CN111744533A

CN111744533A - Preparation method of rare earth type hierarchical pore material

Info

Publication number: CN111744533A
Application number: CN201910236268.8A
Authority: CN
Inventors: 郑金玉; 王成强; 罗一斌; 满征
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-03-27
Filing date: 2019-03-27
Publication date: 2020-10-09

Abstract

The preparation method of the rare earth type hierarchical pore material is characterized by comprising the step of depositing rare earth by modifying a silicon-aluminum material by rare earth through two-cross two-baking, wherein the silicon-aluminum material has an FAU crystal phase structure and a pseudo-boehmite structure, and has a few pore distributions with two characteristics of 3-4 nm and 7-10 nm or particle size parameters of D (V, 0.5) 1.8-2.5 and D (V, 0.9) 4.0-8.0. The material prepared by the method has a micropore structure and a mesopore structure, and the modification treatment of the rare earth effectively promotes the improvement of the reaction performance.

Description

Preparation method of rare earth type hierarchical pore material

Technical Field

The invention relates to a preparation method of a hierarchical pore material, in particular to a preparation method of a rare earth type hierarchical pore material.

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 residues of heavier components 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. Crystalline molecular sieves are porous materials with a pore size of less than 2nm and a special crystalline phase structure, and materials with a pore size of less than 2nm are named as microporous materials according to the definition of IUPAC, so that crystalline molecular sieves or zeolites generally belong to microporous materials, and the microporous molecular sieve materials have stronger acidity and higher structural stability due to complete crystal structures and special framework structures, show higher catalytic activity in catalytic reactions, and are 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. CN1436727A discloses a modified faujasite and a hydrocarbon cracking catalyst containing the zeolite, which adopts a one-exchange one-baking process, namely NaY firstly carries out a one-exchange reaction with a phosphorus compound and an ammonium compound, then a rare earth solution is added for continuous reaction, and the catalyst is obtained by filtering, washing and hydrothermal roasting.

CN1382631A discloses a high-silicon rare earth Y-type zeolite, which is prepared by gas phase reaction of rare earth Y-type zeolite and silicon tetrachloride, wherein the content of rare earth in crystal is 4-15 wt%, the cell constant is 2.450-2.458 nm, the collapse temperature is 1000-1056 ℃, the silica-alumina ratio is 8.3-8.8, and the content of sodium oxide is less than 1.0 wt%.

CN101823726A discloses a modified Y molecular sieve, which is prepared by a one-exchange one-baking process, namely NaY is firstly subjected to a one-exchange reaction with a rare earth solution, then a phosphorus compound is added for continuous reaction, and the modified Y molecular sieve is obtained by filtering, washing and hydrothermal roasting, wherein the content of rare earth is about 11-23 wt%, most of rare earth is positioned in a sodalite cage, the stability of the molecular sieve is improved, meanwhile, the acidity of the molecular sieve can be adjusted, and a catalyst containing the molecular sieve has the characteristics of strong heavy oil conversion capability and good coke selectivity.

CN100344374C discloses a rare earth Y molecular sieve and a preparation method thereof, the content of rare earth is 12-22 wt% calculated by rare earth oxide, and rare earth ions are all positioned in a molecular sieve small cage which is a small cage²⁷In the Al MAS NMR spectrum, no peak was observed at a chemical shift of 0 ppm. The preparation method comprises the steps of adopting a one-way and one-way roasting process, adjusting the pH value of a solution to 8-11 by using an alkaline solution after one-way exchange, then filtering, washing, drying and roasting, or separating a molecular sieve filter cake after one-way exchange, collecting filtrate, adding the alkaline solution into the filtrate to adjust the pH value of the solution to 8-11, adding water into the obtained rare earth hydroxide filter cake and the molecular sieve filter cake, pulping, filtering, washing, drying and roasting. The process makes the excessive rare earth ions in the solution precipitate to avoid the rare earth loss and ensure that the rare earth ions are completely positioned in the molecular sieve small cage.

CN1317547A discloses an olefin reduction catalyst and a preparation method thereof, the catalyst mainly comprises REY molecular sieve with the rare earth content of 12-20 wt% and the crystallinity of more than 50% and a phosphorus and rare earth compound modified PREY molecular sieve with the rare earth content of 2-12 wt%, the phosphorus content of 0.2-3 wt% and the unit cell constant of 2.445-2.465 nm.

CN1506161A discloses a rare earth ultrastable Y molecular sieve, which adopts a double-cross double-baking process, namely, after a first-cross single-baking rare earth sodium Y is obtained, the first-cross single-baking rare earth sodium Y reacts with rare earth and phosphorus-containing substances step by step and is roasted for the second time to obtain a composite modified Y molecular sieve with the rare earth content of 8-25 wt%, the phosphorus content of 0.1-3.0 wt%, the crystallinity of 30-55% and the unit cell constant of 2.455-2.477 nm.

The molecular sieve prepared by adopting the double cross double roasting process also has other characteristics, for example, the molecular sieve which is disclosed in CN101537366A and can improve the coking performance and the preparation method thereof still adopt the double cross double roasting process, the phosphorus content of the molecular sieve is 0.05-5.0%, the rare earth content is less, only 0.05-4.0%, the unit cell constant is 2.430-2.440 nm, and the crystallinity is 35-55%.

Along with the increasing exhaustion of petroleum resources, the trend of crude oil heaving and deterioration is obvious, the slag blending proportion is continuously improved, and the requirement 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, a plurality of refineries begin to blend vacuum residual oil, even normal pressure residual oil is directly used as a cracking raw material, the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefits of oil refining enterprises, and the macromolecular cracking capability of a catalyst therein 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 macromolecular reaction, and also shows a certain inhibiting effect on the cracking reaction of macromolecules 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 size, no diffusion limitation to reactant molecules, and a high cracking activity.

According to the IUPAC definition, a material with a pore size 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 size range, so that the research of mesoporous materials, particularly mesoporous silicon-aluminum materials, has attracted great interest to researchers in the catalysis field. Mesoporous materials are firstly developed and succeeded by Mobil Corporation in 1992 (Beck J S, Vartuli J Z, Roth W J et al, J.Am.Chem.Comm.Soc., 1992, 114, 10834-containing 10843) and named as M41S series mesoporous molecular sieves, including MCM-41(Mobil Corporation Material-41) and MCM-48, etc., wherein the pore diameter of the molecular sieves can reach 1.6-10 nm, and the mesoporous materials are uniform and adjustable, have concentrated pore diameter 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 thickness of the pore walls of the molecular sieves, and if a neutral template agent is adopted, the molecular sieve with thicker pore walls can be obtained, but the defect of weaker acidity still exists. In CN1349929A, a novel mesoporous molecular sieve is disclosed, in which the primary and secondary structural units of zeolite are introduced into the pore walls of the molecular sieve, so that the molecular sieve has the basic structure of the 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 and organic silicon source, and mostly need to be subjected to a high-temperature hydrothermal post-treatment process. In order to reduce the preparation cost and obtain a porous material 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. The method disclosed in US4,708,945 is that firstly silica particles or hydrated silica are loaded on porous boehmite, and then the obtained compound is subjected to hydrothermal treatment for a certain time at the temperature of more than 600 ℃ to prepare the catalyst with the silica loaded on the surface of the boehmite, wherein the silica is combined with hydroxyl of the transitional 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 the high macromolecular cracking performance is shown in a catalytic cracking reaction.

Disclosure of Invention

The invention aims to provide a preparation method of a rare earth type hierarchical pore material different from the prior art.

The preparation method of the rare earth type hierarchical pore material is characterized by comprising the following preparation processes: carrying out first ion exchange treatment on a silicon-aluminum material and a rare earth solution A and/or an ammonium salt solution, filtering, washing and drying; after the obtained mixture is subjected to primary roasting treatment under the condition of 0-100% of water vapor, the obtained mixture is mixed with an ammonium salt solution to perform secondary ion exchange treatment, and the obtained mixture is filtered or not filtered, or is mixed with an acid solution to perform secondary ion exchange treatment and is filtered; mixing the obtained rare earth solution B with the obtained mixture, adjusting the pH value of the slurry to 5-10 by using an alkaline solution, filtering or not filtering, and then carrying out the operation under the condition of 0-100% of water vaporCarrying out secondary roasting treatment; wherein one of the silicon-aluminum materials is characterized in that an XRD spectrogram of the silicon-aluminum material has a characteristic diffraction peak with an FAU crystalline phase structure and a pseudo-boehmite structure, a wrinkled pseudo-boehmite structure alumina mesoporous layer is coated on the surface of the FAU crystalline phase structure, and the two structures are communicated with each other and grow together; the silicon-aluminum material contains 4-12% of sodium oxide, 20-60% of silicon oxide and 30-75% of aluminum oxide by weight of oxides; the silicon-aluminum material has the gradient pore distribution characteristic formed by a microporous structure and a mesoporous structure, and can be distributed in several pores with two characteristics at 3-4 nm and 7-10 nm, and the specific surface area is 420-720 m²(ii) a total pore volume of 0.35 to 0.50cm³A characteristic of/g; or the second silicon-aluminum material is a mesoporous alumina layer containing both a Y-type molecular sieve and a pseudo-boehmite structure, the mesoporous alumina layer grows on the surface of the crystal grain of the Y-type molecular sieve and uniformly coats the crystal grain of the molecular sieve, 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 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.

One of the silicon-aluminum materials is prepared by the following steps: adding water into molecular sieve dry powder with FAU crystal phase structure, pulping and homogenizing; adding an aluminum source and an alkali solution into the slurry at the room temperature to 85 ℃ in a parallel flow mode to perform a neutralization reaction, and controlling the pH value of the slurry system to be 8-10.5; and after the neutralization reaction, continuously aging for 1-10 hours at the temperature of room temperature to 90 ℃ and recovering the product, or aging for 1-4 hours, then transferring to a closed crystallization kettle, and continuously crystallizing for 3-30 hours at the temperature of 95-105 ℃ and recovering the product. In the process, a mesoporous alumina layer with typical mesoporous aperture and excellent diffusion property is grown on the surface of the crystal grain of the Y-type molecular sieve to form a composite structure in which a mesoporous pore passage and a microporous pore passage are connected with each other, so that not only can gradient pore passage distribution be formed, but also gradient acid center distribution can be formed.

In the preparation process of one of the above-mentioned silicon-aluminum materials, the molecular sieve with FAU crystal phase structure may be a dried molecular sieve powder obtained by direct synthesis and filtration drying, or may be a commercial molecular sieve dried powder product, and may be NaY molecular sieves with different silicon-aluminum ratios, different crystallinities and different crystal grain sizes, and the crystallinity is preferably greater than 70%, more preferably greater than 80%. For example, the NaY molecular sieve dry powder can be obtained by mixing and stirring water glass, sodium metaaluminate, aluminum sulfate, a directing agent and deionized water in a specific feeding sequence in proportion, crystallizing for a plurality of times at a temperature of 95-105 ℃, filtering, washing and drying. The adding proportion of the water glass, the sodium metaaluminate, the aluminum sulfate, the guiding agent and the deionized water can be the feeding proportion of a conventional NaY molecular sieve or the feeding proportion of a NaY molecular sieve for preparing special performance, such as the feeding proportion of a large-grain or small-grain NaY molecular sieve, and the feeding proportion and the concentration of each raw material are not specially limited as long as the NaY molecular sieve with an FAU crystal phase structure can be obtained. The order of addition may be various, and is not particularly limited. The directing agent can be prepared by various methods, for example, the directing agent can be prepared according to the methods disclosed in the prior art (US3639099 and US3671191), and the typical directing agent is prepared by mixing a silicon source, an aluminum source, an alkali solution and deionized water according to (15-18) Na₂O:Al₂O₃:(15～17)SiO₂:(280～380)H₂And mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at the temperature of room temperature to 70 ℃. The silicon source used for preparing the guiding agent is water glass, the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.

In the preparation process of one of the above-mentioned silicon-aluminum materials, the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate or aluminum chloride; the alkali solution is selected from one or more of ammonia water, potassium hydroxide, sodium hydroxide or 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. Sodium metaaluminate(s) may be presentThe sodium metaaluminate with different causticity ratios and different concentrations is adopted. 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 190gAl₂O₃/L。

In the preparation process of one of the above-mentioned silicon-aluminum materials, the concept of the concurrent flow mode of adding the aluminum source and the alkali solution at the same time 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 a container at the same time 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 can be used in the specific operation, the flow parameters per unit time of the peristaltic pumps for respectively conveying the aluminum source and the alkali solution are controlled, and the process is performed at a constant speed so as to ensure that the aluminum source and the alkali solution are added in the same time.

In the preparation process of one of the silicon-aluminum materials, the neutralization reaction is carried out at the temperature of between room temperature and 85 ℃, and preferably at the temperature of between 30 and 70 ℃. The aging temperature is between room temperature and 90 ℃, preferably 40-80 ℃, and the time is 1-10 hours, preferably 2-8 hours; the process for recovering the product generally comprises the steps of filtering, washing and drying the aged product.

The second silicon-aluminum material can be obtained by the following process: preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then statically crystallizing at the temperature of 95-105 ℃; filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; mixing, pulping and homogenizing a NaY molecular sieve filter cake and deionized water, adding an aluminum source and an alkali solution into the NaY molecular sieve filter cake simultaneously in a parallel flow mode under the condition that the temperature is between room temperature and 85 ℃ and under the condition of vigorous stirring, and controlling the pH value of a slurry system in the mixing process to be 9-11; 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.

In the first ion exchange treatment process of the silicon-aluminum material and the rare earth solution A and/or the ammonium salt solution, the weight ratio of the rare earth solution to the silicon-aluminum material calculated by rare earth oxide is 0-0.14, preferably 0.02-0.13, the weight ratio of the ammonium salt to the silicon-aluminum material is 0.05-1.0, the exchange temperature is 40-90 ℃, preferably 50-80 ℃, and the exchange time is 0.5-3.0 hours, preferably 1-2 hours.

In the present invention, the first baking treatment and the second baking treatment are performed at 500 to 700 ℃ and preferably 530 to 650 ℃ under the condition of 0 to 100% steam and preferably 20 to 100% steam for 0.5 to 4.0 hours and preferably 1 to 3 hours.

In the second ion exchange treatment with ammonium salt, the weight ratio of the ammonium salt to the ammonium salt obtained in the previous step is 0.3-0.5, the exchange temperature is 40-90 ℃, preferably 50-80 ℃, and the exchange time is 0.5-3.0 hours, preferably 1-2 hours. In the ion exchange treatment process with the acid solution, the weight ratio of the acid solution to the acid solution obtained in the previous step is 0.03-0.12, preferably 0.05-0.1, the exchange temperature is room temperature-60 ℃, and the exchange time is 0.5-3.0 hours, preferably 1-2 hours.

In the invention, the weight ratio of the mixture to the rare earth solution B is 0.01-0.10, preferably 0.02-0.08, calculated by the rare earth oxide; and adjusting the pH value of the slurry to 5-10, preferably 6-9, wherein the alkaline solution is one or more selected from sodium hydroxide, water glass and ammonia water.

In the present invention, the rare earth solution is well known to those skilled in the art, and may be rare earth chloride or rare earth nitrate, or rare earth chloride or rare earth nitrate composed of a single rare earth element, wherein the rare earth solution commonly includes lanthanum chloride, lanthanum nitrate, cerium chloride or cerium nitrate, etc., or may be a mixed rare earth of different rare earth element ratios, such as cerium-rich or lanthanum-rich mixed rare earth, and may be of any concentration; the ammonium salt can be one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate. The filtration, water washing and drying processes are well known to those skilled in the art and will not be described herein.

The rare earth type hierarchical porous material prepared by the invention contains 2-20 wt% of rare earth, preferably 4-18 wt% of rare earth oxide, and also contains a Y-type molecular sieve microporous structure and gamma-Al₂O₃A mesoporous structure, 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 in an XRD spectrogram represent Y-type molecular sieves, diffraction peaks at 20-30 degrees and about 66 degrees represent alumina structures, and the two structures are communicated with each other; the unit cell constant is 2.445-2.470 nm, preferably 2.448-2.465 nm, the relative crystallinity is 30-60%, preferably 32-55%, and the total specific surface area is 350-600 m²(ii) a total pore volume of 0.25 to 0.45cm³/g。

Drawings

FIG. 1 is an X-ray diffraction pattern of the rare earth type hierarchical pore material RHL-1 of example 1.

FIG. 2 is an X-ray diffraction pattern of the sialon material MMC-1 of example 5.

FIG. 3 is an SEM scanning electron micrograph of the silicoalumina material MMC-1 of example 5.

FIG. 4 is a TEM transmission electron micrograph of the silicoalumina material MMC-1 in example 5.

FIG. 5 is the BJH pore size distribution curve of the silicoaluminophosphate material MMC-1 in example 5.

FIG. 6 is an X-ray diffraction pattern of the rare earth-based hierarchical pore material RPL-1 of example 17.

Detailed Description

The following examples further illustrate the invention but are not intended to limit the invention thereto.

In each example, RE of the sample₂O₃、Na₂O、Al₂O₃、SiO₂The content was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP methods of experiments)", eds Yang Cui et al, published by scientific Press, 1990). The phase, unit cell constant, crystallinity, and the like were measured by X-ray diffraction. Wherein, the crystallinity is measured 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 measured: NaY molecular sieve (GS BG 75004-.

The SEM test adopts a Hitachi S4800 type Japan field emission scanning electron microscope with an accelerating voltage of 5 kV.

Transmission Electron microscope TEM test was carried out using a transmission electron microscope model of FEI Tecnai F20G 2S-TWIN, operating at a voltage of 200 kV.

The specific surface, pore volume and pore size distribution are measured by a low-temperature nitrogen adsorption-desorption volumetric method.

The particle size distribution test is carried out by mixing trace materials with deionized water, adding a small amount of slurry into a 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.

The preparation process of the directing agent used in the examples was: 5700g of water glass (available from Changling catalysts, Inc., SiO)₂261g/L, modulus 3.31, density 1259g/L) was placed in a beaker and 4451g of high alkali sodium metaaluminate (provided by Changling catalysts, Inc., Al) was added with vigorous stirring₂O₃39.9g/L，Na₂O279.4 g/L, density 1326g/L) and aging at 30 ℃ for 18 hours to obtain Na with the molar ratio of 16.1₂O:Al₂O₃:15SiO₂:318.5H₂A directing agent for O.

Examples 1 to 8 illustrate the preparation of the first silicon aluminum material and the process for obtaining rare earth type hierarchical pore materials based on the first silicon aluminum material.

Example 1

With 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂And synthesizing the NaY molecular sieve by using the gel feeding molar ratio of O. Respectively mixing water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water according to the above proportion, and vigorously stirring for 1 hour, wherein the adding proportion of the guiding agent is 5% by weight, crystallizing the mixed gel at 100 ℃ for 25 hours, filtering, washing and drying to obtain the NaY molecular sieve dry powder.

Mixing the NaY molecular sieve dry powder with a proper amount of deionized water, pulping, and simultaneously adding AlCl in a parallel flow mode at 30 DEG C₃Solution (concentration 60 gAl)₂O₃L) and NaOH solution (concentration is 1M) are added into the solution to carry out neutralization reaction, the pH value of the slurry system is kept at 9.4 by adjusting the flow rate of the two materials, the aging treatment is continued for 2 hours at 60 ℃ after the neutralization reaction, and the silicon-aluminum material is obtained after filtering, washing and dryingMaterial YCA-2.

The X-ray diffraction spectrum of YCA-2 shows that characteristic diffraction peaks appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 14 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, which shows that the crystal structure contains FAU crystal phase structure and pseudo-boehmite structure. The scanning electron microscope SEM photo shows that the fold-shaped structure can be seen, the faujasite structure of the NaY molecular sieve can be seen occasionally, and the fold-shaped structure is coated on the surface of the molecular sieve crystal grain. The TEM photograph of a transmission electron microscope shows that two different structures are connected together, the structure with regular diffraction fringes is an FAU crystal phase structure, the disordered structure is a pseudo-boehmite structure of alumina, and the disordered structure grows along the edges of the regular diffraction fringes to form a composite structure. YCA-2 contains 9.3 percent of sodium oxide, 43.6 percent of silicon oxide and 46.2 percent of aluminum oxide by weight of oxides; the specific surface area is 600m²In terms of/g, total pore volume of 0.428cm³The BJH pore size distribution curve shows a variable distribution at about 4nm and 7nm, respectively, indicating that the material has a graded pore distribution profile.

According to the weight ratio of 0.04 of rare earth oxide to YCA-2 and the weight ratio of 0.2 of ammonium salt to YCA-2, carrying out first ion exchange treatment on YCA-2, rare earth solution and ammonium salt solution at 75 ℃ for 1 hour, filtering, washing and drying; then roasting for 2 hours at 580 ℃ under the condition of 100 percent of water vapor; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.4, carrying out secondary ion exchange treatment at 75 ℃ for 1 hour, filtering, adding a rare earth solution according to the proportion of 0.04 of rare earth oxide, adjusting the pH value of the slurry to 8.0 by using ammonia water, stirring for a certain time, filtering and drying; and then carrying out secondary roasting treatment at 580 ℃ under the condition of 100% steam for 2 hours to obtain the rare earth type hierarchical porous material RHL-1.

The XRD diffraction pattern of RHL-1 is shown in figure 1, wherein the microporous structure of the Y-type molecular sieve and gamma-Al are simultaneously contained₂O₃The diffraction peaks at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 ° and 31.4 ° of the mesoporous structure represent Y-type molecular sieve (corresponding to # in the figure), and the diffraction peaks at 20-30 ° and 66 °The diffraction peaks on the left and right represent the alumina structure (peaks in the figure corresponding to parenthesis). The rare earth content is 7.7 wt% calculated by rare earth oxide, the unit cell constant is 2.455nm, the relative crystallinity is 40%, and the total specific surface area is 521m²G, total pore volume 0.400cm³/g。

Example 2

With 8.5SiO₂：Al₂O₃：2.65Na₂O：210H₂And synthesizing the NaY molecular sieve by using the gel feeding molar ratio of O. Respectively mixing water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water according to the above proportion, and vigorously stirring for 1 hour, wherein the adding proportion of the guiding agent is 5% by weight, crystallizing the mixed gel at 100 ℃ for 26 hours, filtering, washing and drying to obtain the NaY molecular sieve dry powder.

Mixing the NaY molecular sieve dry powder with a proper amount of deionized water, pulping, and simultaneously carrying out Al in a parallel flow mode at room temperature₂(SO₄)₃Solution (concentration 50 gAl)₂O₃/L) and NaAlO₂Solution (concentration 182gAl₂O₃L) adding the silicon-aluminum material into the solution to perform neutralization reaction, keeping the pH value of the slurry system at 9.0 by adjusting the flow rate of the two materials, continuing aging treatment for 5 hours at 70 ℃ after the neutralization reaction, and filtering, washing and drying to obtain the silicon-aluminum material YCA-4.

The X-ray diffraction spectrum of YCA-4 shows that characteristic diffraction peaks appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 14 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, which shows that the crystal structure contains FAU crystal phase structure and pseudo-boehmite structure. The scanning electron microscope SEM photo shows that the fold-shaped structure can be seen, the faujasite structure of the NaY molecular sieve can be seen occasionally, and the fold-shaped structure is coated on the surface of the molecular sieve crystal grain. The TEM photograph of a transmission electron microscope shows that two different structures are connected together, the structure with regular diffraction fringes is an FAU crystal phase structure, the disordered structure is a pseudo-boehmite structure of alumina, and the disordered structure grows along the edges of the regular diffraction fringes to form a composite structure. YCA-4 contains sodium oxide 11.9%, silicon oxide 57.3%, and aluminum oxide 30.3% by weight(ii) a The specific surface area is 680m²(ii)/g, total pore volume of 0.379cm³The BJH pore size distribution curve shows a fractional distribution at about 4nm and 8nm, respectively, indicating that the material has a graded pore distribution profile.

Performing first ion exchange treatment on the rare earth oxide and YCA-4 according to the weight ratio of 0.12 and the rare earth solution at 70 ℃, wherein the exchange time is 1 hour, and filtering, washing and drying; then roasting for 2 hours at 600 ℃ under the condition of 100 percent of water vapor; mixing the obtained mixture with a hydrochloric acid solution according to the weight ratio of 1:0.1, carrying out secondary ion exchange treatment for 1 hour at room temperature, filtering, adding a rare earth solution according to the proportion of 0.06 of rare earth oxide, adjusting the pH value of the slurry to 7.5 by using ammonia water, stirring for a certain time, filtering and drying; and then carrying out secondary roasting treatment at 600 ℃ under the condition of 100% water vapor for 2 hours to obtain the rare earth type hierarchical porous material RHL-2.

The XRD diffraction spectrum of RHL-2 has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 18.0 wt% calculated by rare earth oxide, the unit cell constant is 2.468nm, the relative crystallinity is 48%, and the total specific surface area is 580m²Per g, total pore volume 0.322cm³/g。

Example 3

Preparing NaY molecular sieve gel according to the gel feeding molar ratio and the same feeding sequence in the embodiment 2, crystallizing the mixed gel at 100 ℃ for 38 hours, filtering, washing and drying to obtain NaY molecular sieve dry powder.

Mixing the NaY molecular sieve dry powder with a proper amount of deionized water, pulping, and simultaneously adding Al (NO) in a parallel flow mode at 35 DEG C₃)₃Solution (concentration 60 gAl)₂O₃L) and NaOH solution (concentration is 1M) are added into the solution to carry out neutralization reaction, the pH value of the slurry system is kept at 9.8 by adjusting the flow rate of the two materials, aging treatment is continued for 4 hours at 65 ℃ after the neutralization reaction, and the silicon-aluminum material YCA-6 is obtained after filtration, washing and drying.

The X-ray diffraction spectrum of YCA-6 shows that the X-ray diffraction spectrum of the crystal is respectively 6.2 degrees, 10.1 degrees, 11.9 degrees, 14 degrees,Characteristic diffraction peaks appear at 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, indicating that it contains both the FAU crystal phase structure and the pseudo-boehmite structure. The scanning electron microscope SEM photo shows that the fold-shaped structure can be seen, the faujasite structure of the NaY molecular sieve can be seen occasionally, and the fold-shaped structure is coated on the surface of the molecular sieve crystal grain. The TEM photograph of a transmission electron microscope shows that two different structures are connected together, the structure with regular diffraction fringes is an FAU crystal phase structure, the disordered structure is a pseudo-boehmite structure of alumina, and the disordered structure grows along the edges of the regular diffraction fringes to form a composite structure. YCA-6 contains 9.8% of sodium oxide, 48.2% of silicon oxide and 41.3% of aluminum oxide by weight of oxides; the specific surface area is 635m²(ii)/g, total pore volume 0.420cm³The BJH pore size distribution curve shows a fractional distribution at about 4nm and 8nm, respectively, indicating that the material has a graded pore distribution profile.

Performing first ion exchange treatment on the rare earth oxide and YCA-6 according to the weight ratio of 0.12 and the rare earth solution at 55 ℃, wherein the exchange time is 2 hours, and filtering, washing and drying; then roasting for 4 hours at 550 ℃ under the condition of 100 percent of water vapor; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.35, carrying out secondary ion exchange treatment at 50 ℃ for 2 hours, directly adding a rare earth solution into the exchange slurry according to the proportion of 0.02 of rare earth oxide without filtering, adjusting the pH value of the slurry to 7.8 by using a sodium hydroxide solution, stirring for a certain time, filtering and drying; and then carrying out secondary roasting treatment at 550 ℃ under the condition of 100% water vapor for 2 hours to obtain the rare earth type hierarchical porous material RHL-3.

The XRD diffraction spectrum of RHL-3 has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 13.9 wt% calculated by rare earth oxide, the unit cell constant is 2.463nm, the relative crystallinity is 45%, and the total specific surface area is 565m²(ii)/g, total pore volume 0.389cm³/g。

Example 4

Preparing NaY molecular sieve gel according to the gel feeding molar ratio and the same feeding sequence in the embodiment 2, crystallizing the mixed gel at 100 ℃ for 40 hours, filtering, washing and drying to obtain NaY molecular sieve dry powder.

Mixing the NaY molecular sieve dry powder with a proper amount of deionized water, pulping, heating to 40 ℃, and simultaneously carrying out AlCl in a parallel flow mode at the temperature₃Solution (concentration 60 gAl)₂O₃/L) and NaAlO₂Solution (concentration 102 gAl)₂O₃L) adding the silicon-aluminum material into the solution to perform neutralization reaction, keeping the pH value of the slurry system at 9.5 by adjusting the flow rate of the two materials, continuing aging treatment at 80 ℃ for 1 hour after the neutralization reaction, and filtering, washing and drying to obtain the silicon-aluminum material YCA-7.

The X-ray diffraction spectrum of YCA-7 shows that characteristic diffraction peaks appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 14 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, which shows that the crystal structure contains FAU crystal phase structure and pseudo-boehmite structure. The scanning electron microscope SEM photo shows that the fold-shaped structure can be seen, the faujasite structure of the NaY molecular sieve can be seen occasionally, and the fold-shaped structure is coated on the surface of the molecular sieve crystal grain. The TEM photograph of a transmission electron microscope shows that two different structures are connected together, the structure with regular diffraction fringes is an FAU crystal phase structure, the disordered structure is a pseudo-boehmite structure of alumina, and the disordered structure grows along the edges of the regular diffraction fringes to form a composite structure. YCA7 contains sodium oxide 7.1%, silicon oxide 21.4%, and aluminum oxide 70.9%; its specific surface area is 428m²(ii)/g, total pore volume of 0.456cm³The BJH pore size distribution curve shows a fractional distribution at about 4nm and 8nm, respectively, indicating that the material has a graded pore distribution profile.

According to the weight ratio of 0.06 of rare earth oxide to YCA-7 and the weight ratio of 0.1 of ammonium salt to YCA-7, carrying out first ion exchange treatment on YCA-7, rare earth solution and ammonium salt solution at 60 ℃ for 1 hour, filtering, washing and drying; then roasting for 2 hours at 530 ℃ under the condition of 100 percent of water vapor; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.4, carrying out secondary ion exchange treatment at 60 ℃ for 1 hour, filtering, adding a rare earth solution according to the proportion of 0.02 of rare earth oxide, adjusting the pH value to 6.5 by using ammonia water, stirring for a certain time, and directly drying; and then carrying out secondary roasting treatment at 530 ℃ under the condition of 100% water vapor for 2 hours to obtain the rare earth type hierarchical porous material RHL-4.

The XRD diffraction spectrum of RHL-4 has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 5.6 percent by weight calculated by rare earth oxide, the unit cell constant is 2.450nm, the relative crystallinity is 32 percent, and the total specific surface area is 369m²G, total pore volume 0.412cm³/g。

Example 5

A commercial conventional NaY molecular sieve dry powder (relative crystallinity 88%, Si/Al ratio 5.0) is mixed with a proper amount of deionized water and pulped, the temperature is raised to 50 ℃, and Al is simultaneously carried out in a parallel flow mode at the temperature₂(SO₄)₃Solution (concentration 90 gAl)₂O₃/L) and NaAlO₂Solution (concentration 102 gAl)₂O₃and/L) adding the mixture into the solution to perform neutralization reaction, keeping the pH value of the slurry system at 9.0 by adjusting the flow rate of the two materials, continuing to age the slurry for 2 hours at 50 ℃ after the neutralization reaction, then transferring the slurry into a stainless steel crystallization kettle to seal the kettle, performing crystallization treatment for 20 hours at 100 ℃, filtering, washing and drying to obtain the silicon-aluminum material MMC-1.

The X-ray diffraction spectrum of MMC-1 is shown in figure 2, and characteristic 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, 31.4 degrees, 14 degrees, 28 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively, which indicates that the MMC-1 contains both FAU crystal phase structure and pseudo-boehmite structure. The SEM photograph is shown in FIG. 3, which shows that the aluminum oxide layer is coated on the surface of the molecular sieve grains. The TEM photograph of the transmission electron microscope is shown in FIG. 4, and it can be seen that two structures coexist, the structure with regular and ordered diffraction fringes is the FAU crystal phase structure, the disordered structure of the alumina layer grows along the edge of the ordered diffraction fringes of the FAU crystal phase, and the two structures are connected together to form a microporous and mesoporous composite structure. Calculated by weight of oxideMMC-1 contains 10.5 percent of sodium oxide, 50.5 percent of silicon oxide and 38.4 percent of aluminum oxide; the specific surface area is 639m²In terms of/g, total pore volume of 0.428cm³The BJH pore size distribution curve is shown in fig. 5, where two pore size distributions appear at 4nm and 8nm, respectively, indicating that the material has a graded pore distribution profile.

According to the weight ratio of MMC-1 to ammonium salt of 1: 0.8, performing first ion exchange treatment on the MMC-1 and an ammonium salt solution at 65 ℃ for 2 hours, filtering, washing and drying; then roasting for 2 hours at 650 ℃; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.4, carrying out secondary ion exchange treatment at 65 ℃ for 1 hour, directly adding a rare earth solution according to the proportion of 0.04 of rare earth oxide without filtering, adjusting the pH value to 8.5 by using ammonia water, stirring for a certain time, filtering and drying; and then carrying out secondary roasting treatment at 600 ℃ under the condition of 100% water vapor for 2 hours to obtain the rare earth type hierarchical porous material RHL-5.

The XRD diffraction spectrum of RHL-5 has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 4.0 wt% calculated by rare earth oxide, the unit cell constant is 2.452nm, the relative crystallinity is 50%, and the total specific surface area is 538m²G, total pore volume 0.400cm³/g。

Example 6

The gel feeding mol ratio of a conventional NaY molecular sieve is as follows, such as 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂And synthesizing the NaY molecular sieve according to the proportion of O. Respectively mixing water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water according to the above proportion, and vigorously stirring for 1 hour, wherein the adding proportion of the guiding agent is 5% by weight, crystallizing the mixed gel at 100 ℃ for 28 hours, filtering, washing and drying to obtain the NaY molecular sieve dry powder. Mixing the obtained NaY molecular sieve dry powder with a proper amount of deionized water, pulping, and simultaneously carrying out Al in a parallel flow mode at room temperature₂(SO₄)₃Solution (concentration 90 gAl)₂O₃L) and ammonia water (mass fraction is 8%) are added to carry out neutralization reaction, andand adjusting the flow rates of the two materials to keep the pH value of the slurry system at 10.1, continuously aging at 60 ℃ for 4 hours after neutralization reaction, then transferring the slurry into a stainless steel crystallization kettle for sealing, performing crystallization treatment at 100 ℃ for 15 hours, filtering, washing and drying to obtain the silicon-aluminum material MMC-2.

The X-ray diffraction spectrum of MMC-2 has the characteristics shown in figure 2, and characteristic 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, 31.4 degrees, 14 degrees, 28 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively, which shows that the MMC-2 contains both FAU crystal phase structure and pseudo-boehmite structure. The SEM photograph thereof has the characteristics shown in FIG. 3, and it can be seen that the corrugated structure of the alumina layer is coated on the surface of the molecular sieve crystal grain. The TEM picture of the transmission electron microscope has the characteristics shown in figure 4, two structures coexist, the structure with regular ordered diffraction fringes is an FAU crystal phase structure, the disordered structure of the alumina layer extends and grows along the edges of the ordered diffraction fringes of the FAU crystal phase, and the two structures are connected together to form a microporous and mesoporous composite structure. The MMC-2 contains 10.0 percent of sodium oxide, 54.1 percent of silicon oxide and 35.5 percent of aluminum oxide by weight of oxides; the specific surface area is 687m²(ii)/g, total pore volume 0.399cm³The BJH pore size distribution curve has the characteristics shown in figure 5, and two pore size distributions appear at 4nm and 9nm respectively, which shows that the material has the characteristic of gradient pore distribution.

According to the weight ratio of 0.08 of the rare earth oxide to the MMC-2 and the weight ratio of 0.05 of the ammonium salt to the MMC-2, carrying out first ion exchange treatment on the MMC-2, the rare earth solution and the ammonium salt solution at 80 ℃, wherein the exchange time is 1 hour, and filtering, washing and drying are carried out; then roasting for 3 hours at the temperature of 600 ℃ and under the condition of 100 percent of water vapor; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.35, carrying out secondary ion exchange treatment at 80 ℃ for 1 hour, filtering, adding a rare earth solution according to the proportion of 0.04 of rare earth oxide, adjusting the pH value to 7.0 by using ammonia water, stirring for a certain time, filtering and drying; and then carrying out secondary roasting treatment at 600 ℃ under the condition of 100% water vapor for 2 hours to obtain the rare earth type hierarchical porous material RHL-6.

XR of RHL-6The D diffraction spectrum has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 11.9 wt% calculated by rare earth oxide, the unit cell constant is 2.458nm, the relative crystallinity is 53%, and the total specific surface area is 567m²G, total pore volume 0.350cm³/g。

Example 7

Mixing commercial NaY molecular sieve dry powder (relative crystallinity 85%, Si/Al ratio 5.1) with appropriate amount of deionized water, pulping, heating to 55 deg.C and simultaneously adding Al (NO) in parallel flow mode at the temperature₃)₃Solution (concentration 60 gAl)₂O₃/L) and NaAlO₂Solution (concentration 102 gAl)₂O₃and/L) adding the solution into the solution to perform neutralization reaction, keeping the pH value of the slurry system at 10.5 by adjusting the flow rate of the two materials, continuing to age the slurry for 2 hours at 80 ℃ after the neutralization reaction, then transferring the slurry into a stainless steel crystallization kettle to seal the kettle, performing crystallization treatment for 10 hours at 100 ℃, filtering, washing and drying to obtain the silicon-aluminum material MMC-6.

The MMC-6 has the characteristics shown in figure 2, and characteristic 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, 31.4 degrees, 14 degrees, 28 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively, which shows that the MMC-6 simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The SEM photograph thereof has the characteristics shown in FIG. 3, and it can be seen that the corrugated structure of the alumina layer is coated on the surface of the molecular sieve crystal grain. The TEM picture of the transmission electron microscope has the characteristics shown in figure 4, two structures coexist, the structure with regular ordered diffraction fringes is an FAU crystal phase structure, the disordered structure of the alumina layer extends and grows along the edges of the ordered diffraction fringes of the FAU crystal phase, and the two structures are connected together to form a microporous and mesoporous composite structure. The MMC-6 contains 6.4 percent of sodium oxide, 32.4 percent of silicon oxide and 60.7 percent of aluminum oxide by weight of oxides; the specific surface area is 508m²(iv)/g, total pore volume of 0.467cm³The BJH pore size distribution curve has the characteristics shown in figure 5, and two pore size distributions appear at 4nm and 7nm respectively, which shows that the material has the characteristic of gradient pore distribution.

Performing first ion exchange treatment on the rare earth oxide and the MMC-6 at 65 ℃ for 1 hour according to the weight ratio of 0.13 of the rare earth oxide to the MMC-6 and a rare earth solution, filtering, washing and drying; then roasting for 2 hours at 550 ℃ under the condition of 100 percent of water vapor; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.35, carrying out secondary ion exchange treatment at 65 ℃ for 1 hour, filtering, adding a rare earth solution according to the proportion of 0.03 of rare earth oxide, adjusting the pH value of the slurry to 6.0 by using ammonia water, stirring for a certain time, and directly drying; and then carrying out secondary roasting treatment at 550 ℃ under the condition of 100% water vapor for 2 hours to obtain the rare earth type hierarchical porous material RHL-7.

The XRD diffraction spectrum of RHL-7 has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 16.0 wt% calculated by rare earth oxide, the unit cell constant is 2.465nm, the relative crystallinity is 33%, and the total specific surface area is 410m²In terms of/g, total pore volume 0.415cm³/g。

Example 8

The gel feeding mol ratio of a conventional NaY molecular sieve is 8.7SiO₂：Al₂O₃：2.75Na₂O：200H₂And synthesizing the NaY molecular sieve according to the proportion of O. Respectively mixing water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water according to the above proportion, vigorously stirring for 1 hour, wherein the adding proportion of the guiding agent is 5% by weight, crystallizing the gel at 100 ℃ for 49 hours, filtering, washing and drying to obtain the NaY molecular sieve dry powder. Mixing the obtained NaY molecular sieve dry powder with a proper amount of deionized water, pulping, and simultaneously adding Al (NO) in a parallel flow mode at room temperature₃)₃Solution (concentration 60 gAl)₂O₃adding/L) and NaOH solution (with the concentration of 1M) into the solution to perform neutralization reaction, keeping the pH value of the slurry system at 10.3 by adjusting the flow rate of the two materials, continuing to age for 4 hours at 65 ℃ after the neutralization reaction, then transferring the slurry into a stainless steel crystallization kettle to seal, performing crystallization treatment for 20 hours at 100 ℃, filtering, washing and drying to obtain the silicon-aluminum material MMC-8.

X-ray diffraction spectrum of MMC-8The diffraction peak is shown in figure 2, and the 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, 31.4 degrees, 14 degrees, 28 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively, which shows that the crystal structure contains both FAU crystal phase structure and pseudo-boehmite structure. The scanning electron micrograph has the characteristics shown in fig. 3, and it can be seen that the corrugated structure of the alumina layer covers the surface of the molecular sieve grains. The TEM picture of the transmission electron microscope has the characteristics shown in figure 4, two structures coexist, the structure with regular ordered diffraction fringes is an FAU crystal phase structure, the disordered structure of the alumina layer extends and grows along the edges of the ordered diffraction fringes of the FAU crystal phase, and the two structures are connected together to form a microporous and mesoporous composite structure. The MMC-8 contains 8.4 percent of sodium oxide, 28.9 percent of silicon oxide and 62.1 percent of aluminum oxide by weight of oxides; the specific surface area is 500m²(ii)/g, total pore volume 0.472cm³The BJH pore size distribution curve has the characteristics shown in figure 5, and two pore size distributions appear at 4nm and 9nm respectively, which shows that the material has the characteristic of gradient pore distribution.

According to the weight ratio of 0.04 of rare earth oxide to MMC-8 and the weight ratio of 0.2 of ammonium salt to MMC-8, carrying out first ion exchange treatment on MMC-8, a rare earth solution and an ammonium salt solution at 70 ℃ for 2 hours, filtering, washing with water and drying; then roasting for 3 hours at 580 ℃ under the condition of 100 percent of water vapor; mixing the obtained mixture with an ammonium salt solution according to the weight ratio of 1:0.4, carrying out secondary ion exchange treatment at 70 ℃ for 1 hour, directly adding a rare earth solution according to the proportion of 0.06 of rare earth oxide without filtering, adjusting the pH value to 8.0 by using ammonia water, stirring for a certain time, filtering and drying; and then carrying out secondary roasting treatment at 580 ℃ under the condition of 100% steam for 2 hours to obtain the rare earth type hierarchical porous material RHL-8.

The XRD diffraction spectrum of RHL-8 has the characteristics shown in figure 1, and simultaneously contains a microporous structure of a Y-type molecular sieve and gamma-Al₂O₃A mesoporous structure. The rare earth content is 9.5 wt% calculated by rare earth oxide, the unit cell constant is 2.457nm, the relative crystallinity is 40%, and the total specific surface area is 405m²G, total pore volume 0.425cm³/g。

Examples 9 to 16

Examples 9-16 illustrate the reactivity of the rare earth-type hierarchical pore materials prepared in accordance with the present invention.

The rare earth type hierarchical porous materials RHL-1 to RHL-8 in the above examples 1 to 8 and ammonium chloride solution are exchanged again until the content of sodium oxide is washed to be below 0.3 weight percent, filtered, dried, tableted and sieved into particles of 20 to 40 meshes, aged for 17 hours under the conditions of 800 ℃ and 100 percent of water vapor, and then the microreactivity index MA is 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
				RHL-1	59	RHL-5	57
RHL-2	67	RHL-6	62
				RHL-3	63	RHL-7	62
RHL-4	57	RHL-8	58

As can be seen from the micro-inversion activity index MA in Table 1, the rare earth type hierarchical porous materials RHL-1 to RHL-8 obtained in the embodiments 1 to 8 have good activity stability and cracking activity, and the MA can still reach 57 to 67 after being aged for 17 hours by 100 percent of water vapor at the temperature of 800 ℃.

Examples 17-24 illustrate the preparation of the second aluminosilicate material and the subsequent formation of a rare earth type hierarchical pore material.

Example 17

Mixing water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water according to 8.5SiO₂：Al₂O₃：2.65Na₂O：210H₂Mixing the guiding agent according to a molar ratio of 5%, violently stirring to form NaY molecular sieve gel, placing the gel in a crystallization kettle for static crystallization at 100 ℃ for 18 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 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. The Transmission Electron Microscope (TEM) picture shows a regular and ordered diffraction fringe and a disordered structure without fixed crystal face orientation, wherein the ordered diffraction fringe represents FAU crystalThe body structure and the disorder structure are pseudo-boehmite structures, the disorder structure is derived and grown from the edges of the ordered diffraction fringes, 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 0.350cm³(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) ═ 1.97 and D (V, 0.9) ═ 4.11.

According to the following steps of 1: 0.12, mixing AFCY-2 with the rare earth solution, carrying out first contact treatment at 70 ℃ for 1 hour, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100% of water vapor and 600 ℃, wherein the roasting time is 2 hours; then, according to the following steps of 1: mixing the roasted product with ammonium salt solution in the proportion of 0.35, carrying out secondary contact treatment at 70 ℃ for 1 hour, and filtering; then mixing with rare earth solution according to the proportion of 1: 0.04, adjusting the pH value to 7.8 by using ammonia water, directly drying the mixture without filtering, and then performing secondary roasting treatment for 2 hours under the conditions of 100 percent of water vapor and 600 ℃ to obtain the rare earth type hierarchical porous material RPL-1.

An XRD diffractogram of RPL-1 is shown in fig. 6, 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. It contains 16 wt% of rare earth oxide, unit cell constant 2.465nm, relative crystallinity 44%, total specific surface area 550m²In terms of/g, total pore volume 0.313cm³(V, 0.5) particle size distribution D2.4, D (V, 0.9) 6.1.

Example 18

Preparing NaY molecular sieve gel according to the molar ratio in the example 17, statically crystallizing at 100 ℃ for 26 hours, cooling after crystallization andfiltering and washing the 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 8 mass percent of ammonia water and/L) into the slurry, 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.

AFCY-4 was mixed according to 1: 0.1: 0.05, mixing with the rare earth solution and the ammonium salt solution, carrying out first contact treatment at 80 ℃ for 1 hour, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100% water vapor and 550 ℃, wherein the roasting time is 2 hours; then, according to the following steps of 1:0.35, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 80 ℃ for 1 hour, and directly mixing the rare earth solution according to the weight ratio of 1: adding 0.02 of the amount of the rare earth element into the mixture, adjusting the pH value to 6.0 by using ammonia water, filtering and drying the mixture, and then carrying out secondary roasting treatment for 2 hours under the conditions of 100 percent of water vapor and 550 ℃ to obtain the rare earth type hierarchical porous material RPL-2.

The XRD diffraction pattern of the RPL-2 has the characteristics shown in figure 6, and meanwhile, the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen. It contains rare earth oxide 11.9 wt%, unit cell constant 2.460nm, relative crystallinity 35%, and totalSpecific surface area 441m²(g) total pore volume 0.401cm³(V, 0.5) 2.8 and (V, 0.9) 7.7, respectively.

Example 19

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 102 gAl)₂O₃and/L) adding the silicon-aluminum material, 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.

AFCY-5 was mixed as follows: 0.04: 0.2, mixing with the rare earth solution and the ammonium salt solution, carrying out first contact treatment at 60 ℃ for 2 hours, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100 percent of water vapor and 580 ℃, wherein the roasting time is 3 hours; then, according to the following steps of 1:0.4, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 60 ℃ for 1 hour, filtering, and mixing the rare earth solution according to the weight ratio of 1: adding 0.04 of the weight percent, adjusting the pH value to 7.5 by using a sodium hydroxide solution, filtering and drying, and then carrying out secondary roasting treatment for 3 hours under the conditions of 100 percent of water vapor and 580 ℃ to obtain the rare earth type hierarchical porous material RPL-3.

The XRD diffraction pattern of the RPL-3 has the characteristics shown in figure 6, and meanwhile, the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen. It contains 8 wt% of rare earth oxide, unit cell constant 2.454nm, relative crystallinity 48%, total specific surface area 549m²Per g, total pore volume 0.346cm³(V, 0.5) particle size distribution D (V, 0.5) 2.5, D (V, 0.9) 6.5.

Example 20

Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 19, 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.

AFCY-6 was mixed as 1: 0.08: 0.1, mixing with the rare earth solution and the ammonium salt solution, carrying out first contact treatment at 65 ℃ for 1 hour, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100% of water vapor and 630 ℃, wherein the roasting time is 2 hours; then, according to the following steps of 1:0.4, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 65 ℃ for 1 hour, filtering, and mixing the rare earth solution according to the weight ratio of 1: adding 0.06 of the amount of the rare earth element into the mixture, adjusting the pH value to 8.5 by using ammonia water, filtering and drying the mixture, and then carrying out secondary roasting treatment for 2 hours under the conditions of 100 percent of water vapor and 630 ℃ to obtain the rare earth type hierarchical porous material RPL-4.

The XRD diffraction pattern of the RPL-4 has the characteristics shown in figure 6, and meanwhile, the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen. It contains rare earth oxide 13.9 wt%, unit cell constant 2.463nm, relative crystallinity 54%, and total specific surface area 580m²(ii)/g, total pore volume 0.311cm³(V, 0.5) particle size distribution D (V, 0.9) 2.3 and D (V, 0.9) 5.6.

Example 21

According to 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂In the molar ratio of O, water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water are violently mixed to form NaY molecular sieve gel, the mass ratio of the guiding 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.

The 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 the Y-type molecular sieveThe FAU crystal phase structure and the pseudo-boehmite structure; 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) ═ 2.30 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 0.440cm³(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.

AFYH-2 was added as 1: 0.08: 0.1, mixing with the rare earth solution and the ammonium salt solution, carrying out first contact treatment at 75 ℃ for 2 hours, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100% of water vapor and 530 ℃, wherein the roasting time is 4 hours; then, according to the following steps of 1:0.35, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 75 ℃ for 1 hour, and directly mixing the rare earth solution according to the weight ratio of 1: adding 0.02 of the amount of the rare earth element into the mixture, adjusting the pH value to 7.0 by using ammonia water, filtering and drying the mixture, and then carrying out secondary roasting treatment for 2 hours under the conditions of 100 percent of water vapor and 530 ℃ to obtain the rare earth type hierarchical porous material RPL-5.

The XRD diffraction pattern of the RPL-5 has the characteristics shown in figure 6, and meanwhile, the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen. It contains rare earth oxide 10 wt%, unit cell constant 2.456nm, relative crystallinity 45%, total specific surface area 520m²G, total pore volume 0.408cm³(V, 0.5) particle size distribution D2.9, D (V, 0.9) 7.5.

Example 22

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 parallel flow at the temperatureMixing Al₂(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 structure contains both FAU crystal phase structure of Y-type molecular sieve and pseudo-boehmite structure; 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 465m²(ii)/g, total pore volume 0.458cm³(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.

AFYH-7 was added as 1: 1, mixing with an ammonium salt solution, carrying out first contact treatment at 80 ℃ for 1 hour, filtering, washing with water, and drying; carrying out primary roasting treatment at 550 ℃ for 2 hours; then, according to the following steps of 1:0.35, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 80 ℃ for 1 hour, filtering, and mixing the rare earth solution according to the weight ratio of 1: adding 0.06 of the amount of the rare earth element into the mixture, adjusting the pH value to 8.0 by using ammonia water, filtering and drying the mixture, and then carrying out secondary roasting treatment for 3 hours under the conditions of 100 percent of water vapor and 550 ℃ to obtain the rare earth type hierarchical porous material RPL-6.

The XRD diffraction pattern of the RPL-6 has the characteristics shown in figure 6, and the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen at the same time. It contains rare earth oxide 6 wt%, unit cell constant 2.450nm, relative crystallinity 38%, total specific surface area 408m²Per g, total pore volume 0.422cm³(V, 0.5) particle size distribution D2.7 and D (V, 0.9) 8.6.

Example 23

Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 22, 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 treatment 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 structure contains both FAU crystal phase structure and pseudo-boehmite structure of 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 426m²Per g, total pore volume of 0.468cm³(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.

AFYH-8 was added as 1: 1, mixing with an ammonium salt solution, carrying out first contact treatment at 70 ℃ for 1 hour, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100% of water vapor and 600 ℃, wherein the roasting time is 2 hours; then, according to the following steps of 1:0.4, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 70 ℃ for 1 hour, and directly mixing the rare earth solution according to the weight ratio of 1: adding 0.04 percent of the mixed solution into the mixed solution, adjusting the pH value to 7.2 by ammonia water, filtering and drying, and then carrying out secondary roasting treatment for 2 hours under the conditions of 100 percent of water vapor and 600 ℃ to obtain the rare earth type hierarchical porous material RPL-7.

Of RPL-7The XRD diffraction pattern has the characteristics shown in figure 6, and the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen at the same time. It contains rare earth oxide 4 wt%, unit cell constant 2.450nm, relative crystallinity 33%, total specific surface area 369m²G, total pore volume 0.430cm³(V, 0.5) particle size distribution D (V, 0.7) and D (V, 0.9) 8.8.

Example 24

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 8 mass percent of/L) and ammonia water into the slurry, controlling the pH value of the slurry to be 10.2, mixing for a certain time, stirring for 3 hours at the constant temperature of 65 ℃, then transferring the slurry into a stainless steel crystallization kettle, carrying out hydrothermal crystallization for 15 hours at the temperature of 100 ℃, filtering, washing and drying 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 672m²In terms of/g, total pore volume of 0.378cm³(ii)/g; the BJH pore size distribution curve shows a bimodal distribution.

AFYH-3 was added as 1: mixing with rare earth solution at a ratio of 0.09, performing first contact treatment at 65 ℃ for 2 hours, filtering, washing with water, and drying; carrying out primary roasting treatment under the conditions of 100% water vapor and 650 ℃, wherein the roasting time is 2 hours; then, according to the following steps of 1:0.35, mixing the roasted product with an ammonium salt solution, carrying out secondary contact treatment at 65 ℃ for 1 hour, filtering, and mixing the rare earth solution according to the weight ratio of 1: adding 0.03 into the mixture, adjusting the pH value to 7.9 by using ammonia water, directly drying the mixture without filtering, and then performing secondary roasting treatment for 2 hours at the temperature of 650 ℃ by using 100 percent of water vapor to obtain the rare earth type hierarchical porous material RPL-8.

The XRD diffraction pattern of the RPL-8 has the characteristics shown in figure 6, and meanwhile, the characteristic diffraction peaks of the Y-type molecular sieve and the alumina can be seen. It contains rare earth oxide 11.9 wt%, unit cell constant 2.458nm, relative crystallinity 50% and total specific surface area 575m²In terms of/g, total pore volume 0.342cm³(V, 0.5) particle size distribution D2.3 and D (V, 0.9) 5.9.

Examples 25 to 32

Examples 25-32 illustrate the cracking performance of the rare earth-type hierarchical pore materials prepared according to the present invention.

The rare earth type hierarchical porous materials RPL-1 to RPL-8 described in the above examples 17 to 24 were mixed with an ammonium chloride solution and exchanged, 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 conditions for 12 hours, and then the microreflection index MA was measured on a light oil microreflection analyzer.

The micro-inversion activity data shown in Table 2 show that the MA of the rare earth type hierarchical porous materials RPL-1 to RPL-8 obtained in examples 17 to 24 can reach 58 to 68 after 12 hours of hydrothermal aging treatment, and the rare earth type hierarchical porous materials also show very excellent cracking performance.

TABLE 2

Sample (I)	MA	Sample (I)	MA
				RPL-1	68	RPL-5	61
RPL-2	60	RPL-6	59
				RPL-3	62	RPL-7	58
RPL-4	67	RPL-8	64

Therefore, the hierarchical pore material obtained by the method has a hierarchical pore structure, namely a microporous structure of the Y-type molecular sieve and a mesoporous structure of the alumina exist at the same time, so that the accessibility of an active center is effectively improved, and the improvement of the reaction performance of the hierarchical pore material is promoted by modification treatment of rare earth on the structural stability and the retention of an acid center of the Y-type molecular sieve and appropriate modification of the mesoporous part of the alumina.

Claims

1. A preparation method of a rare earth type hierarchical pore material is characterized by comprising the following preparation processes: carrying out first ion exchange treatment on a silicon-aluminum material and a rare earth solution A and/or an ammonium salt solution, filtering, washing and drying; after the obtained mixture is subjected to primary roasting treatment under the condition of 0-100% of water vapor, the obtained mixture is mixed with an ammonium salt solution to perform secondary ion exchange treatment, and the obtained mixture is filtered or not filtered, or is mixed with an acid solution to perform secondary ion exchange treatment and is filtered; mixing the obtained mixture with a rare earth solution B, adjusting the pH value of the slurry to 5-10 by using an alkaline solution, filtering or not, and then carrying out secondary roasting treatment under the condition of 0-100% of water vapor; wherein the silicon-aluminum material is selected from one of the following silicon-aluminum materials and/or two of the following silicon-aluminum materials:

one of the silicon-aluminum materials is characterized in that an XRD spectrogram of the silicon-aluminum material has a characteristic diffraction peak with an FAU crystalline phase structure and a pseudo-boehmite structure, a wrinkled pseudo-boehmite structure alumina mesoporous layer is coated on the surface of the FAU crystalline phase structure, and the two structures are communicated with each other and grow together; the silicon-aluminum material contains 4-12% of sodium oxide, 20-60% of silicon oxide and 30-75% of aluminum oxide by weight of oxides; the silicon-aluminum material has the gradient pore distribution characteristic formed by a microporous structure and a mesoporous structure, and can be distributed in several pores with two characteristics at 3-4 nm and 7-10 nm, and the specific surface area is 420-720 m²(ii) a total pore volume of 0.35 to 0.50cm³A characteristic of/g;

the second silicon-aluminum material is a mesoporous alumina layer which simultaneously contains a Y-type molecular sieve and a pseudo-boehmite structure, the mesoporous alumina layer grows on the surface of the crystal grain of the Y-type molecular sieve and uniformly coats the crystal grain of the molecular sieve, 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 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 one of said silicon-aluminum materials is prepared by the steps of: adding water into molecular sieve dry powder with FAU crystal phase structure, pulping and homogenizing; adding an aluminum source and an alkali solution into the slurry at the room temperature to 85 ℃ in a parallel flow mode to perform a neutralization reaction, and controlling the pH value of the slurry system to be 8-10.5; after the neutralization reaction, continuing to age for 1-10 hours at the temperature of room temperature to 90 ℃ and recovering the product, or after the neutralization reaction, aging for 1-4 hours, transferring to a closed crystallization kettle, continuing to crystallize for 3-30 hours at the temperature of 95-105 ℃ and recovering the product.

3. The method of claim 1, wherein said second silica-alumina material is obtained by: preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then statically crystallizing at the temperature of 95-105 ℃; filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; mixing, pulping and homogenizing a NaY molecular sieve filter cake and deionized water, adding an aluminum source and an alkali solution into the NaY molecular sieve filter cake simultaneously in a parallel flow mode under the condition that the temperature is between room temperature and 85 ℃ and under the condition of vigorous stirring, and controlling the pH value of a slurry system in the mixing process to be 9-11; 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.

4. The method according to claim 2 or 3, wherein the aluminum source is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride.

5. A process according to claim 2 or 3, wherein the alkali solution is selected from one or more of aqueous ammonia, potassium hydroxide, sodium hydroxide or sodium metaaluminate, and when sodium metaaluminate is used as the alkali solution, the alumina content thereof is calculated to the total alumina content.

6. The preparation method according to claim 1, wherein in the first ion exchange treatment, the weight ratio of the rare earth solution A to the silicon-aluminum material in terms of rare earth oxide is 0 to 0.14, preferably 0.02 to 0.13, the weight ratio of the ammonium salt to the silicon-aluminum material is 0.05 to 1.0, the exchange temperature is 40 to 90 ℃, preferably 50 to 80 ℃, and the exchange time is 0.5 to 3.0 hours, preferably 1 to 2 hours.

7. The process according to claim 1, wherein the first baking treatment and the second baking treatment are carried out at 500 to 700 ℃, preferably 530 to 650 ℃,0 to 100% steam, preferably 20 to 100% steam, for 0.5 to 4.0 hours, preferably 1 to 3 hours.

8. The process according to claim 1, wherein the second ion exchange treatment with an ammonium salt is carried out at a weight ratio of 0.3 to 0.5, an exchange temperature of 40 to 90 ℃, preferably 50 to 80 ℃, and an exchange time of 0.5 to 3.0 hours, preferably 1 to 2 hours; in the ion exchange treatment with the acid solution, the weight ratio of the acid solution to the acid solution obtained in the previous step is 0.03-0.12, preferably 0.05-0.1, the exchange temperature is room temperature-60 ℃, and the exchange time is 0.5-3.0 hours, preferably 1-2 hours.

9. The process according to claim 1, wherein the rare earth solution B is mixed in a weight ratio of 0.01 to 0.10, preferably 0.02 to 0.08, in terms of rare earth oxide; and in the process of adjusting the pH value of the slurry by the alkaline solution, the pH value is 6-9, and the alkaline solution is selected from one or more of sodium hydroxide, water glass and ammonia water.

10. The method according to claim 1, wherein the rare earth-based hierarchical porous material is prepared to have a rare earth content of 2 to 20 wt%, preferably 4 to 18 wt%, in terms of rare earth oxide, and contains a Y-type molecular sieve microporous structure and gamma-Al₂O₃The 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 in an XRD spectrogram represent Y-type molecular sieves, and the diffraction peaks at 20-30 degrees and about 66 degrees represent Y-type molecular sievesRepresents an alumina structure, and the two structures are communicated with each other; the rare earth content is 2-20 wt%, preferably 4-18 wt% calculated by rare earth oxide, the unit cell constant is 2.445-2.470 nm, preferably 2.448-2.465 nm, the relative crystallinity is 30-60%, preferably 32-55%, and the total specific surface area is 350-600 m²(ii) a total pore volume of 0.25 to 0.45cm³/g。