CN111036288A - Catalytic cracking catalyst and preparation method thereof - Google Patents

Catalytic cracking catalyst and preparation method thereof Download PDF

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Publication number
CN111036288A
CN111036288A CN201811183711.1A CN201811183711A CN111036288A CN 111036288 A CN111036288 A CN 111036288A CN 201811183711 A CN201811183711 A CN 201811183711A CN 111036288 A CN111036288 A CN 111036288A
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molecular sieve
zsm
mesoporous
macroporous
catalytic cracking
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黄校亮
李景锋
姚文君
刘从华
田爱珍
郑云锋
孙书红
段宏昌
潘志爽
李雪礼
袁程远
慕彦君
谭争国
张海涛
刘超伟
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Petrochina Co Ltd
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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
    • B01J29/80—Mixtures of different zeolites
    • B01J35/615—
    • B01J35/633—
    • B01J35/647—
    • B01J35/651—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • B01J29/084—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
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/80—Mixtures of different zeolites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a catalytic cracking catalyst, which comprises 5-40% of clay by taking 100% of the mass of the catalyst as a reference; 15-50% of zeolite molecular sieve; 5-20% of a binder; 0.5-30% of alumina is added; wherein the zeolite molecular sieve comprises a mesoporous-macroporous ZSM-5 molecular sieve. The catalyst of the invention can effectively improve the yield of propylene and the concentration of propylene in liquefied gas, reduce the yield of heavy oil and increase the yield of target products of cracking reaction.

Description

Catalytic cracking catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalytic cracking catalyst preparation, and particularly relates to a catalytic cracking catalyst containing a mesoporous-macroporous ZSM-5 molecular sieve and a preparation method thereof.
Background
Research and manufacturers of refinery catalysts at home and abroad have long been devoted to research on improving the performance of an FCC catalyst by using a shape-selective molecular sieve ZSM-5 so as to improve the propylene yield of an FCC unit. A typical product is that Grace Davison company develops FCC catalyst Apex series catalysts with the function of increasing the propylene, the yield of the propylene can reach more than 15%, the yield of propylene is increased by 0.9% when the addition amount of propylene additive Olefins Max is 3-4%; the catalyst AFX for increasing the yield of the propylene developed by Albemarle company can improve the yield of the propylene to the maximum extent; the SelectZ propylene yield increasing assistant developed by BASF company can increase propylene yield without diluting the activity of the main catalyst, and other propylene yield increasing Penta series assistants developed by Intercat company also have certain propylene yield increasing effect.
The ZSM-5 molecular sieve was first developed by Mobil corporation of America in 1972. The molecular sieve has a unique pore channel structure, an adjustable acid center, and excellent thermal stability and hydrothermal stability, and is one of the most important molecular sieve catalytic materials at present, and the molecular sieve is widely applied to the catalytic fields of petroleum refining, petrochemical industry, coal chemical industry, fine chemical industry and the like. However, the pore size of the micropores of ZSM-5 molecular sieves is small, which is detrimental to the adsorption, reaction and diffusion of reactant molecules at the acid sites within their pores. There are two approaches to solve this problem: one is to prepare ZSM-5 molecular sieve with nanometer grain size; the other is to prepare a mesoporous or mesoporous-macroporous ZSM-5 molecular sieve. However, nanocrystalline grain sized ZSM-5 molecular sieve crystallites agglomerate at high temperatures. Therefore, the introduction of the mesopores or the mesopores-macropores is an effective way for improving the catalytic performance of the ZSM-5 molecular sieve.
There are a large number of research reports on mesoporous ZSM-5 molecular sieves, preparation methods thereof and catalytic applications. CN103101930 synthesizes the ordered mesopore of 2-50 nm by using silicon dioxide containing the ordered mesopore as a silicon source
ZSM-5 molecular sieve. Yan G and the like [ Yan G, Guang W, Fangwei M, et al, MicroporousMesoporous Mater, 2016,226:251] synthesize the mesoporous ZSM-5 molecular sieve by utilizing N-phenylaminopropyl trimethoxy silane under the induction of seed crystals, and the molecular sieve shows high stability in the aromatization reaction of methanol. Jian Z et al [ JianZ, Jiawei T, Liping R, et al, j.catal.,2016,340:166] crystallized the monolithic material composed of binder and ZSM-5 molecular sieve to obtain the ZSM-5 molecular sieve monolithic material with mesopores within the ZSM-5 molecular sieve crystal, which exhibited excellent catalytic activity and stability in the reaction of converting methanol into hydrocarbons.
Compared with the mesoporous ZSM-5 molecular sieve, the mesoporous-macroporous ZSM-5 molecular sieve can provide more accessible acid centers and has better catalytic performance. Thus, meso-macroporous ZSM-The 5 molecular sieve, the preparation method and the catalytic application thereof become the research hotspot of the ZSM-5 molecular sieve. CN201510288341.8 takes tetrapropylammonium hydroxide as a structure directing agent and ordered macroporous-mesoporous carbon as a mesoporous-macroporous template agent, and prepares micron-sized silicon-aluminum molecular sieve ZSM-5 single crystals with macroporous, mesoporous and microporous structures under the conventional dry glue synthesis condition, wherein the single crystals are formed by mutually connected molecular sieve nano-structure units in a highly ordered face-to-center close packing manner, have highly ordered macroporous structures, and simultaneously have a multi-stage pore channel structure and a single crystal structure, and have better flow diffusivity and structural stability. CN104226360A takes tetrapropylammonium hydroxide and tetrapropylammonium bromide as structure directing agents and starch, carbon powder and the like as mesoporous-macroporous template agents to prepare a mesoporous-macroporous full-crystalline ZSM-5 molecular sieve catalyst, and the catalyst shows high activity, selectivity and stability for the reactions of preparing propylene from hydrocarbon and preparing propylene from methanol. CN201210594606.3 discloses a method for preparing three-dimensional ordered hierarchical pore molecular sieve catalyst by using micro-jet free-forming system in the presence of structure-directing agent. The preparation method comprises the steps of preparing a molecular sieve containing ordered mesopores, designing different macroporous structures by computer software, and finally preparing the three-dimensional ordered macroporous-mesoporous-microporous ZSM-5 molecular sieve by adopting a jet free forming system. The ZSM-5 molecular sieve has 0.2-2 nm micropores, 2-30 nm ordered mesopores and 0.02-0.5 mm ordered macropores, has a larger specific surface area, and has important application prospects in the aspects of petrochemical industry and separation catalysis. CN201410203175.2 provides a synthesis method of a novel ordered macroporous-mesoporous-microporous silicon-aluminum molecular sieve. The method organically combines a template method and a molecular sieve crystal transformation process, and prepares the mutually communicated three-dimensional ordered macroporous-mesoporous hierarchical pore molecular sieve with different pore sizes by controllable selection of a macroporous template and a mesoporous template. The macroporous template used in the method is monodisperse polymer microspheres or monodisperse inorganic microspheres, and the polymer microspheres are polystyrene microspheres, polymethyl methacrylate microspheres or polystyrene-polymethyl methacrylate-sodium polymethacrylate copolymer microspheresOne kind, the microsphere particle size of the macroporous template is uniform and the size and the dimension are adjustable within the range of 100-1000 nm, and the nanosphere particle size of the mesoporous template is uniform and the size and the dimension are adjustable within the range of 5-50 nm. The method is simple and feasible, the operation condition is easy to control, the synthesis period is short, and the application of the molecular sieve is expected to be expanded to the field of organic macromolecular catalysis which cannot be related to the traditional molecular sieve. CN200610001333.1 relates to a method for synthesizing hierarchical porous ZSM-5 zeolite, which comprises the steps of dipping a silica gel monolithic column by using a sucrose solution, drying, polymerizing and carbonizing to obtain a carbon-silicon compound, mixing an aluminum source, an inorganic base, a structure directing agent and water, fully wetting the carbon-silicon compound, and crystallizing to obtain the hierarchical porous ZSM-5 zeolite. The ZSM-5 zeolite material synthesized by the method has micron-sized macropores, mesopores, micropores and other multi-level pore channels, overcomes the limitation of zeolite molecular sieve micropores on the catalytic performance, wherein the existence of the permeable macropores can shorten the diffusion distance of reaction molecules, reduce the pressure drop of the device, improve the unit processing capacity of the device, facilitate the regulation and control of the selectivity of products, and the mesopores can provide rich internal specific surface area, thereby having very important significance for macromolecular catalytic reaction. CN201310322470.5 relates to a method for preparing a ZSM-5 zeolite molecular sieve with a hierarchical pore structure, a product and application thereof, and more particularly, the ZSM-5 zeolite molecular sieve with the hierarchical pore structure is obtained by a hydrothermal synthesis method under an alkaline condition by taking a gemini type cationic surfactant as a structure directing agent. The total specific surface area of the molecular sieve is 240-1000 m2·g-1The total pore volume is 0.30-1.40 cm3·g-1The catalyst can be used as a catalyst in the reaction of preparing olefin from methanol, can greatly prolong the service life of the catalyst, and can be used in other fields of catalysis of coal and petrochemical industry, conversion of natural gas, adsorption and separation and the like. CN201110219618.3 relates to a zeolite molecular sieve material with a three-dimensional communicated hierarchical pore structure and a preparation method thereof. The method comprises the following steps: firstly, taking an anionic surfactant and a cationic surfactant as primary structural units, and forming secondary structural units by self-assembly in a solution; self-assembling in the solution to compound into an amphiphilic block copolymer; then, the amphiphilic block copolymer is used as a moldThe plate agent is self-assembled in solution by a structure directing agent and inorganic silicon to obtain a silicon dioxide/surfactant/template agent composite material; and finally, calcining to remove the surfactant and the template agent to obtain the multilevel-structure mesoporous zeolite molecular sieve material consisting of communicated mesopores, micropores and macropores. The material has high specific surface area and high hydrothermal stability, and has wide application prospect in the fields of petrochemical industry, heavy oil catalytic cracking, biological separation, adsorption and the like. The material obtained by the invention has excellent performance, simple synthesis method and easily obtained raw materials, and is suitable for industrial production. CN201510856191.6 discloses a hierarchical pore molecular sieve catalyst, which has a framework structure of macropores, mesopores and micropores, and comprises synthesis and application of a molecular sieve, wherein the pore size of the porous molecular sieve is 0.5-100 nm, the particle size of a solidified metal catalyst of the porous molecular sieve is 0.5-2 mu m, the metal content in the catalyst is 1-30%, and the particle size of the metal particles is 1-50 nm; its preparing process is also disclosed. The size of the molecular sieve pore in the catalyst is adjustable; the metal center and the acid center can be effectively matched; the catalyst has high activity; the selectivity of the target product is high; the Fischer-Tropsch synthesis reaction activity is high; the catalyst has simple preparation process, low cost, high mechanical strength and high wear resistance, and is suitable for large-scale industrial production and application. CN201110070493.2 relates to a preparation method of a hierarchical porous hollow ZSM-5 molecular sieve nanosphere: taking 64mL of tetraethoxysilane, 0.54g of aluminum isopropoxide and 2.24g of sodium hydroxide (1mol/L) as initial raw materials, taking 100g of tetrapropyl ammonium hydroxide aqueous solution with the mass concentration of 15.7% as a structure directing agent, and drying and roasting the product to obtain the nano ZSM-5 molecular sieve, wherein the crystallization temperature is 100-200 ℃; adding a nano ZSM-5 molecular sieve into an alkali solution, treating the nano ZSM-5 molecular sieve by using microwave, and then centrifugally drying the nano ZSM-5 molecular sieve to obtain a hierarchical porous ZSM-5 molecular sieve nanosphere with a macroporous-microporous or mesoporous-microporous structure; the microwave treatment time is 1-25 s, and the microwave output power is 400-900W; the concentration of the alkali solution is 0.1-2 mol/L; the microwave treatment time is changed, and the pore diameter of the hollow pore of the ZSM-5 molecular sieve nanosphere can be regulated and controlled within 30-150 nm.
By integrating the disclosure of the mesoporous-macroporous ZSM-5 molecular sieve, the preparation method thereof and the catalytic application, it can be seen that the mesoporous-macroporous ZSM-5 molecular sieve as the catalyst material shows better catalytic performance than the mesoporous ZSM-5 molecular sieve, but the existing preparation method of the mesoporous-macroporous ZSM-5 molecular sieve has the following defects: the used structure directing agents (tetrapropylammonium hydroxide, tetrapropylammonium bromide and the like) are expensive and have nitrogen oxide emission in the roasting process; the used mesoporous-macroporous template agent (starch, carbon powder, polymer microspheres and the like) has poor dispersibility in mixed gel and no mutual crosslinking effect, and the obtained mesoporous-macroporous has poor connectivity; acid/base etching to make the meso-macroporous molecular sieve comes at the expense of the microporous molecular sieve.
Disclosure of Invention
Aiming at the defects of the prior art, the invention synthesizes a mesoporous-macroporous ZSM-5 molecular sieve by taking cheap rubber microemulsion with mutual crosslinking as a mesoporous-macroporous template agent under the condition of no structure-directing agent, and prepares the molecular sieve into a catalytic cracking catalyst, and the catalyst can effectively improve the yield of propylene and the concentration of propylene in liquefied gas, reduce the yield of heavy oil and increase the yield of target products of cracking reaction.
The invention discloses a catalytic cracking catalyst, which comprises 5-40% of clay by taking 100% of the mass of the catalyst as a reference; 15-50% of zeolite molecular sieve; 5-20% of a binder; 0.5-30% of alumina is added; wherein the zeolite molecular sieve comprises a mesoporous-macroporous ZSM-5 molecular sieve.
Preferably, in the catalytic cracking catalyst, the zeolite molecular sieve is Y-type zeolite and a mesoporous-macroporous ZSM-5 molecular sieve, wherein the ratio of the Y-type zeolite to the mesoporous-macroporous ZSM-5 molecular sieve is 70-95% of the Y-type zeolite and 5-30% of the ZSM-5 molecular sieve.
In the catalytic cracking catalyst, the Y zeolite is preferably one or more of REY, REHY, P-REY and USY.
The catalytic cracking catalyst of the invention is characterized in that the clay is selected from one or more of kaolin, halloysite, montmorillonite and sepiolite.
The catalytic cracking catalyst of the invention has one or more of alumina sol, silica sol and silicon-aluminum composite sol as a binder.
The catalytic cracking catalyst of the invention is added with pseudo-boehmite as alumina.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following specific steps:
1. preparation of composite matrix slurry: and uniformly mixing the clay and the deionized water, adding the additional alumina component under the stirring state, stirring and reacting for 0.1-3 hours, adding the binder, and uniformly mixing to obtain the composite matrix slurry.
2. Preparing composite molecular sieve slurry: mixing the molecular sieve and deionized water uniformly, and stirring for 0.5-2 hours to prepare the composite molecular sieve slurry.
3. And uniformly mixing the composite matrix slurry and the composite molecular sieve slurry, and then spray-drying to obtain the catalytic cracking catalyst.
The mesoporous-macroporous ZSM-5 molecular sieve takes the rubber microemulsion as a template agent, and the aperture, the total pore volume and the total specific surface area of the ZSM-5 molecular sieve are respectively 2-100 nm and 0.20-0.60 m3/g、300～600m2/g。
The aperture and the pore volume of the mesoporous-macroporous ZSM-5 molecular sieve can be effectively adjusted according to the molecular weight and the adding amount of the template agent, and the aperture, the total pore volume and the total specific surface area can be 2-100 nm and 0.20-0.60 m3/g、300～600m2The pore diameter can be adjusted between 2 to 60nm, or 2 to 70nm, or 2 to 90 nm; the pore volume can be 0.20-0.24 m3A/g or 0.25 to 0.30m3A/g, or 0.31 to 0.35m3In the range of,/g, etc.; the total specific surface area can be 300-350 m2The volume of the particles is 360-400 m2G, or 400 to 450m2In the range of,/g, etc.
The nano-scale rubber microemulsion is preferably selected as the template agent rubber microemulsion, has good dispersibility and stronger mutual crosslinking action, is easier to generate macropores, and in addition, the raw materials can be mixed more uniformly, and the molecular sieve is easy to form.
The synthesis method of the mesoporous-macroporous ZSM-5 molecular sieve comprises the following steps:
1、preparing a silicon source, an aluminum source, inorganic acid or inorganic base and deionized water into mixture gel, wherein the molar ratio of each component in terms of oxide is 1.0SiO2:0.00025～0.5Al2O3:10～80H2O, stirring and refluxing the mixture for 2-48 h at the reflux temperature of 60-100 ℃ in a container;
2. and (2) adding the rubber microemulsion into the gel refluxed in the step (1) according to the proportion (R) of the dry basis mass of the rubber microemulsion to the mass of the silicon element in the silicon source of 0.5-50, crystallizing at 150-200 ℃ for 12-72 h, filtering and washing the synthesized product, drying at 80-140 ℃ for 2-12 h, and roasting at 500-600 ℃ for 4-10 h to obtain the mesoporous-macroporous ZSM-5 molecular sieve.
In the above step, the silicon source is one or more of ethyl orthosilicate, sodium silicate (water glass), silica gel and natural minerals.
In the above steps, the aluminum source is one or more of sodium metaaluminate, aluminum sulfate, aluminum nitrate and natural minerals.
In the above step, the molar ratio of each component in the mixed gel calculated by oxide is 1.0SiO2:0.00025～0.5Al2O3:10～80H2O。
In the above steps, the inorganic acid added in the preparation of the reactant gel may be sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid, the inorganic base added may be sodium hydroxide or potassium hydroxide,
in the above step, when the reactant gel is prepared, an inorganic acid or an inorganic base is added to make the pH value of the reactant gel be 9.5-13.0, and the pH value is preferably 10.0-12.0.
According to the method for synthesizing the mesoporous-macroporous ZSM-5 molecular sieve, when reactant gel is prepared, when tetraethoxysilane and sodium metaaluminate are respectively used as a silicon source and an aluminum source, sodium hydroxide or potassium hydroxide is added to adjust the pH value of the reactant gel, and preferably, the sodium hydroxide is added.
According to the method for synthesizing the mesoporous-macroporous ZSM-5 molecular sieve, when reactant gel is prepared, when water glass and aluminum sulfate are respectively used as a silicon source and an aluminum source, sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid is added to adjust the pH value of the reactant gel, and the sulfuric acid is preferably added.
According to the synthesis method of the mesoporous-macroporous ZSM-5 molecular sieve, the rubber microemulsion is added into the refluxed gel according to the proportion that R is 0.5-50.
According to the synthesis method of the mesoporous-macroporous ZSM-5 molecular sieve, before the rubber microemulsion is added, the mixture gel is stirred and refluxed for 2-48 hours at the temperature of 60-100 ℃ in a container, preferably, the reflux temperature is 70-90 ℃, and preferably, the reflux time is 20-28 hours, so that the generation of crystal nuclei of the ZSM-5 molecular sieve is promoted.
According to the synthesis method of the mesoporous-macroporous ZSM-5 molecular sieve, the crystallization temperature of the mixture gel is 150-250 ℃, and the preferable crystallization temperature is 180-200 ℃; the crystallization time of the mixture gel is 12-72 h, and the preferable crystallization time is 24-48 h.
According to the method disclosed by the invention, the silicon/aluminum atom molar ratio of the obtained mesoporous-macroporous ZSM-5 molecular sieve is 10-2000, and the preferable silicon/aluminum atom molar ratio is 10-400.
Compared with the prior art, the catalytic cracking catalyst containing the mesoporous-macroporous ZSM-5 molecular sieve and the preparation method thereof provided by the invention have the following characteristics:
1. under the condition of no structure directing agent and no seed crystal induction, cheap rubber microemulsion is used as a mesoporous-macroporous template agent to prepare the mesoporous-macroporous ZSM-5 molecular sieve, so that the preparation method of the molecular sieve is simple and convenient, has low cost, does not discharge nitride after roasting, and is suitable for industrial production.
2. The rubber microemulsion has good dispersibility in the mixed gel, has mutual crosslinking effect, can effectively adjust the range of the mesopores and the macropores of the prepared ZSM-5 molecular sieve according to the molecular weight and the addition amount of the rubber microemulsion, and the mesopores and the macropores of the prepared ZSM-5 molecular sieve have good connectivity, so the molecular sieve has good application prospect in the fields of heavy oil catalytic cracking, propylene production increase, heavy oil yield reduction, target product yield increase of cracking reaction and the like as a catalytic material.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of the products obtained in examples 1 to 6 of the present invention.
FIG. 2 is a plot of the pore size distribution of the product obtained in example 1 of the present invention.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
In the examples of the present invention, Na2The content of compounds such as O is measured by X-ray fluorescence (see "analytical methods of petrochemical industry (RIPP)", eds., Yanggui et al, published by scientific Press, 1990). The phase and crystallinity were measured by X-ray diffraction (XRD). The specific surface area and the pore volume are measured by a low-temperature nitrogen adsorption-desorption method.
Evaluation of catalytic cracking reaction selectivity: evaluation of the selectivity of the catalyst cracking reaction was carried out in a small Fixed Fluidized Bed (FFB) apparatus (apparatus origin: Luoyang, type: XGL-2). The catalyst is treated for 10 hours at 800 ℃ under the condition of 100 percent of water vapor in advance. The reaction temperature is 500-535 ℃, the space velocity is 12-15 h < -1 >, and the solvent-oil ratio is 5.
The crystallinity in the following examples is expressed as a percentage of the sum of the areas of five characteristic diffraction peaks (2Theta ═ 22.5-25.0 degrees) of an XRD spectrum of the obtained product and a ZSM-5 molecular sieve standard sample (the crystallinity is 96%); the yield is expressed as a percentage of the sum of the mass of the ZSM-5 product and the mass of the silicon/aluminium source in the raw material.
Example 1
Preparation of mesoporous-macroporous ZSM-5 molecular sieve
Firstly, 5000g of water glass, 440g of aluminum sulfate, 38200g of deionized water and 1000g of concentrated sulfuric acid (95-98 wt%) are prepared into components, and the molar ratio of the components in terms of oxides is 1SiO2:0.01Al2O3:0.55Na2O:62.4H2Stirring and refluxing O mixture gel at 80 ℃ for 24h in a container, adding rubber microemulsion according to the proportion of R2.5 into the mixture gel before crystallization, then filtering and washing the synthesized product, drying at 120 ℃ for 6h and roasting at 550 ℃ for 6h when crystallizing at 190 ℃ for 48h, thus obtaining the product, namely the intermediatePore-macropore ZSM-5 molecular sieve 1.
XRD measurement results show that the phase of the product is ZSM-5 molecular sieve, and the crystallinity of the product is 95% (figure 1); the low-temperature nitrogen adsorption-desorption result shows that the aperture of the mesoporous-macroporous is 2-58 nm (figure 2), and the pore volume is 0.23m3Per g, total specific surface area 304m2(ii)/g; the fluorescence analysis result shows that the silicon/aluminum atom molar ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 48.
The mass of the mesoporous-macroporous ZSM-5 molecular sieve obtained in example 1 is 2000g, and the yield is 36.8%.
Preparation of the catalyst
1. 3280g of kaolin is added into 7900g of deionized water, 3350g of pseudo-boehmite is added under stirring, the reaction is continued for 0.5 hour, 4350g of alumina sol is added, and the mixture is uniformly mixed to obtain composite matrix slurry.
2. On a dry basis, 3400g of USY and 600g of mesoporous-macroporous ZSM-5 molecular sieve 1 are taken, 8500g of deionized water is added, the mixture is uniformly mixed and stirred for 2 hours, and the composite molecular sieve slurry is prepared.
3. The two slurry streams are fully and uniformly mixed, and are subjected to conventional spray drying molding, washing and drying to obtain the catalytic cracking catalyst particles A1, wherein the main composition of A1 is shown in Table 1.
Example 2
Preparation of mesoporous-macroporous ZSM-5 molecular sieve
10420g of ethyl orthosilicate, 82g of sodium metaaluminate, 49500g of deionized water and 120g of sodium hydroxide are firstly prepared into the components, and the molar ratio of the oxides is 1.0SiO2:0.01Al2O3:0.04Na2O:55.0H2And (3) stirring and refluxing the mixture gel of O in a container at 85 ℃ for 22h, adding the rubber microemulsion into the mixture gel according to the proportion of R being 5.0 before crystallization, filtering and washing the synthesized product with water when crystallizing at 185 ℃ for 40h, drying at 110 ℃ for 7h, and roasting at 540 ℃ for 5h to obtain the mesoporous-macroporous ZSM-5 molecular sieve 2.
XRD measurement results show that the phase of the product is ZSM-5 molecular sieve, and the crystallinity of the product is 95% (figure 1). The low-temperature nitrogen adsorption-desorption result shows that the aperture of the mesopore-macropore is 2-68 nm, and the total pore volume is 0.27m3(ii)/g, total specific surface area of 365m2(ii)/g; the fluorescence analysis showed that the product had a silicon/aluminium atomic molar ratio of 48.
The mass of the mesoporous-macroporous ZSM-5 molecular sieve obtained in example 2 is 1900g, and the yield is 34.9%.
Preparation of the catalyst
1. Adding 3280g halloysite into 7900g deionized water, adding 3350g pseudo-boehmite under stirring, continuously reacting for 0.5 hour, adding 4350g aluminum sol, and uniformly mixing to obtain composite matrix slurry.
2. On a dry basis, 3400g of REY and 600g of mesoporous-macroporous ZSM-5 molecular sieve 2 are taken, 8500g of deionized water is added, the mixture is uniformly mixed and stirred for 2 hours, and the composite molecular sieve slurry is prepared.
3. The two slurry streams are fully and uniformly mixed, and are subjected to conventional spray drying molding, washing and drying to obtain the catalytic cracking catalyst particles A2, wherein the main composition of A2 is shown in Table 1.
Example 3
Preparation of mesoporous-macroporous ZSM-5 molecular sieve
Preparing mixture gel according to the same procedure as example 2, adding nanometer rubber microemulsion according to the proportion of R ═ 6.3 into the mixture gel before crystallization, then filtering, washing with water, drying at 120 ℃ for 6h and roasting at 540 ℃ for 4h when crystallizing at 180 ℃ for 46h, thus obtaining the mesoporous-macroporous ZSM-5 molecular sieve 3.
XRD measurement results show that the phase of the product is ZSM-5 molecular sieve, and the crystallinity of the product is 95.0 percent (figure 1). The low-temperature nitrogen adsorption-desorption result shows that the aperture of the mesopore-macropore is 2-75 nm, and the total pore volume is 0.31m3(ii)/g, total specific surface area of 410m2(ii)/g; the results of the fluorescence analysis indicated that the product had a silicon/aluminum atomic molar ratio of 45.
The mass of the mesoporous-macroporous ZSM-5 molecular sieve obtained in the example 3 is 1890g, and the yield is 34.0%.
Preparation of the catalyst
1. 4380g of kaolin is added into 14000g of deionized water, 5600g of pseudo-boehmite is added, the reaction is continued for 1.5 hours, 3250g of silica sol is added, and the mixture is uniformly mixed to obtain the composite matrix slurry.
2. On a dry basis, 2050g of USY and 650g of mesoporous-macroporous ZSM-5 molecular sieve 3 are taken, 4200g of deionized water is added, and stirring is carried out for 1.5 hours, so as to prepare composite molecular sieve slurry.
3. The two slurry streams are fully and uniformly mixed, and are subjected to conventional spray drying molding, washing and drying to obtain the catalytic cracking catalyst particles A3, wherein the main composition of A3 is shown in Table 1.
Example 4
Preparation of mesoporous-macroporous ZSM-5 molecular sieve
The mixture gel is prepared according to the same procedure as the example 1, before crystallization, nano-scale rubber microemulsion is added into the mixture gel according to the proportion of R being 12.6, and then when crystallization is carried out for 40 hours at 195 ℃, the synthesized product is filtered, washed by water, dried for 8 hours at 115 ℃ and roasted for 5 hours at 560 ℃, and then the mesoporous-macroporous ZSM-5 molecular sieve 4 is obtained.
XRD measurement showed that the product had a crystallinity of 95.1% (fig. 1). The low-temperature nitrogen adsorption-desorption result shows that the aperture of the mesoporous-macroporous is 2-88 nm, and the total pore volume is 0.37m3Per g, total specific surface area 460m2(ii)/g; the results of the fluorescence analysis indicated that the product had a silicon/aluminum atomic molar ratio of 47.
The mass of the mesoporous-macroporous ZSM-5 molecular sieve obtained in example 4 is 1700g, and the yield is 31.3%.
Preparation of the catalyst
1. Adding 4320g of kaolin into 14500g of deionized water, adding 850g of pseudo-boehmite under stirring, continuously reacting for 3 hours, adding 6500g of alumina sol, and uniformly mixing to obtain composite matrix slurry.
2. On a dry basis, 2000g of REHY, 800g of REY and 628g of mesoporous-macroporous ZSM-5 molecular sieve 4 are added with 4700g of deionized water, mixed uniformly and stirred for 1 hour to prepare the composite molecular sieve slurry.
3. The two slurry streams are fully and uniformly mixed, and are subjected to conventional spray drying molding, washing and drying to obtain the catalytic cracking catalyst particles A4, wherein the main composition of A4 is shown in Table 1.
Example 5
Preparation of mesoporous-macroporous ZSM-5 molecular sieve
Following the same procedure as in example 1, the components were obtained in an oxide molar ratio of 1.0SiO2:0.005Al2O3:0.55Na2O:62.4H2O, stirring and refluxing the mixed gel for 12h at 90 ℃ in a container. Before crystallization, nano-scale rubber microemulsion is added into the mixture gel according to the proportion of R-2.5, and then the mixture gel is crystallized for 24 hours at 200 ℃, and the synthesized product is filtered, washed with water, dried for 5 hours at 110 ℃ and roasted for 7 hours at 540 ℃, so that the mesoporous-macroporous ZSM-5 molecular sieve 5 is obtained.
XRD measurement results show that the phase of the product is ZSM-5 molecular sieve, and the crystallinity of the product is 96.0 percent (figure 1); the low-temperature nitrogen adsorption-desorption result shows that the aperture of the mesopore-macropore is 2-57 nm, and the total pore volume is 0.21m3Per g, total specific surface area 300m2(ii)/g; the results of the fluorescence analysis indicated that the product had a silicon/aluminum atomic molar ratio of 98.
The mass of the mesoporous-macroporous ZSM-5 molecular sieve obtained in example 5 was 2050g, and the yield was 37.7%.
Preparation of the catalyst
1. Adding 3280g of kaolin into 10500g of deionized water, adding 160g of pseudo-boehmite under stirring, continuously reacting for 2.5 hours, adding 8700g of alumina sol, and uniformly mixing to obtain composite matrix slurry.
2. On a dry basis, 4700g P-REY and 600g of mesoporous-macroporous ZSM-5 molecular sieve 5 are taken, 7700g of deionized water is added, the mixture is uniformly mixed and stirred for 0.5 hour, and the composite molecular sieve slurry is prepared.
3. The two slurry streams are fully and uniformly mixed, and are subjected to conventional spray drying molding, washing and drying to obtain the catalytic cracking catalyst particles A5, wherein the main composition of A5 is shown in Table 1.
Example 6
Preparation of mesoporous-macroporous ZSM-5 molecular sieve
According to the same procedure as in example 2, the components were first prepared in a molar ratio of 1.0SiO calculated as oxide2:0.02Al2O3:0.04Na2O:55.0H2O, stirring and refluxing the mixed gel for 18h at 85 ℃ in a container. Before crystallization, in a ratio of R to 2.5Adding the nano-scale rubber microemulsion into the mixture gel, then crystallizing at 195 ℃ for 40h, filtering the synthesized product, washing with water, drying at 110 ℃ for 4h, and roasting at 560 ℃ for 5h to obtain the mesoporous-macroporous ZSM-5 molecular sieve 6.
XRD measurement results show that the phase of the product is ZSM-5 molecular sieve, the crystallinity of the product is 93.0 percent (figure 1), and low-temperature nitrogen adsorption-desorption results show that the aperture of the mesopore-macropore is 2-78 nm, and the total pore volume is 0.35m3Per g, total specific surface area 440m2(ii)/g; the results of the fluorescence analysis indicated that the product had a silicon/aluminum atomic molar ratio of 23.
The mass of the mesoporous-macroporous ZSM-5 molecular sieve obtained in example 6 was 1950g, and the yield was 35.9%.
Preparation of the catalyst
1. Adding 3300g halloysite into 7700g deionized water, adding 3600g pseudoboehmite under stirring, reacting for 0.5 h, adding 8800g silica sol, and mixing to obtain composite matrix slurry.
2. On a dry basis, 1000g of 1000g P-REY, 550g of USY and 500g of mesoporous-macroporous ZSM-5 molecular sieve 6 are added with 1800g of deionized water, mixed uniformly and stirred for 1.5 hours to prepare the composite molecular sieve slurry.
3. The two slurry streams are fully and uniformly mixed, and are subjected to conventional spray drying molding, washing and drying to obtain the catalytic cracking catalyst particles A6, wherein the main composition of A6 is shown in Table 1.
Comparative example 1
Preparation of the catalyst
1. 3280g of kaolin is added into 7900g of deionized water, 3350g of pseudo-boehmite is added under stirring, the reaction is continued for 0.5 hour, 4350g of alumina sol is added, and the mixture is uniformly mixed to obtain composite matrix slurry.
2. On a dry basis, 3400g of USY and 600g of conventional ZSM-5 molecular sieve are taken, 8500g of deionized water is added, the mixture is uniformly mixed and stirred for 2 hours, and the composite molecular sieve slurry is prepared.
3. The two slurry streams were mixed well and subjected to conventional spray drying molding, washing and drying to obtain comparative catalytic cracking catalyst particles B1, B1, the main constituents of which are listed in table 1.
Comparative example 2
Preparation of the catalyst
1. Adding 4320g of kaolin into 14500g of deionized water, adding 850g of pseudo-boehmite under stirring, continuously reacting for 3 hours, adding 6500g of alumina sol, and uniformly mixing to obtain composite matrix slurry.
2. On a dry basis, 2000g of REHY, 800g of REY and 628g of conventional ZSM-5 molecular sieve are taken, 4700g of deionized water is added, the mixture is uniformly mixed and stirred for 1 hour, and the composite molecular sieve slurry is prepared.
3. The two slurry streams were mixed well and subjected to conventional spray drying molding, washing and drying to obtain comparative catalytic cracking catalyst particles B2, B2, the main constituents of which are listed in table 1.
Example 7
On a small-sized fixed fluidized bed reaction device, raw oil is a Xinjiang mixed catalyst, a catalyst sample is treated for 10 hours at 800 ℃ under the condition of 100% steam in advance, the catalyst loading is 150 g, the catalyst-oil ratio is 5.0, the reaction temperature is 500 ℃, and the weight space velocity is 16 hours-1The reaction performances of the catalysts A1-A6 of the present invention and the comparative catalysts B1-B2 were evaluated in comparison, and the product distribution and propylene yield of the cracking reaction and the propylene concentration data in liquefied gas are shown in Table 2. The properties of the feed oil are shown in Table 3.
TABLE 1 Main constitution of inventive and comparative catalysts
Figure BDA0001825645710000161
TABLE 2 evaluation results of the inventive catalyst and the comparative catalyst
Catalyst and process for preparing same A1 A2 A3 A4 A5 A6 B1 B2
Dry gas% 1.84 1.92 2.07 1.89 2.23 1.81 1.83 1.78
Liquefied gas% 22.10 23.28 22.59 20.73 24.21 20.59 22.57 21.25
Gasoline% 52.14 50.07 51.46 52.88 49.75 53.45 51.05 51.71
Diesel oil% 13.76 14.32 14.19 14.42 13.92 14.07 13.09 13.77
Heavy oil% 3.89 4.09 3.48 4.13 3.42 4.45 4.85 5.04
Coke% 6.04 5.66 6.10 5.48 6.31 5.35 5.75 5.72
Conversion rate% 82.36 81.58 82.34 81.45 82.61 81.5 82.03 81.2
The total liquid is collected% 87.99 87.67 88.24 88.03 87.88 88.11 86.71 86.73
Propylene% 8.76 8.89 8.46 8.06 9.66 8.06 8.02 7.41
% propylene concentration 39.6 38.2 37.3 38.8 39.8 39.1 35.5 34.9
Gasoline RON 92.9 93.1 93.0 93.5 94.2 93.7 93.1 93.0
Propylene concentration is defined as: propylene yield/liquefied gas yield × 100%
As can be seen from the data in table 2, the catalytic cracking catalyst disclosed in the present invention has high propylene yield and low heavy oil yield, and has higher propylene concentration, compared to the comparative catalyst, on the fixed fluidized bed reactor, which fully shows the reaction characteristics of the inventive catalyst with high propylene yield and low heavy oil yield.
TABLE 3 analysis results of Xinjiang mix catalysis properties
Figure BDA0001825645710000171
Figure BDA0001825645710000181
*: the above results are measured by the research and development center of lubricating oil in Lanzhou Petroleum
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (10)

1. The catalytic cracking catalyst is characterized by comprising, by mass, 5-40% of clay, 15-50% of zeolite molecular sieve, 5-20% of binder and 0.5-30% of additional alumina, wherein the zeolite molecular sieve comprises a mesoporous-macroporous ZSM-5 molecular sieve.
2. The catalytic cracking catalyst of claim 1, wherein the mesoporous-macroporous ZSM-5 molecular sieve is prepared by using a rubber microemulsion as a template agent, and the pore diameter, the total pore volume and the total specific surface area of the ZSM-5 molecular sieve are respectively 2-100 nm and 0.20-0.60 m3/g、300～600m2/g。
3. The catalytic cracking catalyst of claim 2, wherein the ZSM-5 molecular sieve has a pore size of 2 to 90nm and a total specific surface area of 300 to 350m2/g、360～400m2(ii)/g or 410 to 450m2/g。
4. The catalytic cracking catalyst of claim 2, wherein the ZSM-5 molecular sieves have a pore size of 2 to 70 nm; the pore volume is 0.20-0.24 m3/g、0.25～0.30m3A/g or 0.31 to 0.35m3/g。
5. The catalytic cracking catalyst of claim 2, wherein the rubber microemulsion is a nano-sized rubber microemulsion.
6. The catalytic cracking catalyst of claim 2, wherein the synthesis method of the mesoporous-macroporous ZSM-5 molecular sieve comprises the following steps:
1) preparing a silicon source, an aluminum source, inorganic acid or inorganic base and deionized water into mixture gel, wherein the molar ratio of each component in terms of oxide is 1.0SiO2:0.00025～0.5Al2O3:10～80H2O, stirring and refluxing the mixture for 2-48 h at the reflux temperature of 60-100 ℃ in a container;
2) adding the rubber microemulsion into the gel refluxed in the step 1) according to the proportion that the ratio R of the dry basis weight of the rubber microemulsion to the silicon element weight in the silicon source is 0.5-50, crystallizing at 150-200 ℃ for 12-72 h, filtering and washing the synthesized product, drying at 80-140 ℃ for 2-12 h, and roasting at 500-600 ℃ for 4-10 h to obtain the mesoporous-macroporous ZSM-5 molecular sieve.
7. The catalytic cracking catalyst of claim 1, wherein the zeolite molecular sieve comprises Y-type zeolite and a mesoporous-macroporous ZSM-5 molecular sieve, wherein the mass ratio of the Y-type zeolite to the mesoporous-macroporous ZSM-5 molecular sieve is 70-95% of the Y-type zeolite and 5-30% of the mesoporous-macroporous ZSM-5 molecular sieve.
8. The catalytic cracking catalyst of claim 1, wherein the clay is selected from one or more of kaolin, halloysite, montmorillonite and sepiolite.
9. The catalytic cracking catalyst of claim 1, wherein the binder is selected from one or more of aluminum sol, silica sol and silicon-aluminum composite sol; the additional alumina is pseudo-boehmite.
10. A process for preparing a catalytic cracking catalyst according to any one of claims 1 to 9, characterized by comprising the steps of:
1) preparation of composite matrix slurry: uniformly mixing clay and deionized water, adding unmodified clay and deionized water under a stirring state, continuously adding an additional alumina component, stirring and reacting for 0.1-3 hours, adding a binder, and uniformly mixing to obtain composite matrix slurry;
2) preparing composite zeolite molecular sieve slurry: uniformly mixing the zeolite molecular sieve with deionized water, adding a phosphorus compound, and stirring for reaction for 0.5-2 hours to prepare composite molecular sieve slurry;
3) and uniformly mixing the composite matrix slurry and the composite zeolite molecular sieve slurry, and then spray-drying to obtain the catalytic cracking catalyst.
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