CN110871108B

CN110871108B - Preparation method of porous catalytic material containing Y-type molecular sieve

Info

Publication number: CN110871108B
Application number: CN201810993479.1A
Authority: CN
Inventors: 郑金玉; 王成强; 罗一斌
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: 2018-08-29
Filing date: 2018-08-29
Publication date: 2022-06-28
Anticipated expiration: 2038-08-29
Also published as: CN110871108A

Abstract

A preparation method of a porous catalytic material containing a Y-shaped molecular sieve comprises the step of carrying out double-cross one-baking on a porous material and ammonium salt, wherein a mesoporous structure of the porous material grows on the surface of a Y-shaped molecular sieve grain and coats the molecular sieve grain, the grain size is 1-2 mu m, and the total specific surface area is 300-650 m²(ii) a total pore volume of 0.4 to 1.0cm³The a/b of the porous material is 1.2-9.5, wherein a represents the shift of 500cm in Raman spectrum^‑1B represents a Raman shift of 350cm^‑1Spectral peak intensity of (a). The porous catalytic material prepared by the method has two pore channel structures which are smooth, the accessibility of macromolecules is promoted, and the cracking activity is high.

Description

Preparation method of porous catalytic material containing Y-type molecular sieve

Technical Field

The invention relates to a preparation method of a porous catalytic material, in particular to a preparation method of a porous catalytic material with a mesoporous layer coated on the surface of a Y-shaped molecular sieve.

Background

Catalytic cracking is an important process in petroleum refining, is widely applied to the petroleum processing industry, and plays a significant role in oil refineries. In the catalytic cracking process, heavy fractions such as vacuum distillates or 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 to the fields of catalytic cracking, hydrocracking and the like in a large scale due to the regular pore channel structure, good stability and strong acidity. When the 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 rare earth modification for inhibiting framework dealumination, improving the structural stability of the molecular sieve, increasing the retention degree of acid centers and further improving the cracking activity; or after ultra-stabilization treatment, the silicon-aluminum ratio of the framework is improved, and the stability of the molecular sieve is further improved.

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 the atmospheric residual oil is directly used as a cracking raw material, the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefit of oil refining enterprises, and the macromolecular cracking capability of 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 structure, the Y-type molecular sieve shows a relatively obvious pore 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 the 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 CN 1349929a, a novel mesoporous molecular sieve is disclosed, in which primary and secondary structural units of zeolite are introduced into the pore walls of the molecular sieve to make it have the basic structure of conventional zeolite molecular sieve, and the mesoporous molecular sieve has strong acidity and ultrahigh hydrothermal stability. However, the molecular sieve has the defects that a template agent with high price is required to be used, the aperture is only about 2.7nm, the molecular sieve still has large steric hindrance effect on macromolecular cracking reaction, the structure is easy to collapse under the high-temperature hydrothermal condition, and the cracking activity is poor.

In the field of catalytic cracking, silicon-aluminum materials are widely used due to their strong acid centers and good cracking properties. The proposal of the mesoporous concept provides possibility for the preparation of a novel catalyst, and the current research results mostly focus on the use of expensive organic template 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. US4,708,945 discloses first loading porous boehmite with silica particles or hydrated oxygenCarrying out silicon melting, carrying out hydrothermal treatment on the obtained compound at the temperature of more than 600 ℃ for a certain time to prepare the catalyst with silicon oxide loaded on the surface of the boehmite, wherein the silicon oxide 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-Al ₂O₃Impregnating 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 inventor finds that a mesoporous layer with smooth pore passage, small diffusion resistance and large pore diameter is coated on the surface of the microporous molecular sieve with complete crystal structure, strong acidity, excellent structure stability and high catalytic activity in a grafting mode, so that the two structures are continuously communicated, and the respective advantages are enhanced. Based on this, the present invention was made.

The invention aims to provide a preparation method of a porous catalytic material containing a Y-type molecular sieve, wherein a mesoporous layer is coated on the surface of the molecular sieve, the two structures are communicated and form a composite structure, and the cracking activity is obviously improved compared with that of a mechanical mixing contrast sample.

Therefore, the preparation method of the porous catalytic material containing the Y-type molecular sieve provided by the invention comprises the following steps: (a) performing exchange treatment on a porous material and ammonium salt according to the weight ratio of 1 (0.2-1.2) at the temperature of 40-90 ℃ for 0.5-4 hours, filtering, washing with water,And drying; (b) carrying out hydrothermal roasting treatment on the sample dried in the step (a) for 1-4 hours at the temperature of 500-750 ℃ under the condition of 100% steam; (c) adding water into the roasted sample again for pulping, homogenizing, then carrying out secondary exchange treatment on the sample and ammonium salt at 50-90 ℃ for 0.5-2 hours according to the weight ratio of 1 (0.2-0.8), filtering, washing with water, drying and recovering a product; wherein, the mesoporous structure of the porous material in (a) grows on the surface of a Y-shaped molecular sieve crystal grain and coats the molecular sieve crystal grain therein, the particle size distribution is uniform, the particle size visible in a scanning electron microscope is 1-2 mu m, and the total specific surface area is 300-650 m²(ii) a total pore volume of 0.4 to 1.0cm ³(iv) g; diffraction peaks exist 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 in an XRD spectrogram. The chemical composition of the mesoporous layer is determined by the XPS method of surface chemistry, in atomic mass: 7-20% of aluminum and 5-12% of silicon; the porous material has a/b of 1.2-9.5, wherein a represents a shift of 500cm in a Raman (Raman) spectrum^-1B represents a Raman shift of 350cm^-1Spectral peak intensity of (a).

In the porous material in the step (a), the XRD spectrum of the porous material 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, 31.4 degrees and the like corresponding 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 corresponding to the pseudo-boehmite structure of the mesoporous layer. The scanning electron microscope SEM photo shows that the wrinkled mesoporous structure is coated on the surface of the crystal grains of the Y-shaped molecular sieve, the granularity is uniform and is 1-2 mu m, and the granularity is equivalent to the size of the crystal grains of the Y-shaped molecular sieve. The low-temperature nitrogen adsorption and desorption isotherm of the molecular sieve presents a typical IV type form and has mesoporous characteristics; the mesoporous layer is derived on the surface of the Y-type molecular sieve crystal grain in a crystal attachment growth mode.

The porous material in the step (a) simultaneously contains a microporous structure and a mesoporous structure, and the silicon-aluminum mesoporous layer is derived from the surface of the Y-shaped molecular sieve and is coated on the surface of the molecular sieve, so that the granularity is more uniform, the mesoporous structure on the surface is smooth, a continuous gradient channel structure is formed with the internal molecular sieve, and the accessibility of macromolecules is enhanced.

The porous material in the step (a) has special physical and chemical properties and is obtained through the following preparation processes: (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) adding water into the NaY molecular sieve filter cake again for pulping, uniformly dispersing, adding an aluminum source and an alkali solution into the NaY molecular sieve filter cake at the temperature of between 30 and 70 ℃ under the condition of vigorous stirring for reaction, and controlling the pH value of a slurry system in the reaction process to be between 9 and 11; (4) in terms of SiO, based on the weight of alumina contained in the added aluminum source and alkali solution₂:Al₂O₃Adding a silicon source according to the weight ratio of (1-6), continuing to age at the temperature of 30-90 ℃ for 1-8 hours, recovering the aged product, or aging at the temperature of 30-90 ℃ for 1-4 hours, then placing the slurry in a closed reaction kettle, continuing to crystallize at the temperature of 95-105 ℃ for 3-30 hours, and recovering the product.

The raw materials for synthesizing NaY molecular sieve in step (1) of the process for preparing the porous material in step (a) are usually directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water, and they may be added in the proportion of the conventional NaY molecular sieve, for example, Na₂O：Al₂O₃：SiO₂：H₂O is 1.5-8: 1: 5-18: 100 to 500, the charge ratio of NaY molecular sieve for preparing special performance, for example, the charge ratio of NaY molecular sieve for preparing large or small crystal grains, is not particularly limited as long as NaY molecular sieve having FAU crystal phase structure can be obtained. The guiding agent can be prepared according to the prior art (US3639099 and US3671191), and the guiding agent is prepared by mixing a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na₂O:Al₂O₃:(15～17)SiO₂:(280～380)H₂Mixing the components according to the molar ratio of O, uniformly stirring, and standing and aging for 0.5-48 h at room temperature to 70 ℃. In the NaY molecular sieveIn the feeding proportion, 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.

The aluminum source in the step (3) in the preparation process of said porous material in the step (a) is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate. When sodium metaaluminate is used as the alkali solution, the alumina content is counted in the total alumina content. The reaction temperature in the step (3) is 30-70 ℃, and preferably 35-65 ℃.

In the preparation of the porous material in the step (a), the silicon source in the step (4) is one or more selected from the group consisting of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane and silicon oxide. The aging temperature is 30-90 ℃, preferably 40-80 ℃, and the aging time is 1-8 hours, preferably 2-7 hours.

In the preparation method of the porous catalytic material of the present invention, the ammonium salt in the step (a) and the step (c) may be one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.

Wherein, the exchange ratio of the porous material with the special structure and the ammonium salt in the step (a) is 1 (0.2-1.2), preferably 1 (0.4-1.0) in terms of weight ratio, and the exchange temperature is 40-90 ℃, preferably 50-80 ℃.

Wherein, the hydrothermal roasting treatment in the step (b) is carried out at 500-750 ℃, preferably 550-700 ℃ for 1-4 hours.

Wherein the second exchange treatment with ammonium salt in the step (c) is 1 (0.2-0.8), preferably 1 (0.3-0.6) by weight ratio, and the contact temperature is 40-90 ℃, preferably 50-80 ℃.

The filtration, water washing and drying processes are well known to those skilled in the art and will not be described herein.

The porous catalyst obtained by the preparation method of the inventionThe chemical material comprises a Y-type molecular sieve, wherein a layer of mesoporous structure is coated on the surface of a crystal grain of the Y-type molecular sieve, and the two structures are organically connected together to form a micro-mesoporous composite structure; the characteristic diffraction peaks of the Y-type molecular sieve 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 and the like in an XRD spectrogram, and the wide peaks between 20 degrees and 30 degrees and the gamma-Al appears at about 66 degrees₂O₃Characteristic diffraction peaks of the mesoporous structure; a unit cell constant of 2.453-2.465 nm, preferably 2.455-2.462 nm, a relative crystallinity of 25-75%, preferably 28-70%, and a total specific surface area of 250-550 m²(g) total pore volume of 0.3-1.0 cm³/g。

The porous catalytic material prepared by the preparation method provided by the invention integrates the characteristics of a micropore structure and a mesopore structure, and forms a special gradient characteristic on a pore structure and acid distribution, so that the porous catalytic material shows more excellent macromolecular cracking activity, and is more suitable for macromolecular transmission and cracking than a simple mechanical mixed sample.

Drawings

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

FIG. 2 is a SEM photograph of a typical NaY molecular sieve in example 1.

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

FIG. 4 is a low temperature nitrogen desorption isotherm of the porous material SAYN-1 of example 1.

FIG. 5 is an X-ray diffraction pattern of the porous catalytic material B-1 prepared in example 1.

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

FIG. 7 is an X-ray diffraction pattern of the porous material SAY-2 of example 7.

FIG. 8 is a pore size distribution curve of the porous material SAY-2 of example 7.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

Examples of the present inventionThe preparation process of the used directing agent comprises the following steps: 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 stirring₂O₃ 39.9g/L，Na₂O279.4 g/L, density 1326g/L) and aging at 30 ℃ for 18 hours to obtain Na with the molar ratio of 16.1 ₂O:Al₂O₃:15SiO₂:318.5H₂A directing agent for O.

The chemical composition of the mesoporous layer of the porous material in the examples was determined by X-ray photoelectron spectroscopy. The phase, unit cell constant, crystallinity, etc. 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 pore parameters are measured by a low-temperature nitrogen adsorption-desorption volumetric method.

The porous material test in the examples, SEM test, was performed using a Hitachi S4800, Hitachi, Japan, field emission scanning electron microscope, acceleration voltage 5kV, and energy spectrum collected and processed by Horiba 350 software. The laser Raman spectrum adopts a LabRAM HR UV-NIR type laser confocal Raman spectrometer of HORIBA company of Japan, the wavelength of an excitation light source is 325nm, an ultraviolet 15-time objective lens, a confocal pinhole is 100 mu m, and the spectrum scanning time is 100 s.

Example 1

This example provides the preparation process and the resulting porous catalytic material.

Under the condition of vigorous stirring, water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water are mixed according to 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂Mixing the molar ratio of O to form NaY molecular sieve gel, wherein the mass ratio of the guiding agent is 5%, continuously stirring for 1 hour at room temperature, placing the gel in a crystallization kettle for static crystallization treatment for 40 hours at 100 ℃, quickly cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; adding water again to the obtained NaY molecular sieve filter cake for pulping, dispersing uniformly, and then stirring Al vigorously at 30 DEG C ₂(SO₄)₃Solution (concentration 89 gAl)₂O₃/L) and NaAlO₂Solution (concentration 156 gAl)₂O₃/L) is added into the mixture to react, the pH value of a slurry system in the reaction process is controlled to be 9.5, and after the mixture is added for a certain time, Al is used according to the mixture₂(SO₄)₃Solution and NaAlO₂Total Al in solution₂O₃By weight, in terms of SiO₂:Al₂O₃1:2.3 weight ratio, the desired water glass solution (concentration 100g SiO)₂/L) is added into a reaction system, and then aging is continued for 6 hours at 70 ℃, after the aging is finished, filtration is carried out, washing is carried out, and drying is carried out at 120 ℃, so as to obtain the porous material SAYN-1 with a special structure.

A SEM of SAYN-1 is shown in FIG. 1, and a SEM of a typical NaY molecular sieve is shown in FIG. 2. As can be seen from the comparison between FIG. 1 and FIG. 2, the SAYN-1 has a uniform particle size distribution, a particle size of 1-2 μm, and a wrinkled structure on the surface, which indicates that SAYN-1 is a material having a wrinkled mesoporous structure grown on the surface of NaY molecular sieve grains. The XRD spectrum of the SAYN-1 is shown in fig. 3, and 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 marked ^ correspond to the FAU crystal phase structure of the Y-type molecular sieve and the characteristic diffraction peaks marked a-corresponds to the pseudo-boehmite structure of the mesoporous layer. The low temperature nitrogen desorption isotherm of SAYN-1 is shown in FIG. 4, and exhibits a typical type IV form with mesoporous characteristics having a total specific surface area of 516m ²Per g, total pore volume 0.92cm³(iv) g. The surface chemical composition measured by XPS method was 13.6% aluminum and 7.1% silicon by atomic mass. Raman (Raman) spectrometry with a/b of 2.1, wherein a represents a shift of 500cm in the Raman spectrum^-1B represents a Raman shift of 350cm^-1The spectral peak intensity of (a).

Performing exchange treatment on the porous material SAYN-1 and ammonium chloride at a weight ratio of 1:0.6 at 60 ℃ for 1 hour, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 2 hours at the temperature of 550 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the homogenized sample and ammonium chloride at the temperature of 60 ℃ for 1 hour according to the weight ratio of 1:0.4, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-1 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-1 is shown in FIG. 5, which shows that it contains both FAU crystal phase structure of Y-type molecular sieve and a gamma-Al₂O₃In the structure of (1), diffraction peaks (peaks corresponding to ₂O₃Structural feature diffraction peaks.

The unit cell constant of B-1 was 2.464nm, the relative crystallinity was 33%, and the total specific surface area was 464m²G, total pore volume 0.88cm³/g。

Example 2

The preparation of NaY molecular sieve is the same as example 1 except that the crystallization treatment time is 35 hours; adding water again to the NaY molecular sieve filter cake, pulping, dispersing uniformly, and adding AlCl at 50 ℃ under vigorous stirring₃Solution (concentration 60 gAl)₂O₃/L) and ammonia water (mass fraction is 25%) are added into the mixture for reaction, the pH value of a slurry system in the reaction process is controlled to be 10.5, and after the mixture is added for a certain time, according to the used AlCl₃Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃1:5.7 by weight, the desired water glass solution (concentration 100g SiO)₂/L) is added into the reaction system, and then aging is continued for 4 hours at 50 ℃, after the aging is finished, filtration is carried out, washing is carried out, and drying is carried out at 120 ℃, so as to obtain the porous material SAYN-2 with a special structure.

The scanning electron microscope photo of the SAYN-2 has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 mu m, and the surface of the NaY molecular sieve crystal grain is coated with a wrinkled mesoporous structure. The XRD spectrum has the characteristics shown in figure 3, and contains FAU Crystalline phase structures and pseudo-boehmite structures. The low-temperature nitrogen adsorption and desorption isotherm of SAYN-2 has the characteristics shown in figure 4, is in the form of IV isotherms, has mesoporous characteristics and has a total specific surface area of 572m²In terms of a total pore volume of 0.5cm³(iv) g. The surface chemical composition measured by XPS method was 18.4% aluminum and 5.7% silicon by atomic mass. Raman (Raman) spectroscopy, which gave an a/b of 6.3.

Carrying out exchange treatment on the porous material SAYN-2 and ammonium chloride at a weight ratio of 1:1 at 70 ℃ for 2 hours, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 2 hours at 650 ℃ under the condition of 100% water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the homogenized sample and ammonium chloride at 70 ℃ for 1 hour according to the weight ratio of 1:0.3, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-2 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-2 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-2 was 2.458nm, the relative crystallinity was 65%, and the total specific surface area was 515m²G, total pore volume 0.40cm³/g。

Example 3

Under the condition of vigorous stirring, water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water are mixed according to 8.5SiO₂：Al₂O₃：2.65Na₂O：210H₂Mixing the molar ratio of O to form NaY molecular sieve gel, wherein the mass ratio of the guiding agent is 5%, continuously stirring for 1 hour at room temperature, placing the gel in a crystallization kettle for static crystallization treatment at 100 ℃ for 20 hours, quickly cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; adding water again into the obtained NaY molecular sieve filter cake, pulping, dispersing uniformly, and stirring vigorously at 40 deg.C to obtain Al (NO)₃)₃Solution (concentration 50 gAl)₂O₃/L) and aqueous ammonia are added simultaneouslyWherein the reaction is carried out, the pH value of a slurry system in the reaction process is controlled to be 9.0, and after a certain time, Al (NO) is added according to the use₃)₃Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required tetraethoxysilane into the reaction system according to the weight ratio of 1:3, continuing to age at 80 ℃ for 4 hours, filtering after the aging is finished, washing and drying at 120 ℃ to obtain the porous material SAYN-3 with a special structure.

The scanning electron microscope photo of SAYN-3 has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 mu m, and the surface of the NaY molecular sieve crystal grain is coated with a wrinkled mesoporous structure. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The low-temperature nitrogen adsorption and desorption isotherm of SAYN-3 has the characteristics shown in figure 4, is in the form of IV isotherms, has mesoporous characteristics and has the total specific surface area of 559m ²Per g, total pore volume 0.66cm³(iv) g. The surface chemical composition measured by XPS method was 13.3% aluminum and 7.4% silicon by atomic mass. Raman (Raman) spectroscopy, which gave an a/b of 2.5.

Carrying out exchange treatment on the porous material SAYN-3 and ammonium sulfate at a weight ratio of 1:0.8 at 80 ℃ for 1 hour, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 4 hours at the temperature of 600 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the sample and ammonium sulfate at the temperature of 80 ℃ for 0.5 hour according to the weight ratio of 1:0.5, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-3 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-3 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-3 was 2.462nm, the relative crystallinity was 40%, and the total specific surface area was 499m²G, total pore volume 0.60cm³/g。

Example 4

The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 48 hours; adding water again to the obtained NaY molecular sieve filter cake for pulping, dispersing uniformly, and then stirring Al vigorously at room temperature ₂(SO₄)₃Solution and NaAlO₂Adding the solution into the reaction kettle simultaneously to react, controlling the pH value of a slurry system to be 9.8 in the reaction process, and adding Al according to the used Al after a certain time₂(SO₄)₃Solution and NaAlO₂Total Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required tetraethoxysilane into the reaction system according to the weight ratio of 1:1.5, continuing to age at 60 ℃ for 8 hours, filtering after the aging is finished, washing and drying at 120 ℃ to obtain the porous material SAYN-4 with a special structure.

The scanning electron microscope photo of SAYN-4 has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 mu m, and the surface of the NaY molecular sieve crystal grain is coated with a wrinkled mesoporous structure. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The low-temperature nitrogen adsorption and desorption isotherm of SAYN-4 has the characteristics shown in figure 4, is in the form of IV isotherms, has mesoporous characteristics and has the total specific surface area of 595m²In terms of/g, total pore volume of 0.41cm³(ii) in terms of/g. The surface chemical composition measured by XPS method was 11.4% aluminum and 8.7% silicon by atomic mass. Raman (Raman) spectroscopy, with an a/b of 7.2.

Carrying out exchange treatment on the porous material SAYN-4 and ammonium nitrate at the temperature of 50 ℃ for 4 hours according to the weight ratio of 1:1, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 3 hours at 580 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the sample and ammonium nitrate at the temperature of 70 ℃ for 1 hour according to the weight ratio of 1:0.4, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-4 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-4 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-4 was 2.463nm, the relative crystallinity was 69%, and the total specific surface area was 537m²In terms of/g, total pore volume 0.34cm³/g。

Example 5

The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 32 hours; adding water again into the obtained NaY molecular sieve filter cake, pulping, dispersing uniformly, and stirring vigorously at 35 deg.C to obtain Al (NO)₃)₃Solution and NaAlO₂Adding the solution into the slurry to react, controlling the pH value of the slurry system to be 10.7 in the reaction process, and adding Al (NO) according to the use after a certain time₃)₃Solution and NaAlO₂Total Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required water glass solution into the reaction system according to the weight ratio of 1:1, continuing to age at 75 ℃ for 2 hours, filtering after the aging is finished, washing and drying at 120 ℃ to obtain the porous material SAYN-5 with a special structure.

The scanning electron microscope photo of SAYN-5 has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 mu m, and the surface of the NaY molecular sieve crystal grain is coated with a wrinkled mesoporous structure. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The low-temperature nitrogen adsorption and desorption isotherm of SAYN-5 has the characteristics shown in figure 4, is in the form of IV isotherms, has mesoporous characteristics and has a total specific surface area of 420m ²Per g, total pore volume 0.62cm³(iv) g. The surface chemical composition measured by the XPS method was 7.5% by atomic mass of aluminum and 11.5% by atomic mass of silicon. Raman (Raman) spectroscopy, which gave an a/b of 1.8.

Performing exchange treatment on the porous material SAYN-5 and ammonium chloride at 65 ℃ for 1 hour according to the weight ratio of 1:0.7, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 3 hours at 500 ℃ under the condition of 100% water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the homogenized sample and ammonium chloride at 65 ℃ for 1 hour according to the weight ratio of 1:0.5, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-5 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-5 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-5 was 2.463nm, the relative crystallinity was 29%, and the total specific surface area was 401m²G, total pore volume 0.60cm³/g。

Example 6

The present example provides a process for preparing and the resulting porous catalytic material.

The preparation of NaY molecular sieve is the same as that of example 1, except that the crystallization treatment time is 38 hours; adding water again into the obtained NaY molecular sieve filter cake for pulping, and stirring vigorously at 55 ℃ to obtain AlCl ₃Solution and NaAlO₂Adding the solution into the reaction kettle simultaneously for reaction, controlling the pH value of a slurry system to be 9.7 in the reaction process, and adding AlCl according to the use after a certain time₃Solution and NaAlO₂Total Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required water glass solution into the reaction system according to the weight ratio of 1:1.2, continuing to age at 55 ℃ for 8 hours, filtering after the aging is finished, washing and drying at 120 ℃ to obtain the porous material SAYN-8 with a special structure.

The scanning electron microscope photo of SAYN-8 has the characteristics shown in figure 1, the particle size distribution is uniform, the particle size is 1-2 mu m, and the surface of the NaY molecular sieve crystal grain is coated with a wrinkled mesoporous structure. The XRD spectrum has the characteristics shown in figure 3, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. The low-temperature nitrogen adsorption and desorption isotherm of SAYN-8 has the characteristics shown in figure 4, is in the form of IV isotherms, has mesoporous characteristics and has a total specific surface area of 391m²(ii)/g, total pore volume 0.90cm³(iv) g. The surface chemical composition measured by the XPS method was 9.4% aluminum and 10.1% silicon by atomic mass. Raman (Raman) spectroscopy, which gave an a/b of 1.4.

Performing exchange treatment on the porous material SAYN-8 and ammonium chloride at a weight ratio of 1:0.5 at 75 ℃ for 0.5 hour, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 2 hours at the temperature of 630 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the homogenized sample and ammonium chloride at the temperature of 75 ℃ for 0.5 hour according to the weight ratio of 1:0.5, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-6 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-6 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-6 was 2.460nm, the relative crystallinity was 26%, and the total specific surface area was 358m²In terms of/g, total pore volume 0.82cm³/g。

Example 7

The preparation of NaY molecular sieve is the same as example 1 except that the crystallization treatment time is 46 hours; pulping the obtained NaY molecular sieve filter cake with water, homogenizing, and adding Al (NO) at 30 deg.C under vigorous stirring₃)₃Solution (concentration 60 gAl)₂O₃L) and sodium hydroxide (concentration 1M) are simultaneously subjected to gelling reaction, the pH value of slurry in the gelling process is controlled to be 10.8, and after a certain time, Al (NO) is added according to the use₃)₃Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required tetraethoxysilane into the gel-forming slurry according to the weight ratio of 1:4, aging at 60 ℃ for 4 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 14 hours, filtering, washing and drying at 120 ℃ to obtain the porous material SAY-2 with the special structure.

SAY-2 scanning electron microscope photo has the characteristics shown in figure 6, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. SAY-2 has the characteristic shown in figure 7, and contains FAU crystal phase structure and pseudo-boehmite structure. SAY-2 has an a/b of 1.3, and surface Si-Al atoms measured by XPS method The ratio was 0.41. The BJH pore size distribution curve has the characteristics shown in FIG. 8, presents multi-level pore distribution characteristics, and has a total specific surface area of 420m²Per g, the mesoporous specific surface area is 378m²/g。

Performing exchange treatment on the porous material SAY-2 and ammonium sulfate at a weight ratio of 1:0.4 at 60 ℃ for 0.5 hour, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 2 hours at the temperature of 700 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the sample and ammonium sulfate at the temperature of 60 ℃ for 0.5 hour according to the weight ratio of 1:0.6, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-7 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-7 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (3).

The unit cell constant of B-7 was 2.458nm, the relative crystallinity was 30%, and the total specific surface area was 398m²G, total pore volume 0.90cm³/g。

Example 8

Under the condition of vigorous stirring, water glass, aluminum sulfate, sodium metaaluminate, guiding agent and deionized water are mixed according to 7.5SiO₂：Al₂O₃：2.15Na₂O：190H₂Mixing the molar ratio of O to prepare NaY molecular sieve gel, wherein the mass ratio of the guiding agent is 5%, stirring for 1 hour at room temperature, placing the gel in a crystallization kettle for static crystallization treatment for 35 hours at 100 ℃, cooling after crystallization, and filtering and washing crystallized slurry to obtain a NaY molecular sieve filter cake; adding water again to the NaY molecular sieve filter cake, pulping, homogenizing, and stirring at 55 deg.C under vigorous stirring to obtain Al ₂(SO₄)₃Solution (concentration 90 gAl)₂O₃/L) and ammonia water are added simultaneously to carry out gelling reaction, the pH value of slurry in the gelling process is controlled to be 9.0, and after a certain time, Al is added according to the use₂(SO₄)₃Al of solution₂O₃The weight of the material is measured by the weight meter,according to SiO₂:Al₂O₃Adding the required tetraethoxysilane into the gel-forming slurry according to the weight ratio of 1:2.2, aging at 80 ℃ for 2 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 9 hours, filtering, washing and drying at 120 ℃ to obtain the porous material SAY-3 with a special structure.

SAY-3 scanning electron microscope photo has the characteristics shown in figure 6, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. SAY-3, has an a/b of 3.4, and has a surface silicon to aluminum atomic ratio of 0.52 as measured by XPS. The BJH pore size distribution curve has the characteristics shown in FIG. 8, presents a multistage pore distribution characteristic, and has a total specific surface area of 542m²Per g, the mesoporous specific surface area is 154m²/g。

Exchanging the porous material SAY-3 with ammonium sulfate at a weight ratio of 1:0.9 at 80 deg.C for 1 hr, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 2 hours at 650 ℃ under the condition of 100% water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the homogenized sample and ammonium sulfate at the temperature of 80 ℃ for 1 hour according to the weight ratio of 1:0.4, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-8 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-8 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (3).

The unit cell constant of B-8 was 2.457nm, the relative crystallinity was 51%, and the total specific surface area was 509m²G, total pore volume 0.63cm³/g。

Example 9

The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 42 hours; adding water again into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and then stirring vigorously at room temperatureAlCl₃Adding the solution and sodium hydroxide solution simultaneously to carry out gelling reaction, controlling the pH value of the slurry to be 9.6 in the gelling process, and adding AlCl according to the use after a certain time₃Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required water glass solution into the gel-forming slurry according to the weight ratio of 1:1.2, aging at 70 ℃ for 1 hour, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 18 hours, filtering, washing and drying at 120 ℃ to obtain the porous material SAY-4 with a special structure.

SAY-4 scanning electron microscope photo has the characteristics shown in figure 6, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. SAY-4, has an a/b of 6.0, and has a surface silicon-aluminum atomic ratio of 1.02 as measured by XPS method. The BJH pore size distribution curve has the characteristics shown in FIG. 8, presents multi-level pore distribution characteristics, and has the total specific surface area of 575m ²(g) the mesoporous specific surface area is 80m²/g。

Exchanging the porous material SAY-4 with ammonium carbonate at 75 ℃ for 1 hour according to the weight ratio of 1:1, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 4 hours at the temperature of 600 ℃ and under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, carrying out secondary exchange treatment on the homogenized product and ammonium carbonate at the temperature of 75 ℃ for 1 hour according to the weight ratio of 1:0.5, filtering, washing with water, drying and recovering the product to obtain the porous catalytic material B-9 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-9 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-9 was 2.460nm, the relative crystallinity was 66%, and the total specific surface area was 524m²G, total pore volume 0.48cm³/g。

Example 10

The preparation of NaY molecular sieve is the same as example 3, except that the crystallization treatment time is 38 hours; pulping the obtained NaY molecular sieve filter cake with water, homogenizing, and adding Al (NO) at 50 deg.C under vigorous stirring₃)₃Adding the solution and sodium hydroxide solution simultaneously to carry out gelling reaction, controlling pH of the slurry to 9.3 during gelling, adding for a certain time, and adjusting Al (NO) according to the amount of Al used ₃)₃Al of solution₂O₃By weight, in terms of SiO₂:Al₂O₃Adding the required tetraethoxysilane into the gel-forming slurry according to the weight ratio of 1:1, aging at 50 ℃ for 2 hours, placing the slurry into a stainless steel reaction kettle after aging, crystallizing at 100 ℃ for 15 hours, filtering, washing and drying at 120 ℃ to obtain the porous material SAY-8 with the special structure.

SAY-8 scanning electron microscope photo has the characteristics shown in figure 6, the particle size distribution is uniform, the particle size is 1-2 μm, and the mesoporous structure grows on the surface of NaY molecular sieve crystal grains and covers the NaY molecular sieve crystal grains. The XRD spectrum has the characteristics shown in figure 7, and simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. SAY-8, and a/b is 9.1, and the surface silicon-aluminum atomic ratio measured by XPS method is 1.30. The BJH pore size distribution curve has the characteristics shown in FIG. 8, presents a multistage pore distribution characteristic, and has a total specific surface area of 613m²(g) the mesoporous specific surface area is 53m²/g。

Exchanging the porous material SAY-8 with ammonium nitrate at 75 ℃ for 2 hours according to the weight ratio of 1:1, filtering, washing with water, and drying; then, carrying out hydrothermal roasting treatment for 2 hours at 680 ℃ under the condition of 100 percent of water vapor; and adding water into the roasted sample again for pulping, homogenizing, performing secondary exchange treatment on the sample and ammonium nitrate at the temperature of 75 ℃ for 1 hour according to the weight ratio of 1:0.5, filtering, washing with water, drying and recovering a product to obtain the porous catalytic material B-10 containing the Y-type molecular sieve.

The XRD diffraction pattern of B-10 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve containing FAU crystal phase structure and gamma-Al simultaneously₂O₃The structure of (1).

The unit cell constant of B-10 is 2.456nm, relative junctionThe crystallinity is 73 percent, and the total specific surface area is 570m²G, total pore volume 0.37cm³/g。

Examples 11 to 20

This example illustrates the cracking reaction performance of the composite material containing Y-type molecular sieve after aging treatment for 8 hours at 800 ℃ under 100% steam.

The composite materials B-1 to B-10 in the above examples 1 to 10 were mixed with an ammonium chloride solution for exchange, the sodium oxide content was further washed to 0.3 wt% or less, after filtration and drying, the resulting mixture was tableted and sieved into 20 to 40 mesh particles, the particles were aged at 800 ℃ under 100% steam conditions for 8 hours, and then the cracking reaction performance was tested on a heavy oil microreaction 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 1.4, 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

Comparative examples 1 to 10

Comparative examples 1-10 are presented to illustrate the cracking reaction performance of comparative samples of the same composition, prepared by mechanical mixing.

According to the same composition as that of the composite materials B-1 to B-10 described in examples 1 to 10, NaY molecular sieves and mesoporous materials were mechanically mixed, and subjected to contact treatment and hydrothermal calcination treatment twice with ammonium salts according to the treatment methods of B-1 to B-10, thereby obtaining comparative samples DB-1 to DB-10.

And mixing DB-1 to DB-10 with an ammonium chloride solution again for exchange until the content of sodium oxide is washed to be below 0.3 weight percent, filtering and drying, tabletting and screening into particles of 20 to 40 meshes, aging for 8 hours at 800 ℃ under the condition of 100 percent water vapor, and then evaluating the cracking performance on a heavy oil micro-reverse evaluation device. The reaction conditions were the same as in example 11.

The evaluation results are shown in Table 3.

TABLE 2

Example numbering	11	12	13	14	15	16	17	18	19	20
											Sample(s)	B-1	B-2	B-3	B-4	B-5	B-6	B-7	B-8	B-9	B-10
Yield/%)
											Dry gas	2.02	2.10	2.10	1.98	2.03	2.11	2.04	2.21	2.30	1.86
Liquefied gas	8.70	8.34	8.49	8.27	8.83	8.55	8.54	8.76	8.57	8.15
											Gasoline (gasoline)	46.99	45.78	47.67	45.13	46.75	46.39	44.12	47.54	46.81	44.59
Diesel oil	21.07	21.06	20.75	21.42	21.44	21.27	21.64	20.38	20.49	22.23
											Heavy oil	10.57	11.81	10.16	12.13	11.01	11.62	12.58	10.35	10.82	13.56
Coke	10.65	10.91	10.83	11.07	9.94	10.06	11.08	10.76	11.01	9.61
											Conversion rate/%	68.36	67.13	69.09	66.45	67.55	67.11	65.78	69.27	68.69	64.21
Coke/conversion ratio	0.156	0.162	0.157	0.166	0.147	0.150	0.168	0.155	0.160	0.150

TABLE 3

Comparative example no	1	2	3	4	5	6	7	8	9	10
											Sample (I)	DB-1	DB-2	DB-3	DB-4	DB-5	DB-6	DB-7	DB-8	DB-9	DB-10
Yield/%)
											Dry gas	1.99	2.00	2.09	1.91	1.89	1.97	1.92	2.01	2.05	1.81
Liquefied gas	8.44	8.49	8.37	7.98	8.79	8.26	8.31	8.36	8.74	7.89
											Gasoline (gasoline)	43.68	42.68	43.96	42.17	42.98	42.30	41.88	43.91	42.69	41.87
Diesel oil	22.12	22.23	22.41	23.16	22.95	22.97	22.96	22.80	23.10	23.25
											Heavy oil	12.61	13.17	11.87	14.10	12.94	13.42	14.15	11.71	11.53	14.97
Coke	11.16	11.43	11.31	10.68	10.45	11.08	10.78	11.21	11.89	10.21
											Conversion rate/%	65.27	64.60	65.72	62.74	64.11	63.61	62.89	65.49	65.37	61.78
Coke/conversion ratio	0.178	0.177	0.172	0.170	0.163	0.174	0.171	0.171	0.182	0.165

As can be seen from the heavy oil reaction data shown in Table 2, the composite materials B-1 to B-10 in examples 1 to 10 still show high conversion capability after aging treatment for 8 hours at 800 ℃ and 100% steam, the conversion rate can reach 64.21 to 69.27%, the gasoline yield can reach 44.12 to 47.67%, and the heavy oil yield is 10.16 to 13.56%, which indicates that the heavy oil conversion capability is strong, and the coke selectivity is excellent.

As can be seen from the heavy oil reaction data of the comparative samples shown in Table 3, the cracking activities of the comparative samples DB-1 to DB-10 after aging treatment for 8 hours at 800 ℃ by 100% of steam are obviously lower than those of the samples B-1 to B-10 of the examples shown in Table 2, the conversion rate is only 61.78-65.72%, the gasoline yield is reduced to some extent, the gasoline yield is about 41.87-43.96%, the heavy oil yield is obviously increased, the coke yield is increased to a certain extent, and the coke selectivity is poor.

Therefore, the porous catalytic material containing the Y-type molecular sieve, which is prepared by the method, integrates the characteristics of micropores and mesopores, and forms a special gradient characteristic on the pore structure and the acid distribution, so that the porous catalytic material shows more excellent macromolecular cracking activity, and is more suitable for macromolecular transmission and cracking compared with a simple mechanical mixed sample.

Claims

1. A preparation method of a porous catalytic material containing a Y-type molecular sieve is characterized by comprising the following preparation processes: (a) carrying out first exchange treatment on a porous material and ammonium salt according to the weight ratio of 1 (0.2-1.2) at 40-90 ℃ for 0.5-4 hours, filtering, washing with water, and drying; (b) carrying out hydrothermal roasting treatment on the sample dried in the step (a) for 1-4 hours at the temperature of 500-750 ℃ under the condition of 100% steam; (c) adding water into the roasted sample again for pulping, homogenizing, then carrying out secondary exchange treatment on the sample and ammonium salt at 50-90 ℃ for 0.5-2 hours according to the weight ratio of 1 (0.2-0.8), filtering, washing with water, drying and recovering the product to obtain the composite material containing the Y-type molecular sieve; wherein, the silicon-aluminum mesoporous layer of the porous material grows on the surface of a Y-type molecular sieve crystal grain and coats the molecular sieve crystal grain, the grain size is 1-2 mu m, and the total specific surface area is 300-650 m ²Per g, total pore volume of 0.4-1.0 cm³(ii)/g; diffraction peaks exist 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 ° in an XRD spectrogram; the chemical composition of the mesoporous layer is determined by XPS method, and the chemical composition is as follows by atomic mass: 7-20% of aluminum and 5-12% of silicon; the porous material has a/b = 1.2-9.5, wherein a represents the shift of 500 cm in Raman spectrum^-1B represents a Raman shift of 350 cm^-1Spectral peak intensity of (a).

2. The production method according to claim 1, wherein the porous material in the step (a) is obtained by: (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) adding water again to the NaY molecular sieve filter cake for pulping, dispersing uniformly, and then violently stirring at 30-70 DEG CAdding an aluminum source and an alkali solution into the mixture for reaction, and controlling the pH value of a slurry system in the reaction process to be 9-11; (4) in terms of SiO, based on the weight of alumina contained in the added aluminum source and alkali solution ₂: Al₂O₃According to the weight ratio of (1-6), adding a silicon source, continuously aging at the temperature of 30-90 ℃ for 1-8 hours, recovering the aged product, or aging at the temperature of 30-90 ℃ for 1-4 hours, then placing the slurry in a closed reaction kettle, continuously crystallizing at the temperature of 95-105 ℃ for 3-30 hours, and recovering.

3. The method according to claim 2, wherein the raw materials for synthesizing the NaY molecular sieve in step (1) are a directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water.

4. The method according to claim 2, 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.

5. The method according to claim 2, wherein the alkali solution in the step (3) is one or more selected from the group consisting of aqueous ammonia, potassium hydroxide, sodium hydroxide and sodium metaaluminate.

6. The process according to claim 2, wherein in the case of sodium metaaluminate as the alkali solution in the step (3), the alumina content is calculated from the alumina content in the step (4).

7. The method according to claim 2, wherein the silicon source in the step (4) is one or more selected from the group consisting of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane and silicon oxide.

8. The method according to claim 1, wherein the ammonium salt in the step (a) and the step (c) is one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.

9. The preparation method according to claim 1, wherein the first exchange treatment of the porous material and the ammonium salt in the step (a) comprises the following steps of (0.4-1.0) by weight ratio of the porous material and the ammonium salt, and the exchange temperature is 50-80 ℃.

10. The method according to claim 1, wherein the hydrothermal roasting treatment in the step (b) is carried out at 550 to 700 ℃ for 1 to 4 hours.

11. The preparation method according to claim 1, wherein the second exchange treatment with the ammonium salt in the step (c) is carried out at a contact temperature of 50-80 ℃ and the porous material and the ammonium salt are 1 (0.3-0.6) in weight ratio.

12. The preparation method of claim 1, wherein the porous catalytic material is prepared by coating a silicon-aluminum mesoporous layer on the surface of a Y-type molecular sieve crystal grain, the unit cell constant is 2.453-2.465 nm, the relative crystallinity is 25-75%, and the total specific surface area is 250-550 m²(g) total pore volume of 0.3-1.0 cm³/g。

13. The preparation method according to claim 1, wherein the obtained porous catalytic material has Y-type molecular sieve characteristic diffraction peaks at 6.2 °, 10.1 °, 11.9 °, 15.7 °, 18.7 °, 20.4 °, 23.7 °, 27.1 ° and 31.4 ° in XRD spectrum, and has γ -Al at wide peak between 20 ° and 30 ° and about 66 ° ₂O₃Characteristic diffraction peaks of the mesoporous structure.

14. The method according to claim 12, wherein the porous catalytic material has a unit cell constant of 2.455 to 2.462 nm and a relative crystallinity of 28 to 70%.