CN111744529A - Method for modifying composite catalytic material by rare earth - Google Patents

Method for modifying composite catalytic material by rare earth Download PDF

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CN111744529A
CN111744529A CN201910236246.1A CN201910236246A CN111744529A CN 111744529 A CN111744529 A CN 111744529A CN 201910236246 A CN201910236246 A CN 201910236246A CN 111744529 A CN111744529 A CN 111744529A
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rare earth
molecular sieve
catalytic material
solution
composite catalytic
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郑金玉
王成强
罗一斌
满征
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves

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  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

A method for modifying composite catalytic material with rare earth is characterized in that a composite catalytic material is modified with rare earth and is baked in a two-way and one-way mode or baked in a two-way and two-way mode, the mesoporous structure of the composite catalytic material grows on the surface of a Y-type molecular sieve crystal grain and coats the molecular sieve crystal grain, and the chemical composition of the mesoporous layer is as follows: 7-20% of aluminum and 5-12% of silicon, wherein in a Raman spectrum, a/b is 1.2-9.5; the porous material is obtained by directly adding an aluminum source, an alkali solution and a silicon source into a filter cake obtained in the FAU crystalline phase structure molecular sieve synthesis process as a raw material, and then carrying out hydrothermal treatment or not.

Description

Method for modifying composite catalytic material by rare earth
Technical Field
The invention relates to a method for modifying a composite catalytic material, in particular to a method for coating a mesoporous layer on the surface of a rare earth modified 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 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 MASNMR spectrum, no peak appears at a chemical shift of 0 ppm. The preparation method comprises the steps of adopting a one-way and one-way roasting process, adjusting the pH value of a solution to 8-11 by using an alkaline solution after one-way exchange, then filtering, washing, drying and roasting, or separating a molecular sieve filter cake after one-way exchange, collecting filtrate, adding the alkaline solution into the filtrate to adjust the pH value of the solution to 8-11, adding water into the obtained rare earth hydroxide filter cake and the molecular sieve filter cake, pulping, filtering, washing, drying and roasting. The process makes the excessive rare earth ions in the solution precipitate to avoid the rare earth loss and ensure that the rare earth ions are completely positioned in the molecular sieve small cage.
CN1317547A discloses an olefin reduction catalyst and a preparation method thereof, the catalyst mainly comprises REY molecular sieve with the rare earth content of 12-20 wt% and the crystallinity of more than 50% and a phosphorus and rare earth compound modified PREY molecular sieve with the rare earth content of 2-12 wt%, the phosphorus content of 0.2-3 wt% and the unit cell constant of 2.445-2.465 nm.
CN1506161A discloses a rare earth ultrastable Y molecular sieve, which adopts a double-cross double-baking process, namely, after a first-cross single-baking rare earth sodium Y is obtained, the first-cross single-baking rare earth sodium Y reacts with rare earth and phosphorus-containing substances step by step and is roasted for the second time to obtain a composite modified Y molecular sieve with the rare earth content of 8-25 wt%, the phosphorus content of 0.1-3.0 wt%, the crystallinity of 30-55% and the unit cell constant of 2.455-2.477 nm.
The molecular sieve prepared by adopting the double cross double roasting process also has other characteristics, for example, the molecular sieve which is disclosed in CN101537366A and can improve the coking performance and the preparation method thereof still adopt the double cross double roasting process, the phosphorus content of the molecular sieve is 0.05-5.0%, the rare earth content is less, only 0.05-4.0%, the unit cell constant is 2.430-2.440 nm, and the crystallinity is 35-55%.
Along with the increasing exhaustion of petroleum resources, the trend of crude oil heaving and deterioration is obvious, the slag blending proportion is continuously improved, and the requirement of the market for light oil products is not reduced, so that in recent years, the deep processing of heavy oil and residual oil is more and more emphasized in the petroleum processing industry, a plurality of refineries begin to blend vacuum residual oil, even normal pressure residual oil is directly used as a cracking raw material, the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefits of oil refining enterprises, and the macromolecular cracking capability of a catalyst therein is a focus of attention. The Y-type molecular sieve is the most main cracking active component in the conventional cracking catalyst, but due to the smaller pore channel structure, the Y-type molecular sieve shows a relatively obvious pore channel limiting effect in macromolecular reaction, and also shows a certain inhibiting effect on the cracking reaction of macromolecules such as heavy oil or residual oil and the like. Therefore, for catalytic cracking of heavy oil, it is necessary to use a material having a large pore size, no diffusion limitation to reactant molecules, and a high cracking activity.
According to the IUPAC definition, a material with a pore size of 2-50 nm is a mesoporous (mesoporous) material, and the size range of macromolecules such as heavy oil or residual oil is in the pore size range, so that the research of mesoporous materials, particularly mesoporous silicon-aluminum materials, has attracted great interest to researchers in the catalysis field. Mesoporous materials are firstly developed and succeeded by Mobil Corporation in 1992 (Beck J S, Vartuli J Z, Roth W J et al, J.Am.Chem.Comm.Soc., 1992, 114, 10834-containing 10843) and named as M41S series mesoporous molecular sieves, including MCM-41(Mobil Corporation Material-41) and MCM-48, etc., wherein the pore diameter of the molecular sieves can reach 1.6-10 nm, and the mesoporous materials are uniform and adjustable, have concentrated pore diameter distribution, large specific surface area and pore volume and strong adsorption capacity; however, the pore wall structure of the molecular sieve is an amorphous structure, so that the molecular sieve has poor hydrothermal stability and weak acidity, cannot meet the operation conditions of catalytic cracking, and is greatly limited in industrial application.
In order to solve the problem of poor hydrothermal stability of mesoporous molecular sieves, part of research work focuses on increasing the thickness of the pore walls of the molecular sieves, and if a neutral template agent is adopted, the molecular sieve with thicker pore walls can be obtained, but the defect of weaker acidity still exists. In CN1349929A, a novel mesoporous molecular sieve is disclosed, in which the primary and secondary structural units of zeolite are introduced into the pore walls of the molecular sieve, so that the molecular sieve has the basic structure of the conventional zeolite molecular sieve, and the mesoporous molecular sieve has strong acidity and ultrahigh hydrothermal stability. However, the molecular sieve has the defects that a template agent with high price is required to be used, the aperture is only about 2.7nm, the molecular sieve still has large steric hindrance effect on macromolecular cracking reaction, the structure is easy to collapse under the high-temperature hydrothermal condition, and the cracking activity is poor.
In the field of catalytic cracking, silicon-aluminum materials are widely used due to their strong acid centers and good cracking properties. The proposal of the mesoporous concept provides possibility for the preparation of a novel catalyst, and the current research results mostly focus on the use of expensive organic template and organic silicon source, and mostly need to be subjected to a high-temperature hydrothermal post-treatment process. In order to reduce the preparation cost and obtain a porous material in the mesoporous range, more research efforts have been focused on the development of disordered mesoporous materials. US5,051,385 discloses a monodisperse mesoporous Si-Al composite material prepared by mixing acidic inorganic aluminium salt and silica sol and adding alkali for reaction, wherein the aluminium content is5 to 40 wt%, a pore diameter of 20 to 50nm, and a specific surface area of 50 to 100m2(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 inventor finds that a mesoporous layer with smooth pore passage, small diffusion resistance and large pore diameter is coated on the surface of a microporous molecular sieve with complete structure, strong acidity, excellent stability and high catalytic activity in a grafting mode, and the cracking activity of the composite catalytic material with two continuous through structures is remarkably improved through rare earth modification treatment. Based on this, the present invention was made.
Therefore, the invention aims to provide a rare earth modification method for a composite catalytic material with a mesoporous layer coated on the surface of a molecular sieve.
In order to achieve the object of the present invention, the present invention provides a method for modifying a composite catalytic material with rare earth, which is characterized by comprising the following stepsThe process is as follows: (a) carrying out first contact treatment on a composite catalytic 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 dried in the step (a) under the condition of 0-100% of water vapor; (c) adding water into the roasted sample again for pulping, homogenizing, then carrying out secondary contact treatment with a rare earth solution and/or an ammonium salt solution, filtering, washing with water and drying; or carrying out secondary roasting treatment under the condition of 0-100% of water vapor; wherein the mesoporous structure of the composite catalytic material grows on the surface of a Y-shaped 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 m2(ii) a total pore volume of 0.4 to 1.0cm3(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 a/b of the composite catalytic 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).
In the composite catalytic material in the step (a), the XRD spectrum of the composite catalytic 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 composite catalytic 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 grown and coated on the surface of the molecular sieve, so that the granularity is more uniform, the mesoporous structure on the surface is unobstructed, a continuous gradient channel structure is formed with the internal molecular sieve, and the accessibility of macromolecules is enhanced.
The composite catalytic 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.
In the preparation process of the composite catalytic material in step (a), the raw materials for synthesizing the NaY molecular sieve in step (1) are usually directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water, and the addition ratio of the raw materials can be the charging ratio of the conventional NaY molecular sieve, for example, the raw materials can be 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)H2Mole of OMixing the components according to the molar ratio, uniformly stirring, and standing and aging for 0.5-48 h at the temperature of 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.
In the preparation of said composite catalytic material in step (a), the aluminum source in step (3) is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the alkali solution is one or more selected from ammonia water, potassium hydroxide, sodium hydroxide and sodium metaaluminate. 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 process of the composite catalytic material in the step (a), the silicon source in the step (4) is one or more selected from 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.
The method for modifying the composite catalytic material by the rare earth comprises the step (a) of carrying out first contact treatment on the composite catalytic material and a rare earth solution and/or an ammonium salt solution, wherein the weight ratio of the rare earth solution to the composite catalytic 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 composite catalytic 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.
Wherein, the first roasting treatment in the step (b) and the second roasting treatment in the step (c) are both carried out at 500-700 ℃, preferably 530-680 ℃, and under the condition of 0-100% of water vapor, preferably 20-100% of water vapor, for 0.5-4.0 hours, preferably 1-3 hours.
Wherein, in the second contact treatment in the step (c), in the contact treatment process with the rare earth solution and/or the ammonium salt solution obtained in the step (2), the weight ratio of the rare earth solution to the rare earth solution obtained in the step (2) calculated by rare earth oxide is 0.02-0.12, preferably 0.04-0.10, the weight ratio of the ammonium salt to the solution obtained in the step (2) 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 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 mixed rare earth of different rare earth element ratios, such as cerium-rich or lanthanum-rich mixed rare earth, and may be of any concentration; the 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 rare earth-containing composite catalytic material obtained by the method for modifying the composite catalytic material with the rare earth has the rare earth content of 2-23 wt% calculated by rare earth oxide, preferably 4-20 wt%; coating a mesoporous layer on the surface of the Y-type molecular sieve, wherein the XRD spectrogram has characteristic diffraction peaks of the Y-type molecular sieve 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, and the wide peak between 20 degrees and 30 degrees and the diffraction peak at about 66 degrees show gamma-Al2O3Structural feature peaks, said mesoporous layer having gamma-Al2O3The structure grows along the edge of a Y-shaped molecular sieve FAU crystal phase structure, and the two structures are organically connected; the unit cell constant is 2.450-2.470 nm, preferably 2.452-2.466 nm, the relative crystallinity is 20-60%, preferably 23-58%, and the total specific surface area is 250-550 m2(g) total pore volume of 0.3-0.9 cm3The particle size is 1 to 2 μm.
The rare earth-containing composite catalytic material obtained by the method integrates the characteristics of a micropore structure and a mesopore structure, and forms more special characteristics on a pore structure and acid distribution through rare earth modification treatment, so that the rare earth-containing composite catalytic material has more excellent macromolecule conversion capability and cracking activity.
Drawings
FIG. 1 is a SEM photograph of the SAYN-1 composite catalytic material of example 1.
FIG. 2 is a SEM photograph of a typical NaY molecular sieve in example 1.
FIG. 3 is an X-ray diffraction spectrum of SAYN-1 as the composite catalytic material in example 1.
FIG. 4 is a low temperature nitrogen desorption isotherm of the composite catalytic material SAYN-1 of example 1.
FIG. 5 is an X-ray diffraction pattern of the rare earth-containing composite catalytic material RB-1 obtained by the method of example 1.
FIG. 6 is a SEM photograph of the composite catalytic material SAY-2 of example 7.
FIG. 7 is an X-ray diffraction pattern of composite catalytic material SAY-2 of example 7.
FIG. 8 is a plot of the pore size distribution of composite catalytic 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.
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.
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, and the like were measured by X-ray diffraction. Wherein the crystals areThe degree is measured according to the industry standards SH/T0340-92 and SH/T0339-92 of China general petrochemical company, and the crystallinity standard sample of the NaY molecular sieve is measured: NaY molecular sieve (GS BG 75004-. The pore parameters are measured by a low-temperature nitrogen adsorption-desorption volumetric method. RE of the Material2O3The content was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP methods of experiments)", eds Yang Cui et al, published by scientific Press, 1990).
Particle size testing of the materials in the examples was performed using a scanning electron microscope SEM using a Hitachi S4800 model Japan field emission scanning electron microscope at an acceleration voltage of 5kV, and energy spectra were collected and processed using Horiba 350 software.
In the examples, the laser Raman spectrum of the material was measured by using a LabRAM HR UV-NIR laser confocal Raman spectrometer of HORIBA, Japan, with an excitation light source wavelength of 325nm, an ultraviolet 15-fold objective lens, a confocal pinhole of 100 μm, and a spectrum scanning time of 100 s.
Example 1
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 C2(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 the reaction system, and then is aged for 6 hours at 70 ℃, and after the aging is finished, the mixture is filtered, washed and dried at 120 ℃ to obtain the composite catalytic material SAYN-1.
The comparison between the images in the FIG. 1 and the FIG. 2 shows that 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 the SAYN-1 is a material with a wrinkled mesoporous structure grown on the surface of the crystal grains of the NaY molecular sieve, the XRD spectrum of the SAYN-1 is shown in the 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 peak labeled ★ corresponds to the FAU crystal phase structure of the Y molecular sieve, the characteristic diffraction peak labeled ▲ corresponds to the pseudo-boehmite structure of the mesoporous layer, the nitrogen desorption isotherm of the SAYN-1 is shown in the FIG. 4, the typical IV-like surface area of the NAY molecular sieve, and the total surface area of the pseudo-like2(ii)/g, total pore volume 0.92cm3(ii) in terms of/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 500cm shift in the Raman (Raman) spectrum-1B represents a Raman shift of 350cm-1Spectral peak intensity of (a).
Contacting SAYN-1 with a rare earth chloride solution and an ammonium salt solution at a temperature of 65 ℃ for 2 hours according to the weight ratio of 0.09 of the rare earth oxide to the composite catalytic material and the weight ratio of 0.05 of the rare earth oxide to the ammonium salt solution, 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 a sample obtained by roasting, pulping, and mixing the materials according to a weight ratio of 1: 0.3, and ammonium salt solution, carrying out secondary contact treatment at 65 ℃ for 1 hour, filtering, washing with water, and drying to obtain the rare earth-containing composite catalytic material, which is recorded as RB-1.
The XRD diffraction pattern of RB-1 is shown in FIG. 5, which shows that the FAU crystal phase structure and gamma-Al containing Y-type molecular sieve simultaneously2O3Structure, at 6.2 °, 10.Diffraction peaks (peaks corresponding to2O3Structural feature diffraction peaks.
RB-1 rare earth oxide 8.8 wt%, unit cell constant 2.459nm, relative crystallinity 36%, total specific surface area 489m2In terms of/g, total pore volume 0.86cm3The particle size is 1 to 2 μm.
Example 2
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 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 is aged for 4 hours at 50 ℃, and after the aging is finished, the mixture is filtered, washed and dried at 120 ℃ to obtain the composite catalytic material SAYN-2.
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 simultaneously contains an FAU crystal phase structure and a pseudo-boehmite structure. 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(ii) in terms of/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.
Contacting SAYN-2 with a rare earth chloride solution at the weight ratio of rare earth oxide to the composite catalytic material of 0.12 at 70 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 3 hours at 580 ℃ under the condition of 100 percent of water vapor; and adding water into the sample obtained by roasting, pulping, mixing the sample with the rare earth solution and the ammonium salt solution according to the weight ratio of the rare earth oxide to the ammonium salt of 0.02 and the weight ratio of the ammonium salt to the ammonium salt of 0.15, carrying out second contact treatment at 70 ℃ for 1 hour, filtering, washing with water, and drying to obtain the rare earth-containing composite catalytic material, which is recorded as RB-2.
The XRD diffraction pattern of RB-2 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
13.7 percent of rare earth oxide in RB-2, a unit cell constant of 2.464nm, a relative crystallinity of 52 percent and a total specific surface area of 526m2In terms of/g, total pore volume 0.42cm3The particle size is 1 to 2 μm.
Example 3
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 ammonia water are added into the mixture at the same time for reaction, the pH value of a slurry system in the reaction process is controlled to be 9.0, and after a certain time, the pH value is adjusted according to the Al (NO) used3)3Al of solution2O3By weight, in terms of SiO2:Al2O3Adding the required tetraethoxysilane into the reaction system according to the weight ratio of 1:3, and then heating at 80 DEG CAnd continuing to age for 4 hours, filtering after the aging is finished, washing and drying at 120 ℃ to obtain the composite catalytic material SAYN-3.
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 559m2(ii)/g, total pore volume 0.66cm3(ii) in terms of/g. The surface chemical composition measured by the XPS method was 13.3% aluminum and 7.4% silicon by atomic mass. Raman (Raman) spectroscopy, with an a/b of 2.5.
Contacting SAYN-3 with a rare earth chloride solution according to the weight ratio of 0.06 of the rare earth oxide to the composite catalytic material and the weight ratio of 0.20 of an ammonium salt solution at 75 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 4 hours at the temperature of 600 ℃ and under the condition of 100 percent of water vapor; adding water into a sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of 0.06 of rare earth oxide, carrying out secondary contact treatment for 1 hour at 75 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment at 600 ℃, and carrying out treatment for 2 hours to obtain the rare earth-containing composite catalytic material, which is marked as RB-3.
The XRD diffraction pattern of RB-3 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
In RB-3, the rare earth oxide accounts for 11.8 percent by weight, the unit cell constant is 2.460nm, the relative crystallinity is 39 percent, and the total specific surface area is 508m2G, total pore volume 0.63cm3The particle size is 1 to 2 μm.
Example 4
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 violently stirring at room temperatureThen, Al is added2(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 a 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 composite catalytic material SAYN-4.
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.
Contacting SAYN-4 with a rare earth chloride solution at a weight ratio of rare earth oxide to the composite catalytic material of 0.12 at 60 ℃ for 2 hours, 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 sample obtained by roasting, pulping, mixing the sample with the rare earth solution and the ammonium salt solution according to the weight ratio of the rare earth oxide to the ammonium salt to be 0.04, carrying out second contact treatment at 60 ℃ for 1 hour, filtering, washing with water, and drying to obtain the rare earth-containing composite catalytic material, which is recorded as RB-4.
The XRD diffraction pattern of RB-4 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
RB-4 contains rare earth oxide 15.9 wt%, unit cell constant 2.466nm, relative crystallinity 47%, and total specific surface area 550m2In g, total pore volume 0.38cm3/g，The particle size is 1 to 2 μm.
Example 5
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 composite catalytic material SAYN-5.
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 420m2(ii)/g, total pore volume 0.62cm3(ii) in terms of/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.
Contacting SAYN-5 and a rare earth chloride solution with an ammonium salt solution at a weight ratio of 0.3 to 0.03 of the weight ratio of the rare earth oxide to the composite catalytic material at 80 ℃ for 1 hour, filtering, washing with water and drying; then roasting for 2 hours at 630 ℃; adding water into a sample obtained by roasting, pulping, and mixing the materials according to a weight ratio of 1: mixing the mixture with ammonium salt solution in the proportion of 0.35, carrying out secondary contact treatment at 80 ℃ for 1 hour, filtering, washing with water, drying, carrying out secondary roasting treatment at 630 ℃ for 2 hours, and obtaining the rare earth-containing composite catalytic material, which is recorded as RB-5.
The XRD diffraction pattern of RB-5 has the characteristics shown in figure 5, and shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
RB-5 contains 3 wt% of rare earth oxide, unit cell constant 2.454nm, relative crystallinity 30%, and total specific surface area 400m2In terms of/g, total pore volume 0.61cm3The particle size is 1 to 2 μm.
Example 6
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 AlCl3Solution 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 composite catalytic material SAYN-8.
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(ii) in terms of/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.
Contacting SAYN-8 with a rare earth chloride solution according to the weight ratio of 0.02 of the rare earth oxide to the composite catalytic material and 0.30 of an ammonium salt solution at 55 ℃ for 3 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 sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.08, carrying out secondary contact treatment for 1 hour at 55 ℃, filtering, washing with water, and drying to obtain the rare earth-containing composite catalytic material, which is recorded as RB-6.
The XRD diffraction pattern of RB-6 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
RB-6 rare earth oxide 9.6 wt%, unit cell constant 2.457nm, relative crystallinity 28%, total specific surface area 372m2G, total pore volume 0.84cm3The particle size is 1 to 2 μm.
Example 7
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 composite catalytic material SAY-2.
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 (a/b: 1.3), surface silicon measured by XPS methodThe atomic ratio of aluminum 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。
SAY-2 and ammonium salt solution are contacted and treated for 1 hour at 70 ℃ according to the weight ratio of 1:1, filtered, washed and dried; then roasting for 4 hours at 550 ℃ under the condition of 100 percent of water vapor; and adding water into the sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.08, carrying out secondary contact treatment at 70 ℃ for 1 hour, filtering, washing with water, and drying to obtain the rare earth-containing composite catalytic material, which is recorded as RB-7.
The XRD diffraction pattern of RB-7 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
In RB-7, the rare earth oxide accounts for 8 percent by weight, the unit cell constant is 2.458nm, the relative crystallinity is 31 percent, and the total specific surface area is 408m2In terms of/g, total pore volume 0.89cm3The particle size is 1 to 2 μm.
Example 8
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and stirring at 55 deg.C under vigorous stirring to obtain Al2(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 solution2O3By weight, in terms of 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 composite catalytic material SAY-3.
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。
SAY-3 and rare earth chloride solution are contacted with ammonium salt solution for 1 hour at 75 ℃ according to the weight ratio of 0.08 of rare earth oxide to composite catalytic material and the weight ratio of 0.10 of ammonium salt solution, and then are filtered, washed and dried; then roasting for 2 hours at 600 ℃ under the condition of 100 percent of water vapor; and adding water into the sample obtained by roasting, pulping, mixing the sample with the rare earth solution and the ammonium salt solution according to the weight ratio of the rare earth oxide to the ammonium salt to be 0.04, carrying out second contact treatment at 75 ℃ for 1 hour, filtering, washing with water, and drying to obtain the rare earth-containing composite catalytic material, which is recorded as RB-8.
The XRD diffraction pattern of RB-8 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
In RB-8, the rare earth oxide accounts for 11.8 percent by weight, the unit cell constant is 2.463nm, the relative crystallinity is 44 percent, and the total specific surface area is 500m2In terms of/g, total pore volume 0.62cm3The particle size is 1 to 2 μm.
Example 9
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
The preparation of NaY molecular sieve is the same as that of example 3, except that the crystallization time is 42 hoursWhen the current is over; adding water again into the obtained NaY molecular sieve filter cake for pulping, homogenizing, and then stirring vigorously at room temperature to obtain AlCl3Adding 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 composite catalytic material SAY-4.
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 575m2(g) the mesoporous specific surface area is 80m2/g。
SAY-4 and rare earth chloride solution are contacted and treated for 1 hour at 80 ℃ according to the weight ratio of the rare earth oxide to the composite catalytic material of 0.12, and then are filtered, washed and dried; then roasting for 2 hours at the temperature of 630 ℃ under the condition of 100 percent of water vapor; adding water into a sample obtained by roasting, pulping, mixing with a rare earth solution according to the weight ratio of the rare earth oxide of 0.06, carrying out secondary contact treatment for 1 hour at 80 ℃, filtering, washing with water, drying, carrying out secondary roasting treatment under the conditions of 630 ℃ and 100% of water vapor for 2 hours, and obtaining the composite catalytic material containing rare earth, which is marked as RB-9.
The XRD diffraction pattern of RB-9 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
RB-9 contains rare earth oxide 17.7 wt%, unit cell constant 2.465nm, relative crystallinity 42%, and total specific surface area 539m2G, totalPore volume 0.50cm3The particle size is 1 to 2 μm.
Example 10
This example illustrates the process of modifying a composite catalytic material with rare earth elements according to the present invention.
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 used3)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 composite catalytic material SAY-8.
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。
SAY-8 and rare earth chloride solution are contacted with ammonium salt solution for 2 hours at 60 ℃ according to the weight ratio of 0.06 of the rare earth oxide to the composite catalytic material and the weight ratio of 0.20 of the ammonium salt solution, and then are filtered, washed and dried; then roasting for 2 hours at 580 ℃ under the condition of 100 percent of water vapor; adding water into a sample obtained by roasting, pulping, and mixing the materials according to a weight ratio of 1: 0.4, carrying out second contact treatment for 1 hour at 60 ℃, filtering, washing, drying, carrying out second roasting treatment at 580 ℃ under the condition of 100% steam, and carrying out treatment for 2 hours to obtain the rare earth-containing composite catalytic material, which is marked as RB-10.
The XRD diffraction pattern of RB-10 has the characteristics shown in figure 5, which shows that the Y-type molecular sieve-containing FAU crystal phase structure and gamma-Al are simultaneously contained2O3And (5) structure.
RB-10 rare earth oxide 5.9 wt%, unit cell constant 2.455nm, relative crystallinity 54%, total specific surface area 542m2G, total pore volume 0.37cm3The particle size is 1 to 2 μm.
Examples 11 to 20
This example illustrates the cracking reaction performance of the rare earth-containing composite catalytic material obtained by the method of the present invention after aging treatment for 12 hours at 800 ℃ under 100% steam.
The rare earth-containing composite materials RB-1 to RB-10 in the embodiments 1 to 10 are mixed and exchanged with an ammonium chloride solution, the sodium oxide content of the mixture is further washed to be below 0.3 weight percent, the mixture is filtered, dried, tableted and sieved into particles of 20 to 40 meshes, the particles are aged for 12 hours under the conditions of 800 ℃ and 100 percent of water vapor, and then the cracking reaction performance is tested on a heavy oil micro-reverse 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 1.4, 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
Figure BDA0002008287760000191
Figure BDA0002008287760000201
TABLE 2
Example numbering 11 12 13 14 15 16 17 18 19 20
Sample (I) RB-1 RB-2 RB-3 RB-4 RB-5 RB-6 RB-7 RB-8 RB-9 RB-10
Yield/%)
Dry gas 1.72 1.86 1.91 1.99 1.63 2.01 1.90 1.80 2.05 1.89
Liquefied gas 8.70 8.59 8.48 8.52 8.93 9.25 8.59 8.70 8.93 8.85
Gasoline (gasoline) 49.60 52.68 51.60 54.30 48.25 49.91 48.72 52.07 53.72 47.90
Diesel oil 20.03 19.06 19.79 18.21 21.04 20.27 21.31 19.67 18.49 22.05
Heavy oil 9.75. 7.81 9.34 7.11 10.01 9.82 10.15 9.12 7.30 10.52
Coke 10.2 10.00 8.88 9.87 10.14 8.74 9.33 8.64 9.51 8.79
Conversion rate/% 70.22 73.13 70.87 74.68 68.95 69.91 68.54 71.21 74.21 67.43
Coke/conversion ratio 0.145 0.137 0.125 0.132 0.147 0.125 0.136 0.121 0.128 0.130
As can be seen from the heavy oil reaction data shown in table 2, the rare earth modified composite catalytic materials RB-1 to RB-10 in examples 1 to 10 still have high conversion capability after aging treatment with 100% steam at 800 ℃ for 12 hours, the conversion rate reaches 67.43 to 74.68%, the gasoline yield reaches 47.90 to 54.30%, the heavy oil yield is 7.11 to 10.52%, the heavy oil conversion capability is high, the coke yield is low, and the coke selectivity is good.
Therefore, the rare earth-containing composite catalytic material obtained by the method provided by the invention further modulates the channel structure and the acid distribution through rare earth modification on the basis of integrating two structural characteristics of micropores and mesopores, so that the composite material has more excellent conversion capability and macromolecule cracking activity.

Claims (12)

1. A method for modifying a composite catalytic material by using rare earth is characterized by comprising the following steps: (a) carrying out first contact treatment on a composite catalytic 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 dried in the step (a) under the condition of 0-100% of water vapor; (c) adding water into the roasted sample again for pulping, homogenizing, then carrying out secondary contact treatment with a rare earth solution and/or an ammonium salt solution, filtering, washing with water and drying; or carrying out secondary roasting treatment under the condition of 0-100% of water vapor; wherein, the mesoporous structure of the composite catalytic material in the step (a) grows on the surface of a Y-shaped 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 m2(ii) a total pore volume of 0.4 to 1.0cm3(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 a/b of the composite catalytic material is 1.2-9.5, wherein a represents the shift of 500cm in Raman spectrum-1B represents a Raman shift of 350cm-1(ii) spectral peak intensity of;and the composite catalytic material in the step (a) is obtained 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) 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, and recovering an aged product, or adding the silicon source, continuing to crystallize at the temperature of 95-105 ℃ for 3-30 hours, and recovering the slurry, wherein the aged product is aged at the temperature of 30-90 ℃ for 1-4 hours.
2. The method of claim 1, wherein the raw materials for synthesizing NaY molecular sieve in step (1) are directing agent, water glass, sodium metaaluminate, aluminum sulfate and deionized water.
3. The process according to claim 1, wherein in step (3) the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
4. The method according to claim 1, wherein said alkaline solution in step (3) is one or more selected from the group consisting of aqueous ammonia, potassium hydroxide, sodium hydroxide and sodium metaaluminate.
5. A process as claimed in claim 1, wherein in step (3), when sodium metaaluminate is used as the alkali solution, the alumina content is calculated to the alumina content in step (4).
6. The method according to claim 1, wherein the silicon source in step (4) is one or more selected from the group consisting of water glass, sodium silicate, tetraethoxysilane, tetramethoxysilane, and silicon oxide.
7. The method according to claim 1, wherein the first contact treatment of the composite catalytic material and the rare earth solution and/or the ammonium salt solution in step (a) is carried out, the weight ratio of the rare earth solution to the composite catalytic material calculated by the rare earth oxide is 0.02-0.14, preferably 0.03-0.13, the weight ratio of the ammonium salt to the composite catalytic 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.
8. The method according to claim 1, wherein the first or second calcination treatment in steps (b) and (c) is carried out at a temperature of 500 to 700 ℃, preferably 530 to 680 ℃, under the condition of 0 to 100% steam, preferably 20 to 100% steam, for 0.5 to 4.0 hours, preferably 1 to 3 hours.
9. The process according to claim 1, wherein in the second contact treatment in the step (c), the weight ratio of the rare earth solution to the solution obtained in the step (2) is 0.02 to 0.12, preferably 0.04 to 0.10 in terms of rare earth oxide, the weight ratio of the ammonium salt to the solution obtained in the step (2) 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.
10. The method according to claim 1, wherein said ammonium salt in step (a) and step (c) is one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
11. The process according to claim 1, wherein the rare earth-modified composite catalytic material is obtained with a rare earth content of 2 to 23 wt.%, preferably 4 to 20 wt.%, calculated as rare earth oxide.
12. The method of claim 1, wherein the rare earth modified composite catalytic material is prepared by coating a mesoporous layer on the surface of a Y-type molecular sieveA layer, said mesoporous layer having gamma-Al2O3The structure grows along the edge of a Y-shaped molecular sieve FAU crystal phase structure, and the two structures are organically connected; the unit cell constant is 2.450-2.470 nm, preferably 2.452-2.466 nm, the relative crystallinity is 20-60%, preferably 23-58%, and the total specific surface area is 250-550 m2(g) total pore volume of 0.3-0.9 cm3The particle size is 1 to 2 μm.
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