CN108584975A - A kind of porous grade AEI molecular sieves and its preparation method and application - Google Patents
A kind of porous grade AEI molecular sieves and its preparation method and application Download PDFInfo
- Publication number
- CN108584975A CN108584975A CN201810477584.XA CN201810477584A CN108584975A CN 108584975 A CN108584975 A CN 108584975A CN 201810477584 A CN201810477584 A CN 201810477584A CN 108584975 A CN108584975 A CN 108584975A
- Authority
- CN
- China
- Prior art keywords
- molecular sieves
- porous
- aei molecular
- aei
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
-
- 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
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
Abstract
The invention discloses a kind of multi-stage porous AEI molecular sieves and its preparation method and application.Using silicon source, FAU types Si-Al zeolite as silicon source, alkali source, Alkylpiperidine class organic formwork agent and initial feed that deionized water is AEI Zeolite synthesis, a certain amount of organosilan is added into above-mentioned initial feed, is carried out by way of dynamic crystallization.Product after crystallization is filtered, washed, dries and the processes such as high-temperature roasting removed template method, can obtain the highly crystallized porous grade AEI molecular sieves with microporous mesoporous structure.The AEI molecular sieves of this porous grade can overcome the diffusion caused by single micropore canals to limit this defect, it can effectively shorten the diffusion path of reactants and products over a molecular sieve, diffusional resistance is reduced, is with a wide range of applications in fields such as petrochemical industry, coal chemical industry and fine chemistry industries.
Description
Technical field
The present invention relates to a kind of porous grade AEI molecular sieves and its preparation method and application, have more particularly to one kind micro-
The preparation method and application of the porous grade AEI molecular sieves of hole-meso-hole structure.
Background technology
AEI molecular sieves are a kind of micro porous molecular sieve with three-dimensional open-framework being made of octatomic ring hole window, aperture ruler
Very little is 0.38 × 0.38nm, and this unique pore passage structure so that AEI molecular sieves are detached in catalysis and gas absorption in recent years
Field is with a wide range of applications.Although smaller pore passage structure is conducive to the progress of shape selective catalysis in AEI molecular sieves,
Some are related in the reaction of macromolecular participation, these smaller ducts then can limited reactions object and product molecule in micropore
Catalytic active center on diffusion, so as to cause the generation of carbon distribution, and then influence the catalytic performance and service life of molecular sieve.
Therefore, how improving the diffusion of guest molecule in AEI molecular sieves will be heat that AEI molecular sieve researchers will pay close attention to from now on
Point.
In recent years, multistage porous molecular sieve is due to having both the duct advantage of mesoporous material and the highly acid and Gao Shui of micro-pore zeolite
The advantages such as thermal stability so as to cause people extensive concern.Organosilan, high molecular polymer are introduced in the synthesis process
It is the porous grade molecular sieve of synthesis a kind of commonly method that equal Jie, which see template,.For example, patent CN201310019315 discloses one
Organosilan is grafted onto the method that porous grade ZSM-5 molecular sieve is synthesized on zeolite seed crystal by kind, overcomes common cationic surface
Unmatched problem between activating agent and zeolite template.(Journal of Catalysis, 2008,254 (2) such as Ryoo:296-
303) silane coupling agent is introduced to the synthetic system of molecular sieve, the mesoporous micellar structure being self-assembly of by hydrophobic Long carbon chain
Synthesising mesoporous ZSM-5 zeolite.Patent CN201010297898 disclose it is a kind of organosilan is added directly into Molecular sieve raw material,
Organosilan is grafted onto on ZSM-5 molecular sieve under conditions of condensing reflux, being then made by roasting has micropore-mesopore
The method of molecular sieve.Patent 201310117945 generates micropore canals by using conventional template agent tetraethyl ammonium hydroxide, then
Mesoporous mode, which is generated, by addition silane coupling agent obtains multi-stage porous β zeolites.Report about multi-stage porous Zeolite synthesis at present
Road focuses mostly on ZSM-5 and beta-molecular sieve, and the synthesis about multi-stage porous AEI molecular sieves has not been reported.
Invention content
It is an object of the invention to overcome many caused by single micropore canals in the AEI molecular sieves of prior art preparation ask
Topic, provides a kind of preparation method of the multi-stage porous AEI molecular sieves with micropore-mesopore structure.
Another object of the present invention is to provide a kind of porous grade AEI molecular sieve catalysts.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of preparation method of porous grade AEI molecular sieves, includes the following steps：By silicon source, silicon source, alkali source, organic formwork
Agent OSDA and deionized water H2O be uniformly mixed forms colloidal sol, organosilan is then added, at 20~80 DEG C constant temperature stirring 30~
It is transferred to after 120min in hydrothermal synthesis kettle, the dynamic crystallization 3~10 days at 20~60r/min, 140~200 DEG C；Divide after crystallization
Separate out solid product, solid product is washed, dry 12~48h at 100~130 DEG C, at 400~600 DEG C after 3~10h of roasting,
It can be obtained the AEI molecular sieves of porous grade；
Silicon source is with SiO2It calculates, silicon source is with Al2O3It calculates, alkali source is with Na2O calculating, organic formwork agent OSDA and deionized water
H2The molar ratio of O is Na2O：SiO2：Al2O3：OSDA：H2O=0.1~0.5：1.0：0.003~0.08：0.05~0.5：10~
50；The molal quantity of silicon is the 1~5% of silicon source molal quantity in organosilan.
In above-mentioned technical proposal, the silicon source comes from the Si-Al zeolite with FAU configurations；Described has FAU structures
The Si-Al zeolite of type, including X zeolites and Y zeolites.
In above-mentioned technical proposal, the silicon source comes from Si-Al zeolite and/or other silicon sources with FAU configurations；Its
His silicon source, come from waterglass, Ludox, white carbon, ethyl orthosilicate, solid silicone any one, two kinds or more
The mixture formed after being mixed with arbitrary proportion；The Si-Al zeolite with FAU configurations, including X zeolites and Y zeolites.
In above-mentioned technical proposal, the alkali source, any one or two kinds in NaOH, KOH are mixed with arbitrary proportion
Mixture made of conjunction.
In above-mentioned technical proposal, the organic formwork agent is pyrrolidin, including 1,1- dimethyl -3,5-
Lupetidine, 1,1- dimethyl-lupetidine, 1,1- diethyl -3,5- lupetidines, 1,1- diethyls
Base-lupetidine, 1- ethyl -1- methyl -3,5- lupetidines, 1- ethyl -1- methyl -2,6- dimethyl piperazines
Pyridine, 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidines, 1,1,3,5- tetramethyls -
4- oxo-piperidines, 1- hydroxyl -1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1- dimethyl -4,4- dipropoxies piperidines, 3,
5- dimethoxy -1,1- lupetidines, 3,5- dihydroxy -1,1- lupetidines, dimethyl -3 4- ethyl -1,1-,
5- dioxopiperidines, 1- ethyl -1- methyl -2,2,6,6- tetramethyl piperidines, 1- glycidyl -1- methyl -2,2,6,6-
In tetramethyl piperidine any one, two kinds or more the mixtures formed after being mixed with arbitrary proportion；The alkyl
Piperidines organic formwork agent is soluble in water the aqueous solution of a concentration of 5~50wt% is made after reuse.
In above-mentioned technical proposal, the organosilan, which is the organosilan of long-chain or long chain alkyl dimethyl trimethoxy, to be had
Machine silicon ammonium salt, wherein：
The organosilan of long-chain includes：γ-glycidyl ether oxypropyltrimethoxysilane, γ-methacryloxypropyl
Base propyl trimethoxy silicane, N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, N- (β-aminoethyl)-γ-ammonia third
Ethyl triethoxy silicane alkane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, hexadecyl trimethoxy silane, octadecane
Base trimethoxy silane, hexadecyl, octadecyltriethoxy silane；
Long chain alkyl dimethyl trimethoxy organosilicon ammonium salt, general formula structure are [(CH3O)3SiC3H6N(CH3)2CnH2n+1]
X, wherein n=12,14,16 or 18, X F, Cl, Br or I.
The present invention also provides a kind of porous grade AEI molecular sieves, are prepared by the above method.
The present invention also provides a kind of porous grade AEI molecular sieves being prepared by the above method for methanol-to-olefins
Application in reaction or vehicle exhaust in the catalytic removal of nitrogen oxides.
In above-mentioned technical proposal, for the porous grade AEI molecular sieves when for methanol to olefins reaction, needing will be described
Multi-stage porous AEI molecular sieves and NH4 +Solion carries out ammonium exchange, and Hydrogen multi-stage porous is obtained after then washed, dry, roasting
It is reused after AEI molecular sieve catalysts；
The porous grade AEI molecular sieves, NH4 +The solid-to-liquid ratio of solion is 1：5~50；
The NH4 +Solion, the aqueous solution selected from ammonium nitrate, ammonium chloride, ammonium sulfate or ammonium hydrogen carbonate, NH4 +Ion
A concentration of 0.5~1.5mol/L；
The ammonium exchanges, and exchange temperature is 20~80 DEG C, swap time 1-4h；
The drying, drying temperature is 100~130 DEG C, drying time be 4~for 24 hours；
The roasting, calcination temperature is 400~600 DEG C, roasting time is 2~6h.
In above-mentioned technical proposal, porous grade AEI molecular sieves catalysis of nitrogen oxides in for vehicle exhaust disappears
Except when, need the aqueous solution of the multi-stage porous AEI molecular sieves and the presoma containing Cu carrying out ion exchange, then pass through
It is being used after obtaining Cu-AEI molecular sieve catalysts after filter, washing, dry, roasting；
The solid-liquid mass ratio of the porous grade AEI molecular sieves and the aqueous solution of the presoma containing Cu is 1：3~100；
The presoma of the Cu is the mantoquita of solubility, for matching for copper nitrate, copper chloride, copper sulphate, copper acetate or copper
Close any one in object or two kinds or more the mixtures mixed with arbitrary proportion；
In the aqueous solution of the presoma containing Cu, a concentration of 0.1~1.5mol/L of Cu ions；
The ion exchange, exchange temperature be 20~80 DEG C, swap time be 0.5~for 24 hours；
The drying, drying temperature is 100~130 DEG C, drying time be 4~for 24 hours；
The roasting, calcination temperature is 400~600 DEG C, roasting time is 2~6h.
Compared with prior art, the present invention has the following advantages and beneficial effects：
(1) the obtained porous grade AEI molecular sieves of the present invention not only have micro porous molecular sieve it is acid it is strong, that thermal stability is good etc. is excellent
Point also has both the advantages that mesopore molecular sieve aperture can shorten greatly molecule diffusion path, be conducive to the diffusion of macromolecular.
(2) organosilan auxiliary is used to synthesize porous grade AEI molecular sieves, raw material is cheap and easy to get, and building-up process is simple.
Specific implementation mode
The specific implementation mode of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold：
Embodiment 1
A kind of porous grade AEI molecular sieves, are prepared by following methods：
Weigh 44.5972g waterglass (Na2O：7.39wt%, SiO2：23.9wt%), 19.0800g a concentration of 25wt%
1,1- dimethyl -3,5- lupetidines aqueous solution, 0.2083gNaOH particles (purity 96%), 2.9410gHY molecular sieves
(Si/Al=5.2) it is uniformly mixed up to all raw materials with 32.1900g deionized waters, stirring, finally obtaining the group of colloidal sol becomes：
Na2O：SiO2：Al2O3：OSDA：H2O=0.26：1.0：0.033：0.14：20.
It takes 1.1142g γ-glycidyl ether oxypropyltrimethoxysilane to be dissolved into ethanol in proper amount, is then added to
In above-mentioned colloidal sol, the molal quantity of silicon is the 2.2% of silicon source molal quantity in organosilan, is transferred them to after 60 DEG C of stirring 60min
In hydrothermal crystallizing kettle, under 20rpm rotating speeds, 160 DEG C of dynamic crystallizations 6 days.After the completion of crystallization, isolate solid product, then according to
It is secondary to pass through washing, 110 DEG C of dry 12h, 540 DEG C of roasting 4h, you can obtain the AEI molecular sieves of multi-stage porous.
Embodiment 2
Weigh 40.7642g Ludox (Na2O：0.1wt%, SiO2：26.84wt%), 32.0144g a concentration of 25wt%
1,1- diethyl-lupetidine aqueous solution, 2.4943gNaOH particles (purity 96%), 2.5669gHY molecular sieves
(Si/Al=5.2) it is uniformly mixed up to all raw materials with 61.9217g deionized waters, stirring, finally obtaining the group of colloidal sol becomes：
Na2O：SiO2：Al2O3：OSDA：H2O=0.14：1.0：0.0288：0.20：30.
It takes 1.3305g γ-methacryloxypropyl trimethoxy silane to be dissolved into ethanol in proper amount, is then added to
In above-mentioned colloidal sol, the molal quantity of silicon is the 2.5% of silicon source molal quantity in organosilan, is transferred them to after 50 DEG C of stirring 90min
In hydrothermal crystallizing kettle, under 20rpm rotating speeds, 170 DEG C of dynamic crystallizations 6 days.After the completion of crystallization, isolate solid product, then according to
It is secondary to pass through washing, 110 DEG C of dry 12h, 540 DEG C of roasting 6h, you can obtain the AEI molecular sieves of multi-stage porous.
Embodiment 3
Weigh the 1- ethyl -1- methyl -3,5- two of 8.8256g white carbons (99.53%), a concentration of 25wt% of 41.5200g
Methyl piperidine aqueous solution, 3.2163gNaOH particles (purity 96%), 5.4285gHY molecular sieves (Si/Al=5.2) and
46.0028g deionized waters, until all raw materials are uniformly mixed, finally obtaining the group of colloidal sol becomes for stirring：Na2O：SiO2：
Al2O3：OSDA：H2O=0.18：1.0：0.0613：0.28：20.
1.8134gN- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane is taken to be dissolved into ethanol in proper amount, be then added
Into above-mentioned colloidal sol, the dosage of organosilan is the 3.2% of silicon source molal quantity, and hydro-thermal is transferred them to after 80 DEG C of stirring 60min
In crystallizing kettle, under 20rpm rotating speeds, 170 DEG C of dynamic crystallizations 6 days.After the completion of crystallization, solid product is isolated, is then passed through successively
Cross washing, 110 DEG C of dry 12h, 540 DEG C of roasting 6h, you can obtain the AEI molecular sieves of multi-stage porous.
Embodiment 4
Weigh 27.3092g ethyl orthosilicates (SiO2：42wt%), the 1,1,2,2,6 of a concentration of 25wt% of 30.4436g,
6- hexamethyls aqueous piperidine solution, 5.7137gNaOH particles (purity 96%), 1.8647gHY molecular sieves (Si/Al=5.2)
With 54.3101g deionized waters, until all raw materials are uniformly mixed, finally obtaining the group of colloidal sol becomes for stirring：Na2O：SiO2：
Al2O3：OSDA：H2O=0.32：1.0：0.0212：0.19：20.
It takes 3.1198g hexadecyl trimethoxy silanes to be dissolved into ethanol in proper amount, is then added in above-mentioned colloidal sol, has
The dosage of machine silane is the 4.2% of silicon source molal quantity, is transferred them in hydrothermal crystallizing kettle after 60 DEG C of stirring 60min, in 20rpm
Under rotating speed, 180 DEG C of dynamic crystallizations 5 days.After the completion of crystallization, solid product is isolated, then in turn through washing, 110 DEG C of dryings
12h, 540 DEG C of roasting 6h, you can obtain the AEI molecular sieves of multi-stage porous.
Embodiment 5
Weigh 52.0384g waterglass (Na2O：7.39wt%, SiO2：23.9wt%), 29.4686g a concentration of 25wt%
3,5- dimethoxy -1,1- lupetidines aqueous solution, 0.1916gNaOH particles (purity 96%), 0.5801gHY molecules
(Si/Al=5.2) and 38.5716g deionized waters are sieved, stirring is uniformly mixed up to all raw materials, finally obtains the composition of colloidal sol
For：Na2O：SiO2：Al2O3：OSDA：H2O=0.30：1.0：0.0064：0.18：25.
It takes 3.2152g octadecyltriethoxy silanes to be dissolved into ethanol in proper amount, is then added in above-mentioned colloidal sol, has
The dosage of machine silane is the 3.6% of silicon source molal quantity, is transferred them in hydrothermal crystallizing kettle after 80 DEG C of stirring 60min, in 20rpm
Under rotating speed, 170 DEG C of dynamic crystallizations 6 days.After the completion of crystallization, solid product is isolated, then in turn through washing, 110 DEG C of dryings
12h, 540 DEG C of roasting 4h, you can obtain the AEI molecular sieves of multi-stage porous.
Embodiment 6
Weigh 41.3290g waterglass (Na2O：7.39wt%, SiO2：23.9wt%), 26.1943g a concentration of 25wt%
1- ethyl -1- methyl -2,2,6,6- tetramethyl piperidines aqueous solution, 0.3583gNaOH particles (purity 96%),
3.9781gHY molecular sieves (Si/Al=5.2) and 29.0999g deionized waters, stirring are uniformly mixed up to all raw materials, finally
Group to colloidal sol becomes：Na2O：SiO2：Al2O3：OSDA：H2O=0.25：1.0：0.045：0.16：20.
It takes in 3.2969g octadecyldimethyls [3- (trimethoxy silicon substrate) propyl] chloride leach to ethanol in proper amount,
It is then added in above-mentioned colloidal sol, the dosage of organosilan is the 3.1% of silicon source molal quantity, by its turn after 80 DEG C of stirring 60min
It moves in hydrothermal crystallizing kettle, under 20rpm rotating speeds, 180 DEG C of dynamic crystallizations 6 days.After the completion of crystallization, solid product is isolated, so
Afterwards successively by washing, 110 DEG C of dry 12h, 540 DEG C of roasting 4h, you can obtain the AEI molecular sieves of multi-stage porous.
Application examples 1
Respectively by the ammonium nitrate solution of the porous grade AEI molecular sieves and 1.0mol/L that are obtained in embodiment 1-3 at 80 DEG C
According to solid-to-liquid ratio 1：10, which carry out ammonium, exchanges 1h, and it is primary to repeat above-mentioned exchange process after filtration washing；Then through being filtered, washed, 110
The porous grade AEI molecular sieve catalysts of Hydrogen are made after DEG C dry 12h, 500 DEG C of roasting 3h.Then hydrogen type catalyst is pressed
Piece crush look over so as to check 20-40 mesh catalyst granules, be subsequently placed in fixed bed, 450 DEG C progress MTO reaction evaluatings, methanol into
Material air speed is 1h-1, the reactivity worth of catalyst is as shown in table 1：
Table 1：Influence of the different catalysts to methanol to olefins reaction
| Catalyst is numbered | Methanol conversion | Alkene overall selectivity |
| 1 catalyst of embodiment | 99.4% | 85.3% |
| 2 catalyst of embodiment | 99.5% | 85.6% |
| 3 catalyst of embodiment | 99.8% | 86.2% |
As can be seen from Table 1, porous grade AEI molecular sieve catalysts provided by the invention show in methanol to olefins reaction
Go out higher catalytic activity, methanol conversion is 99% or more, and alkene overall selectivity is also up to 85%.
Application examples 2
Respectively by the Cu (NO of the porous grade AEI molecular sieves and 50mL 0.2mol/L that are obtained in 10g embodiments 4-63)2Solution
Ion exchange (50 DEG C, 6h) is carried out, Cu-AEI then is made by being filtered, washed, after 110 DEG C of dry 12h, 450 DEG C of roasting 3h
Molecular sieve catalyst.The catalyst of preparation is looked over so as to check by tabletting crushing, 20-40 mesh particles is taken, is placed in fixed bed,
500ppmNO、500ppmNH3, 10vl%O2, 5vl%H2Under the conditions of O and Ar is Balance Air, in 250-450 DEG C of reaction temperature and
48000h-1SCR catalytic performance tests are carried out under reaction velocity, reaction result is as shown in table 2：
Table 2：The SCR catalytic performance tests of different catalysts
As can be seen from Table 2, Cu-AEI molecular sieve catalysts provided by the invention are in SCR reactions, at 250~400 DEG C
Reaction temperature section in, the conversion ratio of NO can maintain 90% or more, though in 450 DEG C of higher reaction temperature, NO's
Conversion ratio is also up to 85% or more.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of preparation method of porous grade AEI molecular sieves, which is characterized in that include the following steps：By silicon source, silicon source, lye,
Organic formwork agent OSDA and deionized water H2O is uniformly mixed and forms colloidal sol, organosilan is then added, the constant temperature at 20~80 DEG C
It is transferred in hydrothermal synthesis kettle after 30~120min of stirring, the dynamic crystallization 3~10 days at 20~60r/min, 140~200 DEG C；
Isolate solid product after crystallization, solid product is washed, dry 12~48h at 100~130 DEG C, roasts 3 at 400~600 DEG C
After~10h, you can obtain the AEI molecular sieves of porous grade；
Silicon source is with SiO2It calculates, silicon source is with Al2O3It calculates, lye is with Na2O calculating, organic formwork agent OSDA and deionized water H2O's
Molar ratio is Na2O：SiO2：Al2O3：OSDA：H2O=0.1~0.5：1.0：0.003~0.08：0.05~0.5：10~50；Have
The molal quantity of silicon is the 1~5% of silicon source molal quantity in machine silane.
2. preparation method according to claim 1, which is characterized in that the silicon source comes from the silicon with FAU configurations
Aluminium zeolite；The silicon source comes from Si-Al zeolite and/or other silicon sources with FAU configurations；The lye, selected from for
Any one in NaOH, KOH or two kinds of mixtures mixed with arbitrary proportion；The organic formwork agent is Alkylpiperidine
Class compound；The organosilan is the organosilan or long chain alkyl dimethyl trimethoxy organosilicon ammonium salt of long-chain.
3. preparation method according to claim 2, which is characterized in that the Si-Al zeolite with FAU configurations, including
X zeolites and Y zeolites.
4. preparation method according to claim 2, which is characterized in that it is molten to come from waterglass, silicon for other described silicon sources
In glue, white carbon, ethyl orthosilicate, solid silicone any one, two kinds or more mixed with arbitrary proportion after formed it is mixed
Close object.
5. preparation method according to claim 2, which is characterized in that the pyrrolidin, including 1,1-
Dimethyl -3,5- lupetidines, 1,1- dimethyl-lupetidine, 1,1- diethyl -3,5- lupetidines
, 1,1- diethyl-lupetidine, 1- ethyl -1- methyl -3,5- lupetidines, 1- ethyl -1- methyl -
Lupetidine, 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidines, 1,
1,3,5- tetramethyl -4- oxo-piperidines, 1- hydroxyl -1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1- dimethyl -4,4- dipropyls
Oxygroup piperidines, 3,5- dimethoxy -1,1- lupetidines, 3,5- dihydroxy -1,1- lupetidines, 4- ethyls -
1,1- dimethyl -3,5- dioxopiperidines, 1- ethyl -1- methyl -2,2,6,6- tetramethyl piperidines, 1- glycidyl -1-
In methyl -2,2,6,6- tetramethyl piperidines any one, two kinds or more the mixing formed after being mixed with arbitrary proportion
Object.
6. preparation method according to claim 2, which is characterized in that the organosilan of the long-chain includes：γ-shrink
Glyceryl etheroxypropyltrimethoxysilane, γ-methacryloxypropyl trimethoxy silane, N- β-aminoethyl-γ-ammonia
Hydroxypropyl methyl dimethoxysilane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-ammonia third
Base trimethoxy silane, hexadecyl trimethoxy silane, octadecyl trimethoxysilane, cetyl triethoxysilicane
Alkane, octadecyltriethoxy silane；The long chain alkyl dimethyl trimethoxy organosilicon ammonium salt, general formula structure are
[(CH3O)3SiC3H6N(CH3)2CnH2n+1] X, wherein n=12,14,16 or 18, X F, Cl, Br or I.
7. a kind of porous grade AEI molecular sieves, which is characterized in that be by claim 1-6 any one of them preparation method systems
Made of standby.
8. a kind of nitrogen oxygen in for methanol to olefins reaction or vehicle exhaust of the porous grade AEI molecular sieves described in claim 7
Application in the catalytic removal of compound.
9. application according to claim 8, which is characterized in that the porous grade AEI molecular sieves are for methanol alkene
When hydrocarbon reaction, need the multi-stage porous AEI molecular sieves and NH4 +Solion progress ammonium exchange, then washed, dry,
It is reused after obtaining Hydrogen multi-stage porous AEI molecular sieve catalysts after roasting.
10. application according to claim 8, which is characterized in that the porous grade AEI molecular sieves are for vehicle exhaust
When the catalytic removal of middle nitrogen oxides, need by the aqueous solution of the multi-stage porous AEI molecular sieves and the presoma containing Cu into
Row ion exchange is using after then obtaining Cu-AEI molecular sieve catalysts after being filtered, washed, drying, roast.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477584.XA CN108584975A (en) | 2018-05-18 | 2018-05-18 | A kind of porous grade AEI molecular sieves and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477584.XA CN108584975A (en) | 2018-05-18 | 2018-05-18 | A kind of porous grade AEI molecular sieves and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108584975A true CN108584975A (en) | 2018-09-28 |
Family
ID=63631922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810477584.XA Pending CN108584975A (en) | 2018-05-18 | 2018-05-18 | A kind of porous grade AEI molecular sieves and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108584975A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020151721A1 (en) * | 2019-01-23 | 2020-07-30 | Basf Se | An oxidic material comprising a zeolite having framework type aei |
| CN112138724A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Hydroalkylation catalyst and process therefor |
| WO2021004492A1 (en) * | 2019-07-09 | 2021-01-14 | 中国石油化工股份有限公司 | Silicon- and germanium-based scm-25 molecular sieve, preparation method therefor, and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417552A (en) * | 2014-09-17 | 2016-03-23 | 神华集团有限责任公司 | Hierarchical porous SAPO-18 molecular sieve, preparation method thereof and application thereof |
| CN107308980A (en) * | 2017-07-21 | 2017-11-03 | 中触媒新材料股份有限公司 | Preparation method and application for the Cu AEI molecular sieve catalysts of the tail gas clean-up containing NOx |
-
2018
- 2018-05-18 CN CN201810477584.XA patent/CN108584975A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417552A (en) * | 2014-09-17 | 2016-03-23 | 神华集团有限责任公司 | Hierarchical porous SAPO-18 molecular sieve, preparation method thereof and application thereof |
| CN107308980A (en) * | 2017-07-21 | 2017-11-03 | 中触媒新材料股份有限公司 | Preparation method and application for the Cu AEI molecular sieve catalysts of the tail gas clean-up containing NOx |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020151721A1 (en) * | 2019-01-23 | 2020-07-30 | Basf Se | An oxidic material comprising a zeolite having framework type aei |
| CN112138724A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Hydroalkylation catalyst and process therefor |
| WO2021004492A1 (en) * | 2019-07-09 | 2021-01-14 | 中国石油化工股份有限公司 | Silicon- and germanium-based scm-25 molecular sieve, preparation method therefor, and use thereof |
| US11952283B2 (en) | 2019-07-09 | 2024-04-09 | China Petroleum & Chemical Corporation | Silicon-and germanium-based SCM-25 molecular sieve, preparation process and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101643219B (en) | Preparation method of nano-ZSM-5 molecular sieve | |
| CN108264057B (en) | Method for solid-phase synthesis of wettability-controllable ZSM-5 zeolite | |
| CN102774854A (en) | Synthetic method of novel mesoporous-microporous NaY zeolite | |
| CN108584975A (en) | A kind of porous grade AEI molecular sieves and its preparation method and application | |
| CN105712379B (en) | A kind of synthetic method of multi-stage porous ZSM-5 molecular sieve | |
| CN103214006B (en) | Preparation method of composite zeolite with core/shell structure | |
| CN105271294B (en) | Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method | |
| CN102674392A (en) | Hollow capsule nano ZSM-5 molecular sieve and preparation method thereof | |
| CN102001681A (en) | Method for synthesizing ZSM-5 zeolite | |
| CN106145151A (en) | A kind of multi-stage porous HTS and synthetic method thereof | |
| CN109701619A (en) | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method | |
| CN106185980A (en) | A kind of method preparing multi-stage porous ZSM 5 molecular sieve | |
| CN101003380A (en) | Method for synthesizing ZSM-5 zeolite with multilevel pore canals | |
| CN105682795A (en) | Method for synthesizing silicoaluminophosphate-34 molecular sieves | |
| CN112939021B (en) | Structure directing agent, preparation method and application thereof | |
| CN102838131A (en) | Sapo-34 molecular sieve and preparation method thereof | |
| CN104512904B (en) | A kind of method preparing mesoporous titanium-silicon material | |
| CN112794338B (en) | ZSM-5 molecular sieve and preparation method and application thereof | |
| CN102225772A (en) | Method for utilizing molecular sieve systhesis mother liquor | |
| CN105271299A (en) | Mesoporous ZSM-5 zeolite preparing method | |
| CN109996783A (en) | The method that monoethanolamine is converted to ethylenediamine using the copper modified zeolite of MOR framework structure | |
| CN103058208A (en) | Preparation method of SAPO-56 molecular sieve | |
| CN103073019B (en) | Hierarchical pore zeolite molecular sieve preparation method | |
| CN108946756B (en) | Hierarchical pore EUO structure molecular sieve and synthesis method thereof | |
| CN112978756A (en) | Flaky TS-1 molecular sieve, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180928 |