CN101767034B - Preparation method of catalysis material containing ZSM-5/Y type composite molecular sieve - Google Patents

Preparation method of catalysis material containing ZSM-5/Y type composite molecular sieve Download PDF

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CN101767034B
CN101767034B CN 200810247500 CN200810247500A CN101767034B CN 101767034 B CN101767034 B CN 101767034B CN 200810247500 CN200810247500 CN 200810247500 CN 200810247500 A CN200810247500 A CN 200810247500A CN 101767034 B CN101767034 B CN 101767034B
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catalysis material
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molecular sieve
crystallization
acid
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CN101767034A (en
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吕庐峰
何金龙
周健
张占柱
李学锋
田志鸿
刘亚林
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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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Abstract

The invention discloses a preparation method of a catalysis material containing ZSM-5/Y type composite molecular sieve, which comprises the following steps: (1) mixing the solid waste with silicon source and aluminum source, then pulping to ensure the mixture to be stabilized and uniform and the components of the mixture as follows: 2.5-8wt% of Na2O, 25-65wt% of SiO2 and 18-55wt% of Al2O3; (2) drying the material obtained in step (1), then roasting at the temperature of 600-1,100 DEG C for 0.5-4hours; (3) exchanging ions of the material obtained in step (2) with sodium salt, acid or ammonium salt to remove harmful ions contained in waste residue; and (4) adding silicon source, acid and guiding agent into materials of step (3), crystallizing at the temperature of 90-120 DEG C for 8-48 hours to prepare the catalysis material containing the Y type molecular sieve; and (5) cooling the catalysis material containing the Y type molecular sieve prepared in step (3), then adding template agent and regulating the PH value of between 9.5 and 11.5, crystallizing the mixture at the temperature of 140-180 DEG C for 8-36 hours to obtain the catalysis material containing the ZSM-5/Y type composite molecular sieve. Compared with the prior art, the method provided by the invention can effectively eliminates the adverse effect of harmful metallic ions in waste residue, thereby improving the catalysis property of catalysis materials.

Description

A kind of preparation method who contains ZSM-5/Y type composite molecular screen catalysis material
Technical field
The present invention relates to the preparation method of molecular sieve, more particularly, relating to a kind of is raw material with the catalyst plant waste residue, and preparation contains the method for ZSM-5 and Y type composite molecular screen catalysis material.
Background technology
Y zeolite is a kind of silica-rich zeolite; It is made up of the cage structure of big subglobular, and its free diameter is 1.3nm, and cage links to each other through twelve-ring with cage; Forming the aperture that connects each other is the opening pore canal system of 0.74nm, and general gas molecule can both get into wherein.The Y zeolite silica alumina ratio is higher than X type and faujasite, has good heat endurance and hydrothermal stability, is the important activity component of present FCC catalyst.The ZSM-5 zeolite is that a kind of shape with unique three-dimensional channel structure and acid strength distribution is selected zeolite, and most apertures have the characteristic of high silica alumina ratio and oleophilic drainage about 0.55nm, have the high characteristics of heat endurance and catalytic activity simultaneously.It can optionally carry out cracking to some straight chains in the catalytically cracked gasoline cut and short-chain branch alkane in its duct, generate the alkene of side chain, has increased the yield of low-carbon alkene.Therefore, in the catalytic cracking reaction process, often need Y zeolite and ZSM-5 molecular sieve synergy in the catalyst, obtain higher octane number and yield of light olefins.
At petroleum refining catalyst, particularly in the production process of catalytic cracking catalyst, mainly comprise synthetic and the modification and the Preparation of catalysts of molecular screen material, can produce a large amount of industrial solid waste residues.These solid slags mainly contain SiO 2, Al 2O 3, RE 2O 3, Na 2O and Fe 2O 3Deng, and contain a spot of Cl -, SO 4 2-, F -, Ca 2+, Mg 2+, P, As, Pb etc.Learn through XRD analysis in addition, also contain part ZSM-5 and Y zeolite in the waste residue.According to investigation, most catalyst plant adopts the method for landfill to handle these waste residues.Like this, not only environment having been caused pollution, also is the serious waste to resource.Thereby rationally dispose these waste residues and not only can practice thrift the manufacturing cost that a large amount of raw materials reduces catalyst, reduce the pollution of catalyst plant simultaneously surrounding environment.
Have some to administer and utilization again about industrial residue in the prior art, as adopting physical methods such as shaping, briquetting, CN1051523A discloses a kind of method that waste residue is prepared as construction material and filler.From waste residue, extract the technology of useful component for another example, disclose a kind of method of from the waste residue that contains rare earth, extracting rare earth such as CN1044635A.Can not be all effective but extract useful component to various components, can not catapepsis fall waste residue, even increase the amount of waste residue owing to processing procedure.
The waste residue, the liquid waste disposal technique that relate to silicon, aluminium and be main component mainly contain: the mother liquor recycling of (1) synthetic zeolite; Propose to synthesize the mother liquor heating that is produced among the JP6107411 and remove particle; With being settled out silicon with waste liquid in the acid, and mix the back heating, use Na again with mother liquor 2OH and H 2O regulates the composition proportioning makes it become waterglass, can be used further to synthetic zeolite.(2) with the inorganic of silicon-aluminum containing or debirs fusion and be added to boil in alkali such as the NaOH of equivalent at least and be used to prepare zeolite, waste residue is SiO preferably 2/ Al 2O 3=2～4 sludge or its incineration ash.Disclosed method will be less than 300 microns sial waste material with about 20% H among the EP451112 2SO 4Solvent and solute weight ratio 1.3～6 and 150～230 ℃ of following processing 0.25～0.75 hour; Be cooled to 60～150 ℃ then; Use alkali such as naoh treatment again, and in every liter, add 0.2～0.5 gram flocculant, time obtain silicon/aluminium glue body in PH=3.5～4.5; A ℃ following reaction obtains zeolite in pH=8～13 and 60～200 for hydro-oxidation sodium and water, and zeolite type depends on the mixture composition.(3) the JP5514412 disclosed method is with silicate and naoh treatment aluminium oxide sludge, adds flocculant again and adjust the basicity crystallization to go out zeolite, and characteristics are earlier with acid or alkali treatment and add flocculant.Disclosed method is dissolved the silica formation alkali silicate that contains useless cigarette ash with alkali hydroxide soln down at 60～110 ℃ among the USP4226837; Separate to be regardless of with active carbon or oxidant and separate component, at room temperature with the alkali metal aluminate reaction and stir 8～48 hours crystallization down at 70～100 ℃ and obtain the Y zeolite.
CN1299778A discloses a kind of A type prepare zeolite method; The catalyst plant waste residue of siliceous and/or aluminium is added the water making beating; Add or do not add other silicon source; To wherein adding aluminate and mixing, the basicity that feeds intake with acid aluminium salt, acid or alkali adjustment again makes the mole composition of last gained reactant mixture meet (2.0～4.0) Na then 2O: Al 2O 3: (1.8～3.5) SiO 2: (80～200) H 2The proportioning of O, the wherein Al in the waste residue 2O 3Account for the total Al of mixed material 2O 30～45 heavy % of amount, the SiO in the waste residue 2Account for the total SiO of mixed material 25～100 heavy % of amount; Then the gained reactant mixture is obtained A type zeolite by the conventional method hydrothermal crystallizing.
CN1406868A discloses the low silica-alumina ratio X prepare zeolite method of a kind of lattice constant more than or equal to 2.50 nanometers.Comprise: according to the chemical composition of waste residue and/or mother liquor; In catalyst plant waste residue and/or mother liquor; Add NaOH and potassium hydroxide mixed base and waterglass and/or aluminium source according to required charge ratio, and mix, make total mole of composition of gained reactant mixture meet (4.0～6.0) Na 2O: (1.0～2.5) K 2O: Al 2O 3: (1.0～3.0) SiO 2: (50～250) H 2The proportioning of O, the wherein Al in waste residue and the mother liquor 2O 3Account for the total Al of mixed material 2O 30～50 heavy % of amount, the SiO in waste residue and the mother liquor 2Account for the total SiO of mixed material 215～100 heavy % of amount, the alkali in waste residue and the mother liquor accounts for 0～45% of total alkali content.20～50 ℃ of following ageings 1～4 day, preferably 25～45 ℃ of following ageings were 2～3 days with the gained mixture; With the gel after the gained ageing by conventional method 50～90 ℃ of following hydrothermal crystallizings 10～40 hours, preferably 55～75 ℃ of following hydrothermal crystallizings are 10～25 hours.Obtain the low silica-alumina ratio X zeolite of a kind of lattice constant more than or equal to 2.50 nanometers.
CN1245140A discloses a kind of method for preparing y-type zeolite, and this method is made up of the following step: directed agents is prepared according to the method for preparing directed agents that is adopted in the conventional NaY zeolite preparation method in (1); (2) with this directed agents and waterglass, contain SiO 2And Al 2O 3Waste residue, aluminium salt and/or sodium metaaluminate mix, and the basicity of adjustment mixture is formed the mole of gained reactant mixture and is met (1.5～4.5) Na 2O: Al 2O 3: (5.5～12) SiO 2: (I00～300) H 2The proportioning of O, the wherein Al in the directed agents 2O 3Account for the total Al of said mixture 2O 32～8%, preferably 3.5～6.0% of amount; Al in the waste residue 2O 3Account for the total Al of said mixture 2O 30～60%, preferably 0～55% of amount; SiO2 in the waste residue accounts for the total SiO of said mixture 215～50%, preferably 20～40% of amount; Na wherein 2O represents the basicity of mixture, and it does not comprise the part that is neutralized by acid; (3) with (2) gained mixture by the conventional method hydrothermal crystallizing and reclaim product.
CN1362366A also discloses a kind of small cell Y type prepare zeolite method, it is characterized in that this method uses the catalyst plant waste residue to go out parent NaY zeolite as feedstock production; This NaY zeolite is taken off sodium according to conventional method handle the Na that makes zeolite 2O content is less than 6 weight %; Gained is taken off zeolite behind the sodium, and to make the structure cell of zeolite be contracted to lattice constant according to conventional method be 2.440～2.463nm.Adopt this method can under the prerequisite of identical preparation severity, obtain the littler product of structure cell, perhaps reduce the severity of preparation for the product that obtains identical unit cell dimension.
CN1299857A discloses a kind of preparation method of catalyst for cracking petroleum hydrocarbons; This method comprises: with solid content is 10～70 weight %; The catalyst plant waste residue of the siliceous and/or aluminium of preferred 15～50 weight %; Join in the Preparation of Catalyst slurries that contain molecular sieve and carrier according to the preparation of the method for prior art, with replacement a part of carrier wherein; After fully mixing, the gained slurry mixture is pressed the conventional method spray-drying; In the end in the gained slurry mixture, the addition of said waste residue is counted 5～25 weight % of whole catalyst butt gross weight by butt weight, is preferably 10～20 weight %; The addition of said molecular sieve is counted 10～50 weight % of whole catalyst butt gross weight by butt weight, is preferably 15～40 weight %; All the other are the addition of said carrier; The solid content of last gained slurries is confirmed according to prior art, is generally 15～50 weight %.When said carrier was full synthesis carrier, this carrier had adhesive property (promptly can not add other binding agent); When said carrier is semi-synthetic carrier; Said carrier is for example for example boehmite, aluminium colloidal sol, the mixture of Ludox of sour peptization of kaolin, imvite, dust trachelospermum jasminoide or sepiolite and binding agent of natural clay; Wherein the addition of binding agent is counted 10～35 weight % of whole catalyst butt gross weight by butt weight, is preferably 15～25 weight %.Adopting said method can prepare a kind of catalyst for cracking petroleum hydrocarbons.These waste residues are carried out rational modification handle, utilize the ZSM-5 that contains in the waste residue and Y zeolite, can synthesize and contain ZSM-5 and Y type composite molecular screen catalysis material as crystal seed.
In the above prior art with the method for catalyst waste slag as the filler of raw material and the catalyst carrier of the dissimilar molecular sieves of preparation; Though the utilization of catalyst waste slag is rationalized more, can't solve since in the catalyst waste slag the more harmful substance that contains (like F -, Ca 2+, Mg 2+, P, As, Pb etc.), thereby influence the performance of molecular sieve or catalyst.
Summary of the invention
It is the method that the primary raw material preparation contains ZSM-5 and Y type composite molecular screen catalysis material that the present invention provides a kind of solid slag with catalyst plant.
Method provided by the invention may further comprise the steps:
(1) solid slag with catalyst plant mixes making beating with silicon source, aluminium source, makes its stable uniform, and it is consisted of: the Na that mainly contains 2.5～8wt% 2O, the SiO of 25～65wt% 2, the Al of 18～55wt% 2O 3
(2) with the dry materials that obtains in the step (1), 600～1100 ℃ of roastings 0.5～4 hour;
(3) material in the step (2) and sodium salt, acid or ammonium salt are carried out ion-exchange, to remove the harmful ion that contains in the waste residue;
(4) material in the step (3) is added silicon source, acid and directed agents,, prepare the catalysis material that contains Y zeolite 90～120 ℃ of crystallization 8～48 hours;
(5) after preparing the catalysis material cooling that contains Y zeolite in the step (3), add template again and adjust its pH value between 9.5～11.5; Continuation obtains containing the catalysis material of ZSM-5 and Y type composite molecular screen 140～180 ℃ of following crystallization 8～36 hours.
In the method provided by the invention, except that sodium oxide molybdena, silica and aluminium oxide, also contain the element such as rare earth and chlorine, sulphur of surplus in the composition of the mixture that obtains in the described step (1).The Na that preferably contains 4～6wt% 2O, the SiO of 35～60wt% 2, the Al of 25～48wt% 2O 3
In the method provided by the invention, the described silicon source in the step (1) is Ludox, waterglass; Described aluminium source is one or more in kaolin, aluminium oxide, the aluminium colloidal sol, and described acid is hydrochloric acid and/or sulfuric acid.
In the method provided by the invention, the sodium salt described in the step (3) is one or more in sodium chloride, sodium oxide molybdena and the sodium sulphate, and described ammonium salt is ammonium chloride and/or ammonium sulfate.
In the method provided by the invention, the directed agents described in the step (4) is a general directed agents commonly used during Y zeolite synthesizes, and for example, its proportioning is 15.3Na 2O: Al 2O 3: 10SiO 2: 223H 2O.
In the method provided by the invention, the template described in the step (5) is one or more in tetraethyl ammonium hydroxide, tetraethyl hydrogen bromine ammonium, TPAOH and the 4-propyl bromide, preferred tetraethyl hydrogen bromine ammonium and/or 4-propyl bromide.
In the method provided by the invention, the crystallization condition described in the step (4) is preferably 95～110 ℃ of crystallization 18～36 hours.Crystallization condition described in the step (5) is preferably 145～160 ℃ of crystallization 12～24 hours.
In the method that provides among the present invention, related mixing apparatus can be batch-mixed equipment, continous way mixing apparatus, as long as the purpose that reaches pulp, mixes, the present invention does not receive the restriction of the mixing apparatus that uses.
In the method provided by the invention, related firing equipment can be baking oven, Muffle furnace, tube furnace or other firing equipment, as long as can reach heating-up temperature and keep time enough, the present invention does not receive the restriction of institute's use firing equipment.
In the method provided by the invention, related making beating filter plant can be the still formula beating equipment or the miscellaneous equipment of any routine, any type of filter plant, and the present invention does not receive the restriction of the equipment that uses.
Compared with prior art, method provided by the invention has the following advantages:
Compare with recycling the method that catalyst waste slag prepares catalyst in the prior art, method provided by the invention is reasonable processing and utilizing waste residue not only, helps environmental protection, thereby practices thrift a large amount of raw material reduction catalyst manufacturing costs.And in preparation process, molecular sieve is mainly concentrated the outer surface that is grown in particle, and particle is bigger, and the material that can significantly reduce in washing, the filter element runs damage, reduces production costs, and improves operating environment.
In addition, the molecular sieve of method preparation provided by the invention is mainly concentrated the outer surface that is grown in particle, has increased the chance that contacts with the external world, has improved the effective rate of utilization of molecular sieve greatly.Especially method provided by the invention adopts the processing that earlier catalyst waste slag is homogenized and removes harmful ion; Carry out the synthetic of molecular sieve according to the characteristics of catalyst waste slag again; Thereby effectively eliminate the harmful effect of harmful metal ion in the waste residue, improved the catalytic performance that contains Y type and ZSM-5 composite molecular screen catalysis material.Method provided by the invention obtains contains ZSM-5 and Y type composite molecular screen catalysis material can directly use as catalyst after modification is handled.
The specific embodiment
Following embodiment will further explain method provided by the invention, but therefore not limit the present invention.
FA: the solid content of waste residue FA is 21.25wt%, and the percentage composition of butt weight is Na 2O is 4.9wt%, and MgO is 1.6wt%, SiO 2Be 29.1wt%, Al 2O 3Be 44.1wt%, Re 2O 3Be 2.8wt%, SO 4 2-Be 14.1wt%, Fe 2O 3Be 0.62wt%, Cl -Be 0.95wt%;
FA1: get 10 kilograms in FA waste residue, 2 kilograms of deionized waters, 0.75 kilogram of mixing making beating of waterglass, and above-mentioned slurries spray-drying is obtained solid slag FA1.
FA2: waste residue FA1 800 ℃ of following roastings 2 hours, is obtained waste residue FA2, and the solid content of FA2 is 96.73wt%, and the percentage composition of butt weight is: Na 2O is 3.5wt%, and MgO is 1.8wt%, SiO 2Be 36.0wt%, Al 2O 3Be 46.5wt%, Re 2O 3Be 2.1wt%, SO 3Be 6.6wt%, Fe 2O 3Be 0.54wt%, CaO is 0.93wt%;
FA3: the sodium chloride of 2 kilograms of FA2 and 0.2 kilogram is joined in 20 kilograms of deionized waters, stirred 0.5 hour down at 70 ℃, filter then, wash, drying, obtain waste residue FA3, the solid content of FA3 is 92.58wt%, and the percentage composition of butt weight is Na 2O is 5.8wt%, and CaO is 0.53wt%, and MgO is 0.3wt%, SiO 2Be 37.5wt%, Al 2O 3Be 46.3wt%, Re 2O 3Be 0.8wt%, SO 3Be 4.6wt%, Fe 2O 3Be 0.52wt%, Cl -Be 1.55wt%.
The abrasion index of catalyst sample and micro-activity adopt " petrochemical industry analytical method (RIPP test method) " (Yang Cuiding, Gu Kanying volume, 1990, Science Press) among the embodiment.
Embodiment 1
To hang down alkali sodium metaaluminate (Al 2O 3: 11.3wt%, Na 2O:15.8wt%) 90 grams, liquid caustic soda (Al 2O 3: 11.3wt%, Na 2O:15.8wt%) 250 grams and waterglass (SiO 2: 28.4wt%, Na 2O:8.9wt%) 200 grams mix the preparation directed agents, and subsequent use at 40 ℃ times aging 4 hours.In beaker, add deionized water 1150 grams and stirring, add above-mentioned directed agents 300 grams again, add waterglass 700 grams then, add catalyst waste slag FA3 at last, 300 grams.Stir and transfer to after 10 minutes in the airtight stainless steel cauldron 100 ℃ of following crystallization 24 hours.Crystallization product is taken out, add waterglass 280 grams, tetraethyl ammonium hydroxide 35 grams after cooling again, it is 10.5 that dilute sulfuric acid 165 grams are regulated the pH values, stirs, and material is transferred in the airtight stainless steel cauldron 160 ℃ of following crystallization 24 hours again.With product filtration, washing, drying, recording the relative crystallinity that contains Y zeolite in the product is 36%, and the relative crystallinity of ZSM-5 molecular sieve is 23%.
Embodiment 2
In beaker, add deionized water 1800 grams and stirring, adding restrains with embodiment 1 identical directed agents 280 again, adds waterglass 700 grams then, adds catalyst waste slag FA1 at last, 350 grams.Stir and transfer to after 10 minutes in the airtight stainless steel cauldron 90 ℃ of following crystallization 24 hours.Crystallization product is taken out; Add waterglass 350 grams, tetraethyl ammonium hydroxide 32 grams after cooling again; It is 10.5 that dilute sulfuric acid 208 gram is regulated the pH values, stirs, and material is transferred in the airtight stainless steel cauldron 170 ℃ of following crystallization 24 hours product filtration, washing, drying again; Recording the relative crystallinity that contains Y zeolite in the product is 19%, and the relative crystallinity of ZSM-5 molecular sieve is 25%.
Embodiment 3
In beaker, add deionized water 2000 grams and stirring, adding restrains with embodiment 1 identical directed agents 320 again, adds waterglass 800 grams then, adds catalyst waste slag FA3 at last, 350 grams.Stir and transfer to after 10 minutes in the airtight stainless steel cauldron 100 ℃ of following crystallization 24 hours.Crystallization product is taken out; Add waterglass 320 grams, tetraethylammonium bromide 43 grams after cooling again; It is 10.5 that dilute sulfuric acid 186 gram is regulated the pH values, stirs, and material is transferred in the airtight stainless steel cauldron 170 ℃ of following crystallization 24 hours product filtration, washing, drying again; Recording the relative crystallinity that contains Y zeolite in the product is 24%, and the relative crystallinity of ZSM-5 molecular sieve is 17%.

Claims (8)

1. preparation method who contains ZSM-5/Y type composite molecular screen catalysis material is characterized in that may further comprise the steps:
(1) solid slag with catalyst plant mixes making beating with silicon source, aluminium source, makes its stable uniform, and it is consisted of: the Na that mainly contains 2.5～8wt% 2O, the SiO of 25～65wt% 2, the Al of 18～55wt% 2O 3
(2) with the dry materials that obtains in the step (1), 600～1100 ℃ of roastings 0.5～4 hour;
(3) material in the step (2) and sodium salt, acid or ammonium salt are carried out ion-exchange, to remove the harmful ion that contains in the waste residue;
(4) material in the step (3) is added silicon source, acid and directed agents,, prepare the catalysis material that contains Y zeolite 90～120 ℃ of crystallization 8～48 hours;
(5) after preparing the catalysis material cooling that contains Y zeolite in the step (4), add template again and adjust its pH value between 9.5～11.5; Continuation obtains containing the catalysis material of ZSM-5 and Y type composite molecular screen 140～180 ℃ of following crystallization 8～36 hours.
2. according to the method for claim 1, the mixture that it is characterized in that obtaining in the step (1) consist of the Na that mainly contains 4～6wt% 2O, the SiO of 35～60wt% 2, the Al of 25～48wt% 2O 3
3. according to the method for claim 1, it is characterized in that the silicon source in the described step (1) is Ludox and/or waterglass; Described aluminium source is one or more in kaolin, aluminium oxide, the aluminium colloidal sol, and described acid is hydrochloric acid and/or sulfuric acid.
4. according to the method for claim 1, it is characterized in that the sodium salt described in the step (3) is sodium chloride or sodium sulphate, described ammonium salt is ammonium chloride and/or ammonium sulfate.
5. according to the method for claim 1, it is characterized in that template in the step (5) is one or more in tetraethyl ammonium hydroxide, TPAOH and the 4-propyl bromide.
6. according to the method for claim 5, it is characterized in that the template in the step (5) is a 4-propyl bromide.
7. according to the method for claim 1, it is characterized in that the crystallization condition described in the step (4) is for 95～110 ℃ of crystallization 18～36 hours.
8. according to the method for claim 1, it is characterized in that the crystallization condition described in the step (5) is for 145～160 ℃ of crystallization 12～24 hours.
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CN102372553B (en) * 2010-08-23 2013-10-16 中国石油化工股份有限公司 Method for producing olefin by catalytically cracking
CN102371175B (en) * 2010-08-23 2013-05-08 中国石油化工股份有限公司 Preparation method for adhesive-free ZSM-5/ mordenite fluidized bed catalyst
CN102442686B (en) * 2010-09-30 2013-09-04 中国石油化工股份有限公司 Preparation method of ZSM-5 molecular sieve
CN103894076B (en) * 2012-12-28 2018-04-17 中国科学院上海高等研究院 The method that ion exchange prepares high-performance molecular screen membrane is carried out in the molten state
CN103406144B (en) * 2013-08-27 2014-12-10 威海戥同测试设备有限公司 Oil solution water/oil-removal slow-release catalyst, and preparation method and application thereof
CN104591218B (en) * 2013-11-04 2017-01-11 中国石油化工股份有限公司 Y and ZSM-35 composite molecular sieve and synthesizing method thereof
CN105293519A (en) * 2015-11-20 2016-02-03 河南大学 Synthesis method of ZSM-5/Y composite molecular sieve without using template
CN105621441B (en) * 2016-02-05 2019-01-01 青岛惠城环保科技股份有限公司 A kind of phosphorous ZSM-5/Y composite molecular sieves preparation method
CN106824263B (en) * 2017-01-20 2019-07-09 南华大学 A kind of preparation method of composite molecular screen and application in synthesis 3- picoline
CN112570003B (en) * 2020-12-21 2022-10-21 湖南长科诚享石化科技有限公司 Catalytic cracking catalyst and preparation method thereof

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