYH-8 and ammonium chloride at 50 ℃ for 1 hour, filtering, washing with water, and drying; carrying out first hydrothermal roasting treatment on a sample for 4 hours at 500 ℃ under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium chloride at 50 ℃ according to the weight ratio of 1:0.2, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at 500 ℃ under the condition of 100% water vapor to obtain the hierarchical porous composite material, which is marked as PL-7.
The XRD diffraction pattern of PL-7 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-7 is 0.54Na based on the weight of oxide2O·25.1SiO2·73.9Al2O3(ii) a Unit cell constant of 2.455nm, relative crystallinity of 32%, total specific surface area of 358m2G, total pore volume 0.40cm3And/g, the ratio of the amount of acid B to the amount of acid L at 350 ℃, i.e. B/L is 0.25.
Example 8
This example illustrates the preparation of the invention and the resulting hierarchical pore composite.
According to 7.5SiO2：Al2O3：2.15Na2O：190H2Preparing NaY molecular sieve gel according to the molar ratio of O, statically crystallizing for 50 hours at 100 ℃, and cooling, filtering and washing to obtain a NaY molecular sieve filter cake; mixing the obtained NaY molecular sieve filter cake with a proper amount of deionized water, pulping, homogenizing, heating to 45 ℃, and simultaneously carrying out Al parallel flow at the temperature2(SO4)3Solution (concentration 90 gAl)2O3adding/L) and ammonia water (mass fraction is 8%) into the solution, controlling the pH value of the slurry to be 10.2, mixing the solution for a certain time, stirring the mixture for 3 hours at a constant temperature of 65 ℃, then transferring the slurry into a stainless steel crystallization kettle, carrying out hydrothermal crystallization for 15 hours at a temperature of 100 ℃, filtering, washing and drying the slurry to obtain the silicon-aluminum material AFYH-3.
An XRD spectrum of AFYH-3 shows that the FAU crystal phase structure and the pseudo boehmite structure simultaneously contain the Y-type molecular sieve; scanning electron microscope SEM pictures show that the wrinkled structure is coated on the surface of the molecular sieve crystal grains; the transmission electron microscope photo shows regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 1.94 and D (V, 0.9) ═ 4.34. The anhydrous chemical expression of AFYH-3 is 10.2Na based on the weight of oxide2O·54.3SiO2·35.2Al2O3(ii) a The total specific surface area is 672 m2In terms of/g, total pore volume of 0.378cm3(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.
According to the weight ratio of 1:0.7, carrying out primary exchange treatment on AFYH-3 and ammonium sulfate at 75 ℃ for 2 hours, filtering, washing with water and drying; carrying out first hydrothermal roasting treatment on the sample for 2 hours at the temperature of 630 ℃ and under the condition of 100% steam; adding water into the roasted sample, pulping, performing second exchange treatment with ammonium sulfate at 75 ℃ according to the weight ratio of 1:0.3, filtering, washing with water, and drying; and then carrying out second hydrothermal roasting treatment for 2 hours at the temperature of 600 ℃ and under the condition of 100 percent of water vapor to obtain the hierarchical porous composite material, which is marked as PL-8.
The XRD diffraction pattern of PL-8 has the characteristics shown in figure 1, and characteristic diffraction peaks of Y-type molecular sieve and gamma-alumina structures exist simultaneously. The chemical composition of PL-8 is 0.78Na based on the weight of oxide2O·59.0SiO2·39.8Al2O3(ii) a The unit cell constant is 2.449nm, the relative crystallinity is 52 percent, and the total specific surface area is 542m2Per g, total pore volume 0.339cm3And/g, the ratio of the amount of the B acid to the amount of the L acid at 350 ℃, namely B/L is 0.47.
Examples 9 to 16
Examples 9-16 illustrate the catalytic activity of the hierarchical pore composite materials prepared according to the present invention.
The hierarchical porous composite materials PL-1 to PL-8 described in the above examples 1 to 8 were mixed with ammonium chloride solution again for exchange treatment until the sodium oxide content was washed to 0.3 wt% or less, filtered, dried, tableted and sieved into 20 to 40 mesh particles, aged at 800 ℃ under 100% steam for 8 hours, and then the microreactivity index MA was measured on a light oil microreactivity evaluation instrument.
Light oil micro-reverse evaluation conditions: the raw oil is Dagang straight run light diesel oil, the sample loading is 2g, the oil inlet is 1.56g, and the reaction temperature is 460 ℃.
The microreflective index is shown in Table 1.
TABLE 1
| Sample (I) | MA | Sample (I) | MA |
| PL-1 | 61 | PL-5 | 54 |
| PL-2 | 54 | PL-6 | 53 |
| PL-3 | 59 | PL-7 | 51 |
| PL-4 | 62 | PL-8 | 61 |
Comparative examples 1 to 8
Comparative examples 1-8 are presented to illustrate the reactivity of comparative samples of similar composition prepared by mechanical mixing.
According to the similar composition of the hierarchical porous composite materials PL-1 to PL-8 described in examples 1 to 8, NaY molecular sieve and mesoporous material were mechanically mixed, and subjected to twice contact treatment and twice hydrothermal calcination treatment with ammonium salt according to the treatment methods of PL-1 to PL-8, thereby obtaining comparative samples DB-1 to DB-8. Mixing DB-1-DB-8 and ammonium chloride solution again for exchange until the content of sodium oxide is washed to be below 0.3 weight percent, filtering, drying, tabletting and screening into particles of 20-40 meshes, aging for 8 hours under the condition of 800 ℃ and 100 percent of water vapor, and then measuring the micro-reactive index MA on a light oil micro-reactive activity evaluation instrument. The feed oil and evaluation conditions were the same as in examples 9 to 16.
The microreflective index is shown in Table 2.
TABLE 2
| Sample (I) | MA | Sample (I) | MA |
| DB-1 | 58 | DB-5 | 52 |
| DB-2 | 50 | DB-6 | 50 |
| DB-3 | 55 | DB-7 | 48 |
| DB-4 | 59 | DB-8 | 57 |
As can be seen from the micro-inversion activity index MA in Table 1, the hierarchical porous composite materials PL-1 to PL-8 obtained in examples 1 to 8 have high cracking activity, and the MA can reach 51 to 62 after aging treatment for 8 hours at 800 ℃ by 100% steam.
The light oil micro-inversion activity index MA of comparative samples DB-1 to DB-8 shown in Table 2 is obviously lower after aging treatment for 8 hours at 800 ℃ by 100 percent water vapor, and the MA is only 48 to 59 and is obviously lower than that of the sample PL-1 to PL-8 of the embodiment.
Therefore, the hierarchical pore composite material has the advantages that the microporous structure of the Y-type molecular sieve and the mesoporous structure of the gamma-alumina exist at the same time, and the two pore structures are organically combined and communicated with each other, so that the accessibility of an active center is improved, the reaction performance is improved, and the hierarchical pore composite material has better reaction activity compared with a simple mechanical mixed sample.
Claims (11)
1. The preparation method of the hierarchical pore composite material is characterized by comprising the following preparation steps: according to the weight ratio of 1 (0.2-1.2), carrying out first exchange treatment on a silicon-aluminum material and ammonium salt at the temperature of 40-90 ℃ for 0.5-3 hours, filtering, washing and drying; carrying out primary hydrothermal roasting treatment on the sample for 1-4 hours at 500-700 ℃ under the condition of 100% steam; adding water into the roasted sample for pulping, performing second exchange treatment with ammonium salt at the temperature of 40-90 ℃ according to the weight ratio of 1 (0.2-0.8), filtering, washing with water, and drying; carrying out second hydrothermal roasting treatment on the sample for 1-4 hours at 500-700 ℃ under the condition of 100% steam; wherein the silicon-aluminum material simultaneously contains a Y-type molecular sieve and a pseudo-boehmite structure mesoporous alumina layer, and the mesoporous alumina layer generatesThe mesoporous alumina layer grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve in an extending way, and the two structures are built together; the chemical composition of the silicon-aluminum material is (4-12) Na based on the weight of oxide2O·(20～60)SiO2·(30～75)Al2O3(ii) a The silicon-aluminum material has a particle size parameter D (V, 0.5) of 1.8-2.5 and a particle size parameter D (V, 0.9) of 4.0-8.0, and the total specific surface area is 380-700 m2(ii) a total pore volume of 0.32 to 0.48cm3(ii)/g; the silicon-aluminum material has the characteristic of gradient hole distribution, and can be distributed in a plurality of holes at 3-4 nm and 6-9 nm respectively.
2. The method of claim 1, wherein the silica-alumina material is obtained by: (1) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then statically crystallizing at the temperature of 95-105 ℃; (2) filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; (3) mixing the NaY molecular sieve filter cake obtained in the step (2) with deionized water, pulping and homogenizing, adding an aluminum source and an alkali solution into the mixture simultaneously in a parallel flow mode under the conditions that the temperature is between room temperature and 85 ℃ and violent stirring, and controlling the pH value of a slurry system to be 9-11 in the mixing process; (4) and then the mixture is processed for 1 to 10 hours at the constant temperature ranging from room temperature to 90 ℃ and the product is recovered, or the mixture is processed for 1 to 4 hours at the constant temperature ranging from room temperature to 90 ℃ and then is placed in a closed crystallization kettle, and hydrothermal crystallization is carried out for 3 to 30 hours at the temperature ranging from 95 ℃ to 105 ℃ and the product is recovered.
3. The process according to claim 2, wherein the static crystallization in (1) is carried out for 8 to 50 hours.
4. The preparation process according to claim 2, wherein the aluminum source in (3) is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate, and when the sodium metaaluminate is used as the alkali solution, the alumina content is counted in the total alumina content.
5. The process according to claim 2, wherein the temperature during the mixing in (3) is 30 to 70 ℃.
6. The process according to claim 2, wherein the constant temperature treatment in (4) is carried out at 40 to 80 ℃ for 2 to 8 hours.
7. The method according to claim 1, wherein the ammonium salt is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
8. The preparation method according to claim 1, wherein the first exchange treatment of the silicon-aluminum material and the ammonium salt is carried out, the weight ratio of the silicon-aluminum material to the ammonium salt is 1 (0.2-1.2), preferably 1 (0.4-1.0), and the exchange treatment temperature is 40-90 ℃, preferably 50-80 ℃.
9. The method according to claim 1, wherein the hydrothermal calcination treatment is carried out at a temperature of 500 to 700 ℃ for 1 to 4 hours, preferably 550 to 650 ℃.
10. The preparation method according to claim 1, wherein the second exchange treatment with the ammonium salt comprises the steps that the weight ratio of the silicon-aluminum material to the ammonium salt is 1 (0.2-0.8), preferably 1 (0.3-0.6), and the exchange treatment temperature is 40-90 ℃, preferably 50-80 ℃.
11. The preparation method according to claim 1, wherein the hierarchical pore composite material comprises an alumina mesoporous layer and a Y-type molecular sieve, and the alumina layer coats the surface of the molecular sieve, and the two structures are connected with each other; the chemical composition of the hierarchical porous composite material is (0.3-1.0) Na based on the weight of oxides2O·(25～65)SiO2·(30～75)Al2O3(ii) a A unit cell constant of 2.440 to 2.455nm, preferably 2.442 to 2.453nm, a relative crystallinity of 20 to 60%, preferably 25 to 55%, and a total specific surface areaA product of 350 to 550m2(ii) a total pore volume of 0.25 to 0.40cm3The ratio of the amount of B acid to the amount of L acid is 0.20 to 0.50 per gram at 350 ℃.
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