CN110422856A - Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR - Google Patents

Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR Download PDF

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Publication number
CN110422856A
CN110422856A CN201910603200.9A CN201910603200A CN110422856A CN 110422856 A CN110422856 A CN 110422856A CN 201910603200 A CN201910603200 A CN 201910603200A CN 110422856 A CN110422856 A CN 110422856A
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molecular sieve
cha
sial
aei
preparation
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时立辉
包立业
张鹏
陈士辉
王继华
李鹏
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Valiant Co Ltd
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Valiant Co Ltd
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Priority to PCT/CN2019/119648 priority patent/WO2021003947A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48

Abstract

The present invention relates to a kind of sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its in the application of SCR catalysis, it is mainly adjusted by each material material ratio, using hydrothermal synthesis method, and ion exchange technique well known in the art and roasting technology, crystallinity height is prepared, crystallite dimension is adjustable, the different sial type AEI/CHA coexisting molecular sieve of symbiosis ratio (non-silicoaluminophosphate type (SAPO) series), it is exchanged into load with certain density copper salt solution at a certain temperature, filtering, washing, catalyst is made after dry and after baking and compressing tablet process, it is installed in fixed bed reactors, at 200~600 DEG C of active temperature windows, with efficiently except NO is active (NO conversion ratio > 80%), at 250-450 DEG C, denitration activity (NO conversion Rate) it can reach 98% or more, at 258.4 DEG C up to 100%, which shows good activity in motor-vehicle tail-gas SCR catalysis.

Description

Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its SCR catalysis Using
Technical field
The present invention relates to a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst and its in SCR catalysis Using, specifically, be related in gel preparation course by be added the two kinds of structure directing agent R and R ' that matches into Row structure directing needs to be added when necessary sial type pure phase CHA type solid powder crystal seed, makes it in each spontaneous nucleation of crystallization process, By the assembling stacking of same or similar secondary structure unit (SBU), two kinds of bones of AEI and CHA are finally grown into while had Frame infrastructure product and product grains size, the adjustable method of symbiosis ratio.Then, pass through the technical offices such as ion exchange, roasting Reason prepares H-type molecular sieve, then Cu is supported on molecular sieve activated centre by ion exchange means, through drying, secondary roasting The processing such as burning, tabletting, is prepared into catalyst, the catalytic field applied to motor-vehicle tail-gas SCR.
Background technique
As motor vehicles are increasing, more NOXDischarge causes atmosphere pollution, ammine selectivity catalytic reduction technology (NH3- SCR) it is the NO being most widely used in the world at presentXRemoving sulfuldioxide, principle are with NH3As reducing agent, by NOXAlso It originally was harmless N2To reach discharge standard.The key of SCR technology is to develop the catalyst system of efficient stable, with adaline The particular surroundings that motor-car uses.
Americanized scholar Zones has synthesized a kind of new molecular sieve SSZ-13 by hydro-thermal method the 1980s, It is a kind of Si-Al molecular sieve of CHA topological structure, the crystalline structure with octatomic ring shape, pore size only has 0.38nm belongs to small pore molecular sieve, this design feature make it have good thermal stability, simultaneously because in skeleton AlO4 and The tetrahedral presence of SiO4 makes its skeleton have cationic exchangeability and acid adjustability, so that SSZ-13 be made to be provided with very well Catalytic performance, the catalytic cracking including hydrocarbon compound, be hydrocracked and alkene and aromatic hydrocarbons construction reaction.Later period is a large amount of Document report is prepared into Cu loaded catalyst for NH3- SCR react when, show catalytic activity it is high, selectivity it is good, Excellent heat stability, anti-poisoning capability are strong etc. and receive significant attention.US 4544538 makes public for the first time SSZ-13 molecular sieve A kind of synthetic method.The technology has used expensive N, and N, N- trimethyl -1- amantadine organic cation is as structure directing Agent synthesizes SSZ-13 molecular sieve.A kind of use benzyl trimethyl season is proposed in the application specification of United States Patent (USP) US60882010 Ammonium ion (BTMA+) partially replaces N, N, SSZ-13 molecule of the N- trimethyl -1- adamantamrnonium cation as structure directing agent The synthetic method of sieve.With bicyclic [2.2.1] heptane -2- methylene-N, N, N- trimethyl hydroxide in CN106927474B patent Ammonium replaces N, N, N- trimethyl -1- amantadine (TMA+) cation and benzyltrimethylammoncation cation as structure directing agent, The method for reducing SSZ-13 synthesis cost.Although the above patented method makes progress in cost control, obtained SSZ- 13 zeolite crystals are larger, it is difficult to meet the catalytic action of certain reactions.
Corma in 2012 etc. is reported with the SSZ-39 molecular sieve with CHA molecular sieve similar structures, is AEI topology The Si-Al molecular sieve of structure has the SCR catalytic activity more excellent than Cu-CHA molecular sieve after loaded Cu. CN104520548A patent also refers to all have in SCR using Cu-SSZ-39 prepared by distinct methods and structure directing agent Excellent catalytic activity, preferable hydrothermal stability.However, excellent catalytic activity caused by its more acid centre often because urging Agent carbon distribution and inactivate or the service life shortens, keep improving the service life of catalyst while good catalytic activity being always scientific research The tireless pursuit of personnel.
Document report is reacted in conjunction with a large amount of MTO, SAPO-34 (silicon phosphate aluminium profiles CHA structure) molecular sieve has stronger table Face acidity easily causes catalyst carbon deposition to inactivate, and SAPO-18 (silicon phosphate aluminium profiles AEI structure) has weaker surface acidity and keeps Longer catalytic life, and SAPO-34/18 coexisting molecular sieve has both the duct and acidity of two kinds of crystal phase structures, it is anti-for being catalyzed At once advantage is had more than single molecular sieve, it is single effectively to solve single molecular sieve bore diameter, and catalytic activity is low and catalytic life is short The problem of, realize performance complement.
In the recent period, the CN 109701621 A patent report preparation method of SSZ-13/SSZ-39 composite molecular sieve catalyst, And good performance is shown in terms of methanol converts hydrocarbon processed, hence it is evident that improve the yield of ethylene, propylene, isobutene, effectively Solve existing poor catalyst stability, the low problem of yield.But synthesis technology is relative complex in document, at least need two kinds and with Upper silicon source, and two systems is needed respectively to carry out pre- Crystallizing treatment, secondary crystallization is carried out after remixing, can just obtain target production Product.
In addition, the molecular sieve of little crystallite size has relatively large specific surface area, and relatively short is interior as catalyst Portion duct is conducive to the diffusion of reactants and products, can effectively inhibit excessively to be catalyzed, and reduces carbon distribution speed, this is also to extend The conventional means of catalyst life.
Summary of the invention,
An object of the present invention there is provided a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst, It is more simpler than existing report technical matters, it is easy to implement stable industrialization.
The second object of the present invention is to provide a kind of system for adjusting sial type AEI/CHA coexisting molecular sieve grain size Preparation Method makes product have longer service life or higher activity in catalytic applications.
The third object of the present invention is to provide a kind of preparation method for adjusting sial type AEI/CHA symbiosis ratio, makes product Symbiosis ratio can be adjusted according to the difference of catalytic applications demand direction, maximum plays each own advantage, realizes and lives in catalysis The regulation that property and service life balance therebetween, the application field related generally to herein is mainly motor-vehicle tail-gas catalytic treatment The application of process (NH3-SCR).
The technical scheme to solve the above technical problems is that a kind of system of AEI/CHA Intergrown molecular sieve catalyst Preparation Method mainly comprises the following steps:
1) synthetic method of AEI/CHA coexisting molecular sieve:
Including following starting material: first kind structure directing agent the R: the second class formation directed agents R ', alkali source, silicon source, silicon source And deionized water, specifically includes the following steps:
Each starting material, first kind structure directing agent the R: the second class formation directed agents are weighed according to following molar ratio of material examples R ': alkali source: silicon source: silicon source: deionized water is 3~16:0.15~4:18~40:35~100:1:500~2400, is added certain The crystal seed (the 0%~5.0% of gel gross mass) of quality.Wherein R and R ' is quaternary ammonium base (or quaternary ammonium salt)；The silicon source with SiO2Mole calculate, source of aluminium is with Al2O3Mole；The amount of seed with the 0% of gel gross mass~ 5.0% calculates；
Step (1), which mixes to alkali source and silicon source and portions of de-ionized water, to be sufficiently mixed uniformly；Step (2) is by A kind of structure directing agent R, silicon source are added in mixed system, stir 1 hour, and step (3) is by the second class formation directed agents R ', sial Type pure phase CHA type solid powder crystal seed and remaining deionized water sequentially add in above-mentioned mixed liquor, and stirring is equal to mixing Even obtained gel；Gel is transferred in crystallizing kettle by step (4), 6~120h of crystallization under the conditions of being warming up to 130~200 DEG C, is kept Crystallizing kettle speed of agitator is 60~240 revs/min；It is filtered, washed after the completion of step (5) crystallization, dries to obtain target cationic Type molecular sieve obtains molecular sieve dry powder after ion exchange technique and roasting technology processing.
2) preparation method of AEI/CHA Intergrown molecular sieve catalyst:
Including following starting material: deionized water, soluble copper salt (copper sulphate, copper nitrate, the inorganic sour solvable such as copper chloride Property mantoquita and copper formate, the organic acids such as copper acetate soluble copper salt), it is preferred that copper acetate, specifically includes the following steps:
Copper acetate, deionized water are mixed to dissolution by step (1) according to a certain percentage, and are filtered, and are removed solid Body impurity；The molecular sieve dry powder of above-mentioned preparation is added and is beaten into copper acetate solution by step (2), keeps 20~80 DEG C of water Under bath, 1~5h of exchange mashing；Step (3) slurry is filtered, washed, is dried, is roasted, and catalyst fines are obtained；Step (4) will Powder carries out tabletting, and is crushed, and screens the catalyst of 20~40 mesh；The above-mentioned catalysis of 1ml is added in fixed bed reactors in step (5) Agent is passed through motor-vehicle tail-gas simulation gas, carries out activity rating, detect Temperature Activity window and NO conversion ratio.
Detailed description of the invention
Fig. 1 is the XRD diagram of embodiment VZ-1 sample AEI/CHA coexisting molecular sieve；
Fig. 2 is the XRD diagram of embodiment VZ-2 sample AEI/CHA coexisting molecular sieve；
Fig. 3 is the XRD diagram of embodiment VZ-3 sample AEI/CHA coexisting molecular sieve；
Fig. 4 is the XRD diagram of embodiment VZ-4 sample AEI/CHA coexisting molecular sieve；
Fig. 5 is the XRD diagram of embodiment VZ-5 sample AEI/CHA coexisting molecular sieve.
Specific embodiment
The contents of the present invention are described in further detail with reference to embodiments；It is emphasized that: for ability For the those of ordinary skill in domain, it can be modified or changed according to the above description, and all these modifications and variations are all answered Belong to the protection scope of appended claims of the present invention.
Embodiment 1
It is stirred at room temperature under state, successively by 123.3g waterglass (SiO2Content is 28.0%, Na2O content be 9.0%), 25.1g silica solution (SiO2Content is 30%) to put into 160.0g deionized water, is stirred until homogeneous, 77.6g first is then added Class formation directed agents N, N- dimethyl -3,5- lupetidine and USY 13.8g, stirring are sufficiently mixed system, finally The second class formation of 43.1g directed agents TMAmOH aqueous solution and 18.0g deionized water is added, stirring is until form homogeneous gel；With The gel is transferred in 600ml crystallizing kettle afterwards, stirring is warming up to 170 DEG C of heat preservation crystallization 60h.After the completion of crystallization, it will mix The post-processings such as liquid is filtered, washs, drying, ion exchange, roasting obtain target product, are named as VZ-1.By XRD, The discovery of SEM characterization test, the target product VZ-1 that is prepared under this condition have found simultaneously there are AEI and CHA type diffraction maximum, Wherein CHA ratio is 80~85%, as shown in Figure 1, and shooting picture by SEM scanning electron microscope is crystallite dimension at 0.6 μm The cubic crystal form of left and right, proves from consistent crystal form pattern, structure, and gained sample is crystal phase symbiosis rather than mechanical mixture Phase.
Embodiment 2
It is stirred at room temperature under state, successively by 123.3g waterglass (SiO2Content is 28.0%, Na2O content be 9.0%), 25.1g silica solution (SiO2Content is 30%) to put into 160.0g deionized water, is stirred until homogeneous, 87.6g first is then added Class formation directed agents N, N- dimethyl -3,5- lupetidine and USY 13.8g, stirring are sufficiently mixed system, finally The second class formation of 23.6g directed agents TMAmOH aqueous solution and 40.0g deionized water is added, stirring is until form homogeneous gel；With The gel is transferred in 600ml crystallizing kettle afterwards, stirring is warming up to 145 DEG C of heat preservation crystallization 60h.After the completion of crystallization, it will mix The post-processings such as liquid is filtered, washs, drying, ion exchange, roasting obtain target product, are named as VZ-2.By XRD, The discovery of SEM characterization test, the target product VZ-2 being prepared under this condition, while finding that there are AEI and CHA type diffraction Peak, wherein CHA ratio 70%~75%, as shown in Fig. 2, and shooting picture by SEM scanning electron microscope is crystallite dimension 0.3 μm or so cubic crystal form.
Embodiment 3
It is stirred at room temperature under state, successively by 208.2g waterglass (SiO2Content is 28.0%, Na2O content be 9.0%), 15.1g silica solution (SiO2Content is 30%) to put into 110.0g deionized water, is stirred until homogeneous, 60.8g first is then added Class formation directed agents N, N- dimethyl -3,5- lupetidine and USY 13.8g improve speed of agitator to 600 revs/min Clock, stirring are sufficiently mixed system, and it is brilliant to be eventually adding 23.6g the second class formation directed agents TMAmOH aqueous solution, 4.6gSSZ-13 Kind and 25.0g deionized water, stirring is until form homogeneous gel；Then the gel is transferred in 600ml crystallizing kettle, stirring rises Temperature is to 145 DEG C of heat preservation crystallization 60h.After the completion of crystallization, mixed liquor is centrifuged, is washed, is dried, ion exchange, roasting etc. Post-processing obtains target product, is named as VZ-3.It finds by XRD, SEM characterization test, is prepared under this condition Target product VZ-3, while finding there are AEI and CHA type diffraction maximum, wherein CHA ratio 75%~80%, as shown in figure 3, and The class cubic that picture is crystallite dimension < 100nm, which is shot, by SEM scanning electron microscope assembles crystal form.
Embodiment 4
It is stirred at room temperature under state, successively by 123.3g waterglass (SiO2Content is 28.0%, Na2O content be 9.0%), 25.1g silica solution (SiO2Content is 30%) to put into 160.0g deionized water, is stirred until homogeneous, 81.2g first is then added Class formation directed agents N, N- dimethyl -3,5- lupetidine and USY 13.8g, stirring are sufficiently mixed system, finally The second class formation of 15.8g directed agents TMAmOH aqueous solution and 40.0g deionized water is added, stirring is until form homogeneous gel；With The gel is transferred in 600ml crystallizing kettle afterwards, stirring is warming up to 145 DEG C of heat preservation crystallization 60h.After the completion of crystallization, it will mix The post-processings such as liquid is filtered, washs, drying, ion exchange, roasting obtain target product, are named as VZ-4.By XRD, The discovery of SEM characterization test, the target product VZ-4 being prepared under this condition, while finding that there are AEI and CHA type diffraction Peak, wherein CHA ratio about 45-50%, as shown in figure 4, and shooting picture by SEM scanning electron microscope is crystallite dimension at 0.3 μm The class cube that the layer structure of left and right is piled into.
Embodiment 5
It is stirred at room temperature under state, successively by 123.3g waterglass (SiO2Content is 28.0%, Na2O content be 9.0%), 25.1g silica solution (SiO2Content is 30%) to put into 160.0g deionized water, is stirred until homogeneous, 84.8g first is then added Class formation directed agents N, N- dimethyl -3,5- lupetidine and USY 13.8g, stirring are sufficiently mixed system, finally The second class formation of 8.0g directed agents TMAmOH aqueous solution and 20.0g deionized water is added, stirring is until form homogeneous gel；Then The gel is transferred in 600ml crystallizing kettle, stirring is warming up to 145 DEG C of heat preservation crystallization 60h again.After the completion of crystallization, it will mix The post-processings such as liquid is filtered, washs, drying, ion exchange, roasting obtain target product, are named as VZ-5.By XRD, The discovery of SEM characterization test, the target product VZ-5 being prepared under this condition, while finding that there are AEI and CHA type diffraction Peak, wherein AEI ratio 70%~75%, as shown in figure 5, and shooting picture by SEM scanning electron microscope is more obvious stacking Layer structure crystal form.
Embodiment 6
Catalyst the preparation method is as follows:
VZ-1 zeolite product 20g is taken, is beaten after the copper acetate solution 40g of wt%=4% is added, is placed in 80 DEG C Sealing stirring 4 hours, finish in water-bath, filter to slurry and deionized water elutes, be dried and roast, preparation catalysis Agent original powder.The original powder is carried out the broken screening size of tabletting to be put into fixed bed reactors in the catalyst of 20~40 mesh, is tested Condition are as follows: 500ppm NO+500ppm NH3+5%O2+7%H2O+N2, GHSV=300000h-1,200~600 DEG C of test Denitration activity, evaluation results are shown in Table 1.
Embodiment 7~10
The molecular sieve VZ-2/3/4/5 prepared in above-described embodiment is taken, catalyst is prepared according to the method for embodiment 6 and goes forward side by side Row evaluation, the results are shown in Table 1.
Embodiment 11
The catalyst raw powder that VZ-1 preparation is used in embodiment 6 is carried out at 600 DEG C, hydrothermal aging 12 under 10% vapor Hour, then catalyst is prepared, activity rating is carried out, the results are shown in Table 1.
Embodiment 12
Pure phase CHA sial type SSZ-13 molecular sieve (100%CHA) is taken, prepare catalyst according to the method for applying example 6 and is carried out Evaluation, the results are shown in Table 1.
Embodiment 13
Pure phase AEI SSZ-39 molecular sieve (100%AEI) is taken, catalyst is prepared according to the method for applying example 6 and is evaluated, It the results are shown in Table 1.
Table 1
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst, it is characterised in that by the original of following molar ratio Material composition:
And it is made as follows:
Step (1), which mixes to the alkali source and silicon source and portions of de-ionized water, to be sufficiently mixed uniformly；
First kind structure directing agent R, silicon source are added in mixed system step (2), stir 1 hour；
For step (3) by the second class formation directed agents R ', sial type pure phase CHA type solid powder crystal seed, additional amount is the total matter of gel 0%~5.0% and remaining deionized water of amount sequentially add in above-mentioned mixed liquor, stir evenly obtained gel；
Gel is transferred in crystallizing kettle by step (4), 6~120h of crystallization under the conditions of being warming up to 130~200 DEG C, keeps crystallizing kettle Speed of agitator is 60~240 revs/min；Slurry is filtered, washed, dries to obtain target cationic type molecular sieve after the completion of crystallization, After ion exchange technique and roasting technology processing, molecular sieve dry powder is obtained；
Step (5) by molecular sieve dry powder be placed in certain density copper salt solution carry out ion exchange load, be filtered, washed, dry, After baking and tabletting break process are prepared into sial type AEI/CHA Intergrown molecular sieve catalyst.
2. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, wherein institute Stating first kind structure directing agent R is polycyclic quaternary ammonium base cations, is selected from: N, N- dimethyl -3,5- lupetidine, N, N- dimethyl -2- (2- ethoxy) piperidines, N, N- dimethyl -2- ethyl piperidine and 2,2,4,6,6- pentamethyl -2- azepine The one or any of several of bicyclooctane；The second class formation directed agents R ' is selected from: hydroxide N, N, N- trimethyl-outer ammonia Base norbornane ammonium (TMAmOH), TMAmX (X=Cl, Br), hydroxide N, N, N- trimethyl amantadine (TMAdOH), TMAdX One of (X=Cl, Br), hydroxide N- methyl -3- quinoline core alcohol, benzyltrimethylammonium hydroxide are any several.
3. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, the silicon Source is selected from: fumed silica, sodium form silica solution, ammonium type silica solution, waterglass, organosilicon and silicate.
4. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, the aluminium Y type (including USY) molecular sieve that source only selects the silica alumina ratio that can be used for turning brilliant different.
5. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, the alkali Source is selected from: the hydroxide of sodium, potassium, lithium, calcium etc. and the strong base-weak acid salt containing the above metallic element.
6. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, feature exist In: the sial type pure phase CHA type solid powder crystal seed is commercially available routine SSZ-13 molecular sieve.
7. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, feature exist In:
The process that is filtered, washed in the step (4) is to finish slurry in crystallization to collect stoste through filtration treatment, while being added and going Ion water washing filter cake, until the pH of filtrate is 7-10；
The drying course of the step (4) is to carry out drying and processing to filter cake at 80~200 DEG C；
The ion exchange process of the step (4) is carried out using ammonium salt solution, and ammonium salt solution is selected from ammonium chloride, ammonium nitrate, sulfuric acid Ammonium and ammonium bicarbonate aqueous solution；
The roasting process of the step (4) is roasted at 500~700 DEG C, for removing structure directing agent.
8. a kind of preparation method of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, feature exist In:
The mantoquita of the step (5) is selected from copper sulphate, copper nitrate, the inorganic acids such as copper chloride soluble copper salt and copper formate, second The organic acids soluble copper salt such as sour copper；
The ion exchange loading process of the step (5) is carried out at 20~80 DEG C；
The process that is filtered, washed of the step (5) is slurry through filtration treatment, while deionized water washing filter cake is added, until filter The pH of liquid is 5-7；
The drying course of the step (5) is dried at 80~200 DEG C；
The after baking process of the step (5) is activated at 500~700 DEG C；
The tabletting break process of the step (5), which refers to, carries out tabletting to fine catalyst in 0.2~5MPa, is crushed, screening Catalyst of the particle size in 20~40 mesh.
9. a kind of application of sial type AEI/CHA Intergrown molecular sieve catalyst according to claim 1, is that it is applied to In SCR catalysis.
CN201910603200.9A 2019-07-05 2019-07-05 Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR Pending CN110422856A (en)

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PCT/CN2019/119648 WO2021003947A1 (en) 2019-07-05 2019-11-20 Preparation method for silicon-aluminum aei/cha symbiotic molecular sieve catalyst and use thereof in scr catalysis

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN110961144A (en) * 2019-12-14 2020-04-07 中触媒新材料股份有限公司 Symbiotic composite molecular sieve with CHA/LEV topological structure, preparation method thereof and SCR application thereof
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