CN111620350A

CN111620350A - Micro-mesoporous composite material and preparation method thereof

Info

Publication number: CN111620350A
Application number: CN201910149555.5A
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: 2019-02-28
Filing date: 2019-02-28
Publication date: 2020-09-04
Anticipated expiration: 2039-02-28
Also published as: CN111620350B

Abstract

A micro-mesoporous composite material is characterized by simultaneously comprising a mesoporous layer with a gamma-alumina structure and a Y-type molecular sieve with an FAU crystal phase structure, wherein the gamma-alumina mesoporous layer is coated on the surface of the Y-type molecular sieve, and the two structures are mutually connected and communicated; 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 330-580 m²(g) total pore volume of 0.30-0.45 cm³And/g, the particle size distribution D (V, 0.5) is 2-3, and D (V, 0.9) is 5-9. The micro-mesoporous composite material is very beneficial to the transmission of macromolecules and the remarkable improvement of cracking performance due to the organic combination of two structures, the gradient pore distribution characteristic and the combination of rare earth modification.

Description

Micro-mesoporous composite material and preparation method thereof

Technical Field

The invention relates to a composite material containing micro-mesopores and a corresponding preparation method thereof, and further relates to a micro-mesopore composite material which is coated with an alumina mesopore layer on the surface of a Y-shaped molecular sieve and is modified by rare earth and a preparation method thereof.

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 porous materials in the mesoporous range, more research is focused on disordered mesoporosityDevelopment of porous materials. US5,051,385 discloses a monodisperse mesoporous silicon-aluminum composite material, which is prepared by mixing acidic inorganic aluminum salt and silica sol and then adding alkali for reaction, wherein the aluminum content is 5-40 wt%, the aperture is 20-50 nm, and the specific surface area is 50-100 m²(ii) in terms of/g. US4,708,945 discloses a catalyst prepared by loading silica particles or hydrated silica on porous boehmite and hydrothermally treating the obtained composite at a temperature of more than 600 ℃ for a certain time to obtain a catalyst prepared by loading silica on the surface of the boehmite, wherein the silica is combined with hydroxyl of the transition boehmite and the surface area reaches 100-200 m²(iv) g, average pore diameter of 7 to 7.5 nm. A series of acidic cracking catalysts are disclosed in US4,440,872, some of which are supported on gamma-Al₂O₃Impregnating silane, and then roasting at 500 ℃ or treating with water vapor. In CN1353008A, inorganic aluminum salt and water glass are used as raw materials, stable and clear silicon-aluminum sol is formed through the processes of precipitation, washing, dispergation and the like, white gel is obtained through drying, and then the silicon-aluminum catalytic material is obtained through roasting for 1-20 hours at 350-650 ℃. CN1565733A discloses a mesoporous silicon-aluminum material which has a pseudo-boehmite structure, concentrated pore size distribution and a specific surface area of about 200-400 m²The mesoporous silicon-aluminum material has the advantages that the pore volume is 0.5-2.0 ml/g, the average pore diameter is 8-20 nm, the most probable pore diameter is 5-15 nm, an organic template agent is not needed in the preparation of the mesoporous silicon-aluminum material, the synthesis cost is low, the obtained silicon-aluminum material has high cracking activity and hydrothermal stability, and the high macromolecular cracking performance is shown in a catalytic cracking reaction.

Disclosure of Invention

The invention aims to provide a micro-mesoporous composite material which is simultaneously provided with an alumina mesoporous layer and a Y-type molecular sieve, wherein the alumina mesoporous layer is coated on the surface of the Y-type molecular sieve, and the two structures are mutually connected and communicated and are modified by rare earth.

The second purpose of the invention is to provide a preparation method of the micro-mesoporous composite material.

The micro-mesoporous composite material provided by the invention is characterized by simultaneously containing a layer of gamma-alumina structure mesogenThe mesoporous layer and a Y-type molecular sieve with an FAU crystal phase structure, wherein the gamma-alumina mesoporous layer is coated on the surface of the Y-type molecular sieve, and the two structures are mutually connected and communicated; 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 330-580 m²(g) total pore volume of 0.30-0.45 cm³And/g, the particle size distribution D (V, 0.5) is 2-3, and D (V, 0.9) is 5-9.

The invention further provides a preparation method of the micro-mesoporous composite material, which comprises the following preparation processes: (a) carrying out first contact treatment on a porous material and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; (b) carrying out primary roasting treatment on the sample obtained in the step (a) under the condition of 0-100% of water vapor; (c) adding water into the sample obtained in the step (b) for pulping, carrying out secondary contact treatment on the sample and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; or carrying out secondary roasting treatment under the condition of 0-100% of water vapor to obtain the micro-mesoporous composite material; wherein at least one of the first contacting treatment in step (a) and the second contacting treatment in step (c) is performed with a rare earth solution.

In the preparation method, the porous material in the step (a) simultaneously contains a Y-type molecular sieve and a pseudo-boehmite structure mesoporous alumina layer, the mesoporous alumina layer grows on the surface of a 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 an ordered diffraction stripe of an FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together; the chemical composition of the porous material is (4-12) Na based on the weight of the oxide₂O·(20～60)SiO₂·(30～75)Al₂O₃(ii) a The total specific surface area is 380-700 m²(ii) a total pore volume of 0.32 to 0.48cm³The BJH pore size distribution curve shows that two or more pore distributions appear at 3-4 nm and 6-9 nm respectively. The particle size parameter D (V, 0.5) of the porous material is 1.8-2.5, and the particle size parameter D (V, 0.9) is 4.0-8.0. In XRD spectrogram thereofCharacteristic diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, wherein the characteristic diffraction peaks at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 ° and 31.4 ° correspond to the FAU crystal phase structure of the Y-type molecular sieve, and the characteristic diffraction peaks at 28 °, 38.5 °, 49 ° and 65 ° correspond to the pseudo-boehmite structure of the mesoporous layer. The Transmission Electron Microscope (TEM) picture shows that the pseudo-boehmite disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together. A Scanning Electron Microscope (SEM) shows that a corrugated structure is coated on the surface of the molecular sieve crystal grains, and the molecular sieve crystal grains are uniformly coated in the corrugated structure.

In the preparation method, the porous material in the step (a) is prepared by the following steps: (1) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then performing static crystallization at the temperature of 95-105 ℃; (2) filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; (3) mixing the NaY molecular sieve filter cake obtained in the step (2) with deionized water, pulping and homogenizing, adding an aluminum source and an alkali solution into the mixture simultaneously in a parallel flow mode under the conditions that the temperature is between room temperature and 85 ℃ and violent stirring, and controlling the pH value of a slurry system to be 9-11 in the mixing process; (4) and then the mixture is processed for 1 to 10 hours at the constant temperature ranging from room temperature to 90 ℃ and the product is recovered, or the mixture is processed for 1 to 4 hours at the constant temperature ranging from room temperature to 90 ℃, and then the slurry is placed in a closed crystallization kettle and is subjected to hydrothermal crystallization for 3 to 30 hours at the temperature ranging from 95 ℃ to 105 ℃ and the product is recovered.

Wherein, the raw materials for synthesizing NaY molecular sieve in step (1) are usually directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water, and their addition ratio can be the charging ratio of conventional NaY molecular sieve, for example, Na can be added₂O：Al₂O₃：SiO₂：H₂O is 1.5-8: 1: 5-18: 100 to 500, or the charging ratio for preparing a NaY molecular sieve with special performance, such as the charging ratio for preparing a NaY molecular sieve with large crystal grains or small crystal grains, and the like, the charging ratio and the concentration of each raw material are not particularly limited,as long as NaY molecular sieve having FAU crystal phase structure can be obtained. The guiding agent can be prepared according to the prior art (US3639099 and US3671191), and the guiding agent is prepared by mixing a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na₂O:Al₂O₃:(15～17)SiO₂:(280～380)H₂Mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at room temperature to 70 ℃. In the feeding proportion of the NaY molecular sieve, Al in the guiding agent₂O₃The content of (A) is based on the total charge Al₂O₃3 to 15%, preferably 5 to 10% of the total amount. The static crystallization in the step (1) is carried out for 8-50 hours, preferably 10-40 hours, and more preferably 15-35 hours.

Wherein, the aluminum source in the step (3) is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is selected from one or more of ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate, and when the sodium metaaluminate is taken as the alkali solution, the alumina content of the alkali solution is counted in the total alumina content. The sodium metaaluminate can be sodium metaaluminate with different causticity ratios and different concentrations. The caustic ratio is preferably 1.5 to 11.5, more preferably 1.65 to 2.55, and the concentration is preferably 40 to 200gAl₂O₃a/L, more preferably 41 to 190gAl₂O₃/L。

The concept of the concurrent flow mode of adding the aluminum source and the alkali solution simultaneously in the step (3) refers to an operation mode of adding n +1(n is more than or equal to 1) materials (such as the aluminum source and the alkali solution in the invention) into a container simultaneously for mixing, so that each material is added at a constant speed, and the n +1 materials are added within 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. The temperature of the mixing process in the step (3) is between room temperature and 85 ℃, and preferably between 30 and 70 ℃.

In the preparation method, in the first contact treatment process of the porous material and the rare earth solution and/or the ammonium salt solution in the step (a), the weight ratio of the rare earth solution to the porous material calculated by rare earth oxide is 0.02-0.14, preferably 0.03-0.13, the weight ratio of the ammonium salt to the porous material is 0.05-1.0, the contact temperature is 40-90 ℃, preferably 50-80 ℃, and the contact time is 0.5-3.0 hours, preferably 1-2 hours.

In the preparation method of the invention, the first or second roasting treatment in the steps (b) and (c) is carried out at 500-700 ℃, preferably 550-650 ℃, and 0-100% water vapor, preferably 20-100% water vapor, for 0.5-4.0 hours, preferably 1-3 hours.

In the preparation method, the second contact treatment in the step (c), namely in the contact treatment process of the rare earth solution and/or the ammonium salt solution obtained in the step (b), the weight ratio of the rare earth solution to the rare earth solution obtained in the step (b) calculated by rare earth oxide is 0.02-0.08, the weight ratio of the ammonium salt to the solution obtained in the step (b) is 0.05-0.50, preferably 0.1-0.4, the contact temperature is 40-90 ℃, preferably 50-80 ℃, and the contact time is 0.5-3.0 hours, preferably 1-2 hours.

In the preparation method of 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 common rare earth solution includes lanthanum chloride, lanthanum nitrate, cerium chloride or cerium nitrate, etc., or may be a mixed rare earth with different rare earth element ratios, such as cerium-rich or lanthanum-rich mixed rare earth, and may be of any concentration; the mixed solution of the rare earth solution and the ammonium salt can be prepared by mixing the ammonium salt and the rare earth solution in proportion, or adding the ammonium salt and the rare earth solution one by one in proportion, wherein 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 micro-mesoporous composite material provided by the invention is very beneficial to the obvious improvement of the transmission and cracking performance of macromolecules due to the organic combination of the two structures, the distribution characteristics of gradient pore canals and the combination of the rare earth modification.

Drawings

FIG. 1 is a SEM photograph of the porous material AFCY-1 of example 1.

FIG. 2 is a TEM image of the porous material AFCY-1 of example 1.

FIG. 3 is an X-ray diffraction pattern of the porous material AFCY-1 of example 1.

FIG. 4 is a BJH pore size distribution curve of the porous material AFCY-1 in example 1.

FIG. 5 shows the X-ray diffraction pattern of the micro-mesoporous composite material RBL-1 obtained in example 1.

FIG. 6 is an X-ray diffraction pattern of the porous material AFYH-2 of example 6.

FIG. 7 is a SEM photograph of the porous material AFYH-2 of example 6.

FIG. 8 is a TEM image of the porous material AFYH-2 of example 6.

FIG. 9 is the BJH pore size distribution curve of the porous material AFYH-2 of example 6.

Detailed Description

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

The SEM was a Hitachi S4800 field emission SEM, Japan, with an accelerating voltage of 5kV, and the spectra were collected and processed with Horiba 350 software.

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 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 data of specific surface, pore volume, pore size distribution and the like are measured by a low-temperature nitrogen adsorption-desorption method.

The particle size distribution test is carried out by mixing micro porous material with deionized water, adding a small amount of slurry into the laser particle size analyzer, recording a plurality of analysis data after stable analysis, and carrying out average treatment to obtain corresponding particle size distribution data.

Chemical composition was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP methods of experiments)", eds "Yangcui et al, published by scientific publishers, 1990).

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.

Example 1

This example illustrates the micro-mesoporous composite of the present invention and the process for preparing it.

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 34 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, and simultaneously carrying out AlCl in a parallel flow mode at room temperature under the condition of vigorous stirring₃Solution (concentration 60 gAl)₂O₃and/L) and ammonia water (mass fraction is 8%) are added, the pH value of a slurry system is controlled to be 10.8 in the mixing process, after the slurry system is mixed for a certain time, the mixture is treated at the constant temperature of 50 ℃ for 5 hours, and the porous material AFCY-1 is obtained after filtering, washing and drying.

The SEM photograph of AFCY-1 is shown in FIG. 1, and it can be seen that the molecular sieve crystal grain surface is covered with a wrinkled structure. A Transmission Electron Micrograph (TEM) is shown in FIG. 2, showing a regular ordered diffraction pattern and a non-fixed crystal faceThe XRD spectrogram of the disordered structure is shown in figure 3, 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, wherein the characteristic diffraction peak marked as ★ corresponds to the FAU crystal phase structure of the Y-type molecular sieve, and the characteristic diffraction peak marked as ▲ corresponds to the pseudo-boehmite structure of the mesoporous layer₂O·22.0SiO₂·71.1Al₂O₃(ii) a The total specific surface area is 418m²(ii)/g, total pore volume 0.441cm³(ii)/g; the BJH pore size distribution curve is shown in fig. 4, and it can be seen that bimodal distributions appear around 3.8nm and 7.4nm, respectively; the laser particle size analyzer measured D (V, 0.5) ═ 2.50 and D (V, 0.9) ═ 7.80.

According to the weight ratio of 0.08 of the rare earth oxide to the porous material and the weight ratio of 0.1 of the ammonium salt to the porous material, contacting AFCY-1 with a rare earth solution and an ammonium salt solution at 60 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at 580 ℃ under the condition of 100 percent of water vapor; and adding water obtained by roasting, pulping, mixing the mixture with a rare earth solution and an ammonium salt solution according to the weight ratio of the rare earth oxide to the roasted product of 0.02 and the weight ratio of the ammonium salt to the roasted product of 0.2, carrying out secondary contact treatment at 60 ℃ for 1 hour, filtering, washing with water, and drying to obtain the micro-mesoporous composite material, which is marked as RBL-1.

An XRD diffraction pattern of RBL-1 is shown in figure 5, wherein diffraction peaks marked by x 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 and the like are characteristic diffraction peaks of the Y-type molecular sieve, and diffraction peaks marked by braces between 20 degrees and 30 degrees and around 66 degrees are characteristic diffraction peaks of gamma-alumina layer; RBL-1 contains rare earth oxide 9.8 wt%, unit cell constant 2.463nm, relative crystallinity 34%, and total specific surface area 365m²In g, total pore volume 0.420cm³(iv)/g, wherein the particle size distribution D (V, 0.5) ═ 2.8 and D (V, 0.9) ═ 8.7.

Example 2

Preparing NaY molecular sieve gel according to the molar ratio in the embodiment 1, statically crystallizing 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 porous material AFCY-2 is obtained after filtration, washing and drying.

The SEM photograph of AFCY-2 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together. The XRD spectrum has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudoboehmite structure exist; the chemical composition of the oxide-doped sodium titanate is 11.7Na by weight₂O·57.6SiO₂·30.1Al₂O₃(ii) a Total specific surface area 651m²(ii)/g, total pore volume 0.350cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in FIG. 4, and bimodal distribution around about 3.8nm and 6.6nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 1.97 and D (V, 0.9) ═ 4.11.

According to the weight ratio of 0.12 of the rare earth oxide to the porous material, contacting AFCY-2 with a rare earth solution at 70 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at 600 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted product, pulping, mixing the roasted product with a rare earth solution according to the weight ratio of the rare earth oxide to the roasted product of 0.06, carrying out secondary contact treatment for 1 hour at 70 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 600 ℃ under the condition of 100% water vapor for 2 hours, and obtaining the micro-mesoporous composite material, which is marked as RBL-2.

The XRD diffraction pattern of RBL-2 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-2 contains rare earth oxide 17.9 wt%, unit cell constant 2.468nm, relative crystallinity 48%, and total specific surface area 580m²In terms of/g, total pore volume 0.332cm³The particle size distribution D (V, 0.5) ═ 2.4 and D (V, 0.9) ═ 5.5 per gram.

Example 3

Preparing NaY molecular sieve gel according to the molar ratio in the embodiment 1, statically crystallizing at 100 ℃ for 45 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 35 ℃, and simultaneously carrying out AlCl in a parallel flow mode under the condition of vigorous stirring₃Solution (concentration 60 gAl)₂O₃/L) and NaAlO₂Solution (concentration 180 gAl)₂O₃and/L) adding the mixture into the slurry, controlling the pH value of a slurry system in the mixing process to be 10.2, mixing for a certain time, then carrying out constant temperature treatment at 65 ℃ for 4 hours, filtering, washing and drying to obtain the porous material AFCY-3.

The SEM photograph of AFCY-3 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together. The XRD spectrum has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudoboehmite structure exist; the chemical composition of the oxide-based nano-particles is 10.0Na by weight₂O·48.5SiO₂·41.1Al₂O₃(ii) a Total specific surface area of 611m²(ii)/g, total pore volume of 0.397cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in FIG. 4, and bimodal distribution around about 3.8nm and 8.1nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 2.21 and D (V, 0.9) ═ 5.48.

According to the weight ratio of 0.04 of rare earth oxide to the porous material and the weight ratio of 0.2 of ammonium salt to the porous material, contacting AFCY-3 with a rare earth solution and an ammonium salt solution at 80 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at 550 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted product, pulping, mixing the roasted product with a rare earth solution according to the weight ratio of the rare earth oxide to the roasted product of 0.08, carrying out secondary contact treatment for 1 hour at the temperature of 80 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at the temperature of 550 ℃ under the condition of 100% water vapor, and carrying out treatment for 2 hours to obtain the micro-mesoporous composite material, which is marked as RBL-3.

The XRD diffraction pattern of RBL-3 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-3 contains rare earth oxide 11.5 wt%, unit cell constant 2.457nm, relative crystallinity 54%, and total specific surface area 568m²G, total pore volume 0.369cm³The particle size distribution D (V, 0.5) ═ 2.4 and D (V, 0.9) ═ 6.2 per gram.

Example 4

Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 1, statically crystallizing at 100 ℃ for 20 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, and simultaneously adding Al (NO) in a parallel flow mode at 30 ℃ under vigorous stirring₃)₃Solution (concentration 60 gAl)₂O₃/L) and NaAlO₂Solution (concentration 102 gAl)₂O₃and/L) adding the mixture into the reactor, controlling the pH value of a slurry system in the mixing process to be 10.0, mixing for a certain time, then carrying out constant temperature treatment at 70 ℃ for 1 hour, filtering, washing and drying to obtain porous AFCY-7.

The SEM photograph of AFCY-7 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron micrograph has the characteristics shown in figure 2, and regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, wherein the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two parts areSeed structures are built together. The XRD spectrum has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudoboehmite structure exist; the chemical composition of the oxide-based nano-crystalline silicon oxide is 8.6Na by weight₂O·39.4SiO₂·51.5Al₂O₃(ii) a The total specific surface area is 558m²(ii)/g, total pore volume 0.426cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in FIG. 4, and bimodal distribution around about 3.8nm and 7.4nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 2.29 and D (V, 0.9) ═ 6.17.

According to the weight ratio of 0.08 of the rare earth oxide to the porous material and the weight ratio of 0.1 of the ammonium salt to the porous material, contacting AFCY-7 with a rare earth solution and an ammonium salt solution at 75 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at the temperature of 630 ℃ under the condition of 100 percent of water vapor; adding water into the roasted product, pulping, mixing with an ammonium salt solution according to the weight ratio of ammonium salt to the roasted product of 0.35, carrying out secondary contact treatment at 75 ℃ for 1 hour, filtering, washing with water, and drying to obtain the micro-mesoporous composite material, which is marked as RBL-4.

The XRD diffraction pattern of RBL-4 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-4 contains rare earth oxide 7.8 wt%, unit cell constant 2.460nm, relative crystallinity 50%, and total specific surface area 510m²G, total pore volume 0.400cm³The particle size distribution D (V, 0.5) ═ 2.5 and D (V, 0.9) ═ 6.8 per gram.

Example 5

Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 1, statically crystallizing at 100 ℃ for 30 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, and simultaneously adding Al (NO) in a parallel flow mode at 35 ℃ under vigorous stirring₃)₃Solution (concentration 60 gAl)₂O₃Adding 8% of ammonia water and/or water, controlling pH of the slurry system to 9.6, mixing for a certain time, and maintaining at 60 deg.CAnd treating for 7 hours, filtering, washing and drying to obtain the porous material AFCY-8.

The SEM photograph of AFCY-8 has the characteristics shown in FIG. 1, and it can be seen that the surface of the molecular sieve crystal grain is coated with a wrinkled structure. The transmission electron microscope photograph has the characteristics shown in figure 2, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived from the edges of the ordered diffraction fringes and grows, and the two structures are built together. The XRD spectrum has the characteristics shown in figure 3, and both FAU crystal phase structure and pseudoboehmite structure exist; the chemical composition of the oxide-based nano-particles is 6.0Na by weight₂O·25.6SiO₂·67.8Al₂O₃(ii) a The total specific surface area is 451m²In terms of/g, total pore volume of 0.428cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in FIG. 4, and bimodal distribution around about 3.8nm and 8.1nm can be seen; the laser particle size analyzer measured D (V, 0.5) ═ 2.42 and D (V, 0.9) ═ 7.25.

According to the weight ratio of 1 of ammonium salt to the porous material, contacting AFCY-8 with an ammonium salt solution at 65 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 4 hours at 580 ℃; and adding water obtained by roasting, pulping, mixing the mixture with a rare earth solution and an ammonium salt solution according to the weight ratio of the rare earth oxide to the roasted product of 0.04 and the weight ratio of the ammonium salt to the roasted product of 0.1, carrying out secondary contact treatment at 65 ℃ for 1 hour, filtering, washing with water, and drying to obtain the micro-mesoporous composite material, which is marked as RBL-5.

The XRD diffraction pattern of RBL-5 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-5 contains 3.9 wt% of rare earth oxide, has unit cell constant of 2.452nm, relative crystallinity of 32%, and total specific surface area of 419m²G, total pore volume 0.406cm³The particle size distribution D (V, 0.5) ═ 2.9 and D (V, 0.9) ═ 9.0 per gram.

Example 6

According to 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂Preparing NaY molecular sieve gel at 100 deg.CPerforming static crystallization for 42 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, 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 mixture, 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 porous material AFYH-2.

The XRD spectrum of AFYH-2 is shown in FIG. 6, diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, respectively indicating that the composite material simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure of the Y-type molecular sieve; the SEM photograph is shown in FIG. 7, which shows that the molecular sieve crystal grain surface is coated with the wrinkled structure; the transmission electron microscope photo is shown in FIG. 8, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, 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 is 9.1Na based on the weight of the 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 is shown in fig. 9, with a bimodal distribution.

According to the weight ratio of 0.11 of the rare earth oxide to the porous material, contacting AFYH-2 with a rare earth solution at 70 ℃ for 2 hours, filtering, washing with water and drying; then roasting for 2 hours at 650 ℃ under the condition of 100 percent of water vapor; adding water into the roasted product, pulping, mixing with an ammonium salt solution according to the weight ratio of 0.4 of ammonium salt to the roasted product, carrying out secondary contact treatment for 1 hour at 70 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 650 ℃ for 2 hours, and obtaining the micro-mesoporous composite material, which is marked as RBL-6.

The XRD diffraction pattern of RBL-6 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-6 contains rare earth oxide 10.7 wt%, unit cell constant 2.458nm, relative crystallinity 49%, and total specific surface area 530m²In g, total pore volume 0.418cm³The particle size distribution D (V, 0.5) ═ 2.6 and D (V, 0.9) ═ 7.1 per gram.

Example 7

Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 6, statically crystallizing at 100 ℃ for 50 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, 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 porous material AFYH-3.

The XRD spectrum of AFYH-3 has the characteristics shown in FIG. 6, diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, which respectively show that the composite material simultaneously contains the FAU crystal phase structure and the pseudo-boehmite structure of the Y-type molecular sieve; the SEM photograph has the characteristics shown in FIG. 7, and the wrinkled structure is seen to cover the surface of the molecular sieve grains; the transmission electron microscope photo has the characteristics shown in figure 8, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived and grown from the edge of the ordered diffraction fringes, 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 is 10.2Na based on the weight of the 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 has the characteristics shown in fig. 9, and has a bimodal distribution.

According to the weight ratio of 0.06 of the rare earth oxide to the porous material and the weight ratio of 0.15 of the ammonium salt to the porous material, contacting AFYH-3 with a rare earth solution and an ammonium salt solution at 85 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at 600 ℃; and adding water into the roasted product, pulping, mixing the mixture with a rare earth solution according to the weight ratio of the rare earth oxide to the roasted product of 0.08, carrying out secondary contact treatment for 1 hour at 85 ℃, filtering, washing with water, drying, and carrying out secondary roasting treatment at 600 ℃ for 2 hours to obtain the micro-mesoporous composite material, which is marked as RBL-7.

The XRD diffraction pattern of RBL-7 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-7 contains rare earth oxide 13.9 wt%, unit cell constant 2.462nm, relative crystallinity 57%, and total specific surface area 572m²G, total pore volume 0.350cm³The particle size distribution D (V, 0.5) ═ 2.2 and D (V, 0.9) ═ 5.1 per gram.

Example 8

According to 8.5SiO₂：Al₂O₃：2.65Na₂O：210H₂Preparing NaY molecular sieve gel according to the molar ratio of O, statically crystallizing for 44 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 40 ℃, and simultaneously carrying out Al parallel flow at the temperature₂(SO₄)₃Solution (concentration 90 gAl)₂O₃/L) and sodium metaaluminate solution (concentration 102 gAl)₂O₃and/L) adding the mixture into the slurry, controlling the pH value of the slurry to be 10.7, mixing for a certain time, stirring at the constant temperature of 55 ℃ for 4 hours, then transferring the slurry into a stainless steel crystallization kettle, performing hydrothermal crystallization at the temperature of 100 ℃ for 25 hours, filtering, washing and drying to obtain the porous material AFYH-4.

The XRD spectrum of AFYH-4 has the characteristics shown in FIG. 6, namely 6.2 degrees, 10.1 degrees,Diffraction peaks appear at 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 show that the composite material simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure of the Y-type molecular sieve; the SEM photograph has the characteristics shown in FIG. 7, and the wrinkled structure is seen to cover the surface of the molecular sieve grains; the transmission electron microscope photo has the characteristics shown in figure 8, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived and grown from the edge of the ordered diffraction fringes, and the two structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 2.38 and D (V, 0.9) ═ 6.13. The anhydrous chemical expression is 6.2Na based on the weight of the oxide₂O·31.5SiO₂·61.8Al₂O₃(ii) a The total specific surface area is 501m²In terms of/g, total pore volume of 0.450cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in fig. 9, and has a bimodal distribution.

According to the weight ratio of 0.12 of the rare earth oxide to the porous material, contacting AFYH-4 with a rare earth solution at 70 ℃ for 2 hours, filtering, washing with water and drying; then roasting for 2 hours at 580 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted product, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide to the roasted product of 0.04, carrying out secondary contact treatment at 70 ℃ for 1 hour, filtering, washing with water, and drying to obtain the micro-mesoporous composite material, which is marked as RBL-8.

The XRD diffraction pattern of RBL-8 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-8 contains rare earth oxide 15.9 wt%, unit cell constant 2.464nm, relative crystallinity 41%, and total specific surface area 463m²G, total pore volume 0.425cm³(iv)/g, wherein the particle size distribution D (V, 0.5) ═ 2.7 and D (V, 0.9) ═ 7.9.

Example 9

According to 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂The molar ratio of O is that the water glass, the aluminum sulfate, the sodium metaaluminate, the guiding agent and the deionizationViolently mixing water to form NaY molecular sieve gel, wherein the mass ratio of the guiding agent is 5%, statically crystallizing the gel at 100 ℃ for 30 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 adding AlCl in a parallel flow mode at 30 DEG C₃Solution (concentration 60 gAl)₂O₃/L) and sodium hydroxide solution (concentration 1M) are added, the pH value of the slurry is controlled to be 9.6, after a certain time of mixing, the slurry is stirred for 2 hours at the constant temperature of 60 ℃, then the slurry is transferred to a stainless steel crystallization kettle and is subjected to hydrothermal crystallization for 6 hours at the temperature of 100 ℃, and the porous material AFYH-1 is obtained after filtering, washing and drying.

The XRD spectrum of AFYH-1 has the characteristics shown in FIG. 6, diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, which respectively show that the composite material simultaneously contains the FAU crystal phase structure and the pseudo-boehmite structure of the Y-type molecular sieve; the SEM photograph has the characteristics shown in FIG. 7, and the wrinkled structure is seen to cover the surface of the molecular sieve grains; the transmission electron microscope photo has the characteristics shown in figure 8, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived and grown from the edge of the ordered diffraction fringes, and the two structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 2.36 and D (V, 0.9) ═ 5.98. The anhydrous chemical expression is 7.3Na based on the weight of the oxide₂O·26.6SiO₂·65.4Al₂O₃(ii) a The total specific surface area is 475m²In terms of/g, total pore volume of 0.460cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in fig. 9, and has a bimodal distribution.

According to the weight ratio of 0.06 of the rare earth oxide to the porous material and the weight ratio of 0.15 of the ammonium salt to the porous material, contacting AFYH-1 with a rare earth solution and an ammonium salt solution at 60 ℃ for 2 hours, filtering, washing with water and drying; then roasting for 4 hours at 550 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted product, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide to the roasted product of 0.06, carrying out secondary contact treatment at 60 ℃ for 1 hour, filtering, washing with water, and drying to obtain the micro-mesoporous composite material, which is marked as RBL-9.

The XRD diffraction pattern of RBL-9 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-9 contains rare earth oxide 11.9 wt%, unit cell constant 2.459nm, relative crystallinity 37%, and total specific surface area 430m²In terms of/g, total pore volume 0.428cm³The particle size distribution D (V, 0.5) ═ 2.7 and D (V, 0.9) ═ 8.0 per gram.

Example 10

Preparing NaY molecular sieve gel according to the molar ratio of the embodiment 8, statically crystallizing at 100 ℃ for 35 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 adding Al (NO) in a parallel flow mode at room temperature₃)₃Solution (concentration 90 gAl)₂O₃/L) and sodium hydroxide solution (concentration is 1M) are added, the pH value of the slurry is controlled to be 10.5, after a certain time of mixing, the slurry is stirred for 4 hours at the constant temperature of 50 ℃, then the slurry is transferred to a stainless steel crystallization kettle and is subjected to hydrothermal crystallization for 30 hours at the temperature of 100 ℃, and the porous material AFYH-5 is obtained after filtering, washing and drying.

The XRD spectrum of AFYH-5 has the characteristics shown in FIG. 6, diffraction peaks appear at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 °, 28 °, 31.4 °, 38.5 °, 49 ° and 65 °, which respectively show that the composite material simultaneously contains the FAU crystal phase structure and the pseudo-boehmite structure of the Y-type molecular sieve; the SEM photograph has the characteristics shown in FIG. 7, and the wrinkled structure is seen to cover the surface of the molecular sieve grains; the transmission electron microscope photo has the characteristics shown in figure 8, regular and ordered diffraction fringes and a disordered structure without fixed crystal face trend can be seen, the disordered structure is derived and grown from the edge of the ordered diffraction fringes, and the two structures are built together; the particle size distribution is more uniform, and D (V, 0.5) ═ 2.20 and D (V, 0.9) ═ 5.19. The anhydrous chemical expression is 10.2Na based on the weight of the oxide₂O·51.0SiO₂·38.1Al₂O₃(ii) a Total ratio tableArea of 620m²(ii)/g, total pore volume 0.419cm³(ii)/g; the BJH pore size distribution curve has the characteristics shown in fig. 9, and has a bimodal distribution.

According to the weight ratio of 1 of ammonium salt to the porous material, contacting AFYH-5 with an ammonium salt solution at 75 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at 550 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted product, pulping, mixing the roasted product with a rare earth solution according to the weight ratio of the rare earth oxide to the roasted product of 0.06, carrying out secondary contact treatment for 1 hour at 75 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 550 ℃ under the condition of 100% water vapor, and carrying out treatment for 2 hours to obtain the micro-mesoporous composite material, which is marked as RBL-10.

The XRD diffraction pattern of RBL-10 has the characteristics shown in figure 5, and simultaneously contains an FAU crystal phase structure and a gamma-alumina structure. RBL-10 contains rare earth oxide 6 wt%, unit cell constant 2.454nm, relative crystallinity 54%, and total specific surface area 578m²G, total pore volume 0.398cm³The particle size distribution D (V, 0.5) ═ 2.3 and D (V, 0.9) ═ 5.8 per gram.

Examples 11 to 20

This example illustrates the cracking activity of the micro-mesoporous composite material prepared according to the present invention.

The mesoporous composite materials RBL-1 to RBL-10 described in the above examples 1 to 10 were exchanged with ammonium chloride solution again, the sodium oxide content was washed to 0.3 wt% or less, filtered, dried, tableted and sieved into 20 to 40 mesh particles, aged at 800 ℃ under 100% steam for 12 hours, and then the reactivity was evaluated on a heavy oil microreaction evaluation device.

Heavy oil micro-reverse evaluation conditions: the raw oil is vacuum gas oil, the sample loading is 2g, the mass ratio of the sample to the oil is 1.2, the reaction temperature is 500 ℃, and the regeneration temperature is 600 ℃.

The properties of the stock oils are shown in Table 1, and the evaluation results are shown in Table 2.

TABLE 1

TABLE 2

Example numbering	11	12	13	14	15	16	17	18	19	20
											Sample (I)	RBL-1	RBL-2	RBL-3	RBL-4	RBL-5	RBL-6	RBL-7	RBL-8	RBL-9	RBL-10
Yield/%)
											Dry gas	1.67	1.92	1.70	1.69	1.56	1.71	1.50	1.85	1.64	1.60
Liquefied gas	10.23	10.98	10.76	10.44	10.05	10.23	9.89	10.64	10.18	10.28
											Gasoline (gasoline)	50.09	52.41	50.87	50.57	49.84	50.96	50.27	52.00	51.72	50.39
Diesel oil	18.80	17.59	18.69	18.86	19.07	18.51	19.01	18.35	17.90	19.53
											Heavy oil	9.83	8.63	9.48	9.40	10.12	9.37	9.79	8.17	9.61	9.51
Coke	9.38	8.47	8.50	9.04	9.36	9.22	9.54	8.99	8.95	8.69
											Conversion rate/%	71.37	73.78	71.83	71.74	70.81	72.12	71.20	73.48	72.49	70.96
Coke/conversion ratio	0.131	0.115	0.118	0.126	0.132	0.128	0.134	0.122	0.123	0.122

Table 2 shows that the micro-reverse evaluation data of heavy oil shows that the reaction performance of the micro-mesoporous composite materials RBL-1 to RBL-10 in examples 1 to 10 can still reach a high level after aging for 12 hours, the conversion rate reaches more than 70%, the highest conversion rate reaches 73.78%, the gasoline yield reaches 49.84 to 52.41%, the heavy oil yield is relatively low, and is between 8.17 and 10.12%, which indicates that the heavy oil conversion capability of the materials is high, the coke yield is kept at a low level, and the coke conversion ratio is between 0.115 and 0.134, further indicates that the micro-mesoporous composite materials have more excellent conversion capability and coke selectivity, which are closely related to the combination of two micro-mesoporous structures, the characteristics of gradient pore distribution, and suitable rare earth modification, and have a better promotion effect on the transmission of macromolecules and the cracking process.

Claims

1. A micro-mesoporous composite material is characterized by simultaneously comprising a mesoporous layer with a gamma-alumina structure and a Y-type molecular sieve with an FAU crystal phase structure, wherein the gamma-alumina mesoporous layer is coated on the surface of the Y-type molecular sieve, and the two structures are mutually connected and communicated; 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 330-580 m²(g) total pore volume of 0.30-0.45 cm³And/g, the particle size distribution D (V, 0.5) is 2-3, and D (V, 0.9) is 5-9.

2. The preparation method of the micro-mesoporous composite material of claim 1 is characterized by comprising the following preparation processes: (a) carrying out first contact treatment on a porous material and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; (b) carrying out primary roasting treatment on the sample obtained in the step (a) under the condition of 0-100% of water vapor; (c) adding water into the sample obtained in the step (b) for pulping, carrying out secondary contact treatment on the sample and a rare earth solution and/or an ammonium salt solution, filtering, washing and drying; or carrying out secondary roasting treatment under the condition of 0-100% of water vapor to obtain the micro-mesoporous composite material; wherein at least one of the first contacting treatment in step (a) and the second contacting treatment in step (c) is performed with a rare earth solution.

3. The preparation method according to claim 2, wherein the porous material in step (a) comprises a Y-type molecular sieve and a pseudo-boehmite-structured mesoporous alumina layer, and the mesoporous alumina layer grows on the surface of the Y-type molecular sieve crystal grains and uniformly coats the molecular sieve crystal grains, wherein the disordered structure of the mesoporous alumina layer extends 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 porous material is (4-12) Na based on the weight of the oxide₂O·(20～60)SiO₂·(30～75)Al₂O₃(ii) a The total specific surface area is 380-700 m²(ii) a total pore volume of 0.32 to 0.48cm³The BJH pore size distribution curve shows that two or more pore distributions appear at 3-4 nm and 6-9 nm respectively. The particle size parameter D (V, 0.5) of the porous material is 1.8-2.5, and the particle size parameter D (V, 0.9) is 4.0-8.0. The XRD spectrum has characteristic diffraction peaks at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 28 degrees, 31.4 degrees, 38.5 degrees, 49 degrees and 65 degrees respectively, wherein the characteristic diffraction peaks at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees and 31.4 degrees correspond to the FAU crystal phase structure of the Y-type molecular sieve, and the characteristic diffraction peaks at 28 degrees, 38.5 degrees, 49 degrees and 65 degrees correspond to the pseudo-boehmite structure of the mesoporous layer. The Transmission Electron Microscope (TEM) picture shows that the pseudo-boehmite disordered structure of the mesoporous alumina layer extends and grows from the edge of the ordered diffraction stripe of the FAU crystal phase structure of the Y-type molecular sieve, and the two structures are built together. The Scanning Electron Microscope (SEM) shows that a fold-shaped structure is coated on the surface of the molecular sieve crystal grains uniformlyThe molecular sieve crystal grains are coated in the coating layer.

4. The production method according to claim 2, wherein the porous material is produced by: (1) preparing raw materials capable of synthesizing a NaY molecular sieve, uniformly mixing, and then statically crystallizing at the temperature of 95-105 ℃; (2) filtering and washing the slurry after the static crystallization to obtain a NaY molecular sieve filter cake; (3) mixing the NaY molecular sieve filter cake obtained in the step (2) with deionized water, pulping and homogenizing, adding an aluminum source and an alkali solution into the mixture simultaneously in a parallel flow mode under the conditions that the temperature is between room temperature and 85 ℃ and violent stirring, and controlling the pH value of a slurry system to be 9-11 in the mixing process; (4) and then the mixture is processed for 1 to 10 hours at the constant temperature ranging from room temperature to 90 ℃ and the product is recovered, or the mixture is processed for 1 to 4 hours at the constant temperature ranging from room temperature to 90 ℃, and then the slurry is placed in a closed crystallization kettle and is subjected to hydrothermal crystallization for 3 to 30 hours at the temperature ranging from 95 ℃ to 105 ℃ and the product is recovered.

5. The method according to claim 4, wherein the static crystallization in the step (1) is carried out for 8 to 50 hours.

6. The production method according to claim 4, wherein the aluminum source in the step (3) is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate, and when the sodium metaaluminate is used as the alkali solution, the alumina content is counted in the total alumina content.

7. The method according to claim 4, wherein the temperature of the mixing process in the step (3) is 30 to 70 ℃.

8. The process according to claim 4, wherein the constant temperature treatment in the step (4) is carried out at a temperature of 40 to 80 ℃ for 2 to 8 hours.

9. The preparation method according to claim 2, wherein in the first contact treatment of the porous material and the rare earth solution and/or the ammonium salt solution in the step (a), the weight ratio of the rare earth solution to the porous material calculated as rare earth oxide is 0.02 to 0.14, preferably 0.03 to 0.13, the weight ratio of the ammonium salt to the porous material is 0.05 to 1.0, the contact temperature is 40 to 90 ℃, preferably 50 to 80 ℃, and the contact time is 0.5 to 3.0 hours, preferably 1 to 2 hours.

10. The process according to claim 2, wherein the first or second calcination treatment in steps (b) and (c) is carried out at a temperature of 500 to 700 ℃, preferably 550 to 650 ℃, under a condition of 0 to 100% steam, preferably 20 to 100% steam, for 0.5 to 4.0 hours, preferably 1 to 3 hours.

11. The process according to claim 2, wherein the second contact treatment in step (c) is a contact treatment with the rare earth solution and/or the ammonium salt solution, wherein the weight ratio of the rare earth solution to the rare earth solution obtained in step (b) is 0.02 to 0.08 in terms of rare earth oxide, the weight ratio of the ammonium salt to the solution obtained in step (b) is 0.05 to 0.50, preferably 0.1 to 0.4, the contact temperature is 40 to 90 ℃, preferably 50 to 80 ℃, and the contact time is 0.5 to 3.0 hours, preferably 1 to 2 hours.