CN106809862A - A kind of method and its molecular sieve for preparing multi-stage porous SAPO-11 molecular sieves - Google Patents
A kind of method and its molecular sieve for preparing multi-stage porous SAPO-11 molecular sieves Download PDFInfo
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- CN106809862A CN106809862A CN201510855771.3A CN201510855771A CN106809862A CN 106809862 A CN106809862 A CN 106809862A CN 201510855771 A CN201510855771 A CN 201510855771A CN 106809862 A CN106809862 A CN 106809862A
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- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates (SAPO compounds), e.g. CoSAPO
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of method and its molecular sieve for preparing multi-stage porous SAPO-11.It is aided in or Vapor-phase transport method using vapor, with mesoporous SAPO gel as presoma, synthesis obtains a kind of multi-stage porous SAPO-11 molecular sieves that the AEL structure that association (International Zeolite Association) confirms is sieved with International Molecular.Multi-stage porous SAPO-11 molecular sieves of the invention have good hydrothermal stability, there is big specific surface area and pore volume simultaneously, to be with a wide range of applications in catalytic field particularly lube base oil hydroisomerizing field, preparation method economy of the present invention is strong, easy-to-operate, it is environment-friendly.
Description
Technical field
The present invention relates to a kind of synthetic method of silicoaluminophosphamolecular molecular sieves in high yield, more precisely close
In a kind of synthetic method for preparing multi-stage porous SAPO-11 molecular sieves in high yield.
Background technology
SAPO-11 is the silicoaluminophosphamolecular molecular sieves with AEL (International Zeolite Association's appointment codes) structure
(Atlas of Zeolite Framework Types,6thed.,Elsevier,Amsterdam,2007；http://
Www.iza-structure.org/databases/) it has one-dimensional oval 10 yuan of rings straight hole road, aperture size
It is 0.40nm × 0.65nm.Because the pore passage structure size of this molecular sieve is highly beneficial with geometric configuration
In the formation of single branched paraffin isomers, the Pt-Pd/AEL silicoaluminophosphamolecular molecular sieves of Supported Pt Nanoparticles palladium noble metal
Good catalysis activity and selectivity is shown in the isomerization reaction of linear paraffin.But itself
The micropore being had is unfavorable for the diffusion of molecule, limits its catalysis activity.Therefore, researcher is using each
Method is planted to attempt to introduce mesoporous or macropore.(J.Catal.2012,294,161-170；J.Catal.2013,301,
162-173).The common feature of these methods is that the surfactant that costliness is added under conditions of hydro-thermal is closed
Into.Zeolite synthesis yield is low, complex process, operating difficulties；Surfactant is expensive, no
Can reclaim, synthesize high cost.
Xerogel synthesis includes vapor auxiliary law and Vapor-phase transport method, and the method is by China scientist
Xu Wen Yang teach method that proposed in nineteen ninety a kind of new prepare molecular sieve (J.Chem.Soc.,
Chem.Commun.1990,(10),755).The method is typically unformed raw material and water, You Jimo
Unformed gel is prepared into after plate agent is well mixed, precursor mixture is obtained after drying.Precursor is mixed
During thing is as special container, a small amount of water is added in a kettle., to provide the moisture required for reaction,
Then crystallization under steam ambient again.Compared to traditional Hydrothermal Synthesiss, xerogel synthesis has high income,
It is low in the pollution of the environment, the features such as raw material availability is high.
Although report prepare the SAPO-11 molecules with AEL skeletons using vapor auxiliary law before
The preparation of sieve, due to the crystal it typically is needle-like, single micropore limits its answering in terms of catalysis
With.The sol-gal process that this patent employs epoxide participation is prepared with bigger serface,
The mesoporous SAPO gel precursors mixture of big pore volume, the precursor mixture is aided in vapor
Under the conditions of synthesized AEL type multi-stage porous SAPO-11 molecular sieves, because it has in high yield and simultaneously
With micropore and mesoporous, will especially lube base oil hydroisomerizing field obtains more in catalytic field
Good application.
The content of the invention
It is an object of the invention to propose a kind of method for preparing multi-stage porous SAPO-11 molecular sieves in high yield.
To achieve the above object, the technical solution adopted by the present invention is：
It is auxiliary in vapor with organic amine as template with mesoporous SAPO gel as precursor mixture
By the synthesis of SAPO gel with multi-stage porous SAPO-11 molecular sieves in high yield under conditions of helping；Bag
Include following steps：
1) preparation of precursor mixture：Add phosphorus source, silicon source and silicon source in solvent, stirring is to equal
Epoxide is added after even, after continuing to be stirred until homogeneous, it is aging at a certain temperature and dry before
Drive body mixture；
2) precursor mixture is placed in container, and is placed in crystallization system, in crystallization system
Bottom adds water and has organic amine；
3) heating crystallization, after crystallization terminates, separates solid product, and the solid for obtaining is multi-stage porous SAPO-11
Molecular sieve.
Concretely comprise the following steps：
During phosphorus source added into solvent, and stir；Silicon source is added in mixture, is stirred；
Silicon source is added, is stirred；To above-mentioned solution in ethylene compound, stir；By above-mentioned mixing
Thing is aging in 0~200 DEG C, and the aging temperature of optimization is 10~60 DEG C；Mixture after will be aging is dried,
Drying temperature is 40~200 DEG C, and the drying temperature of optimization is 60~120 DEG C, and precursor mixing is obtained after drying
Thing.By precursor mixture in the presence of organic amine, vapor auxiliary crystallization, crystallization temperature be 100~
200 DEG C, crystallization time is more than or equal to 1 minute, and preferred crystallization time is 0.5~480h；
Crystallization separates solid product after terminating, will reactant mixture be cooled to room temperature, plus deionized water,
Filtering, is washed, room temperature~120 DEG C drying with deionized water to sample, and the solid sample for obtaining is
With multi-stage porous SAPO-11 molecular sieves in high yield；
Roasting (300~600 DEG C of air atmosphere roastings are more than or equal to 1 hour) removes organic formwork afterwards
Agent, obtains the multi-stage porous silicoaluminophosphamolecular molecular sieves of duct dredging, and the duct dredging is molecular sieve pore passage
In be free of organic formwork agent.
Step 1) silicon source in precursor mixture：Silicon source：Phosphorus source：Epoxide：Solvent presses Al2O3：
SiO2：P2O5：Epoxide：The molar ratio of solvent meter is 1:0.01~1：0.1~5:0.01~
50：5~200, aging temperature is 0~200 DEG C, and drying temperature is 40~200 DEG C；Step 2) precursor
Mixture：Water：The molar ratio of organic amine is 1:0.01~1000:0.1~50, wherein precursor mixing
The mole of thing is with the molar amount of phosphorus source；Step 3) crystallization temperature be 80 DEG C~300 DEG C, during crystallization
Between be more than or equal to 1 minute.
Step 1) silicon source in precursor mixture：Silicon source：Phosphorus source：Epoxide：Solvent presses Al2O3：
SiO2：P2O5：Epoxide：The mol ratio of solvent meter is 1:0.1~0.8：0.5~3:0.5~20：
10~50, aging temperature is 10~60 DEG C, and drying temperature is 60~120 DEG C；Step 2) precursor mixing
Thing：Water：The molar ratio of organic amine is 1:0.1~100:0.5~30, wherein precursor mixture rubs
You are measured with the molar amount of phosphorus source；Step 3) crystallization temperature be 120~240 DEG C, crystallization time be 1~
240h。
Solvent be water, ethanol, propyl alcohol, isopropanol and ethylene glycol in one or more；Phosphorus source
It is one or two or more kinds in phosphoric acid, ammonium phosphate, monoammonium phosphate and ammonium dihydrogen phosphate, the phosphorus
Sour mass concentration is 50-85%；Silicon source is aluminium isopropoxide, crystal aluminum chloride, boehmite, sulfuric acid
One or two or more kinds in aluminium；During silicon was Ludox, waterglass, white carbon, tetraethyl orthosilicate originally
One or two or more kinds；Epoxide be oxirane and expoxy propane in one or two；
Organic amine is one kind or two kinds in dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, n-butylamine
More than.
Crystallization system is stainless steel cauldron or microwave reactor.
Product has the characteristics of in high yield, and product yield is 40~100%.
After the fired removal organic formwork agent of prepared molecular sieve, the multistage of duct dredging can be obtained
Hole silicoaluminophosphamolecular molecular sieves, the duct dredging is to be free of organic formwork agent in molecular sieve pore passage, roasting is warm
It is 300~600 DEG C to spend, and roasting time is more than or equal to 1 hour.
Molecular sieve prepared by the preparation method provided according to the present invention uses X-ray powder diffraction, X to penetrate
Line spectrofluorimetry and SEM (SEM) are analyzed to the molecular sieve structure and composition,
Determine that its structure is true with International Molecular sieve association by comparing with XRD powder diffraction datas storehouse card
The AEL structure recognized, X-ray fluorescence spectra constituent content analysis result determines Al in the molecular sieve2O3：
P2O5：SiO2Molar ratio, is characterized by SEM and determines its pattern.The molecular sieve for finally giving has state
The AEL structure that border molecular sieve association confirms, while silicon source in the molecular sieve：Silicon source：Phosphorus source presses Al2O3:
SiO2：P2O5Meter, molar ratio is 1:0.1~0.6：0.8~1.2.Its X-ray diffraction spectrogram is extremely
There is diffraction maximum set forth below less,
2 θ values expression diffraction maximum position, 2 θ/°：8.10±0.2,9.51±0.2,13.18±
0.2,13.65±0.2,15.71±0.2,16.23±0.2,19.03±0.2,20.38±0.2,21.08
±0.2,22.12±0.2,22.79±0.2,23.17±0.2,24.77±0.2,26.33±
0.2,28.70±0.2,29.50±0.2。
The beneficial effect of this synthetic method：
The characteristics of this synthetic method is to carry out multi-stage porous SAPO-11 molecules under conditions of vapor auxiliary
The synthesis of sieve, overcomes the characteristics of conventional hydrothermal synthetic product yield is low, and waste discharge is serious.Closed
Into material be the multi-stage porous SAPO-11 molecular sieves with AEL structure.The inventive method has environment
Close friend, easy to operate, the advantage of high income,.
Brief description of the drawings
Fig. 1 is the XRD spectra of the multi-stage porous SAPO-11 molecular sieves synthesized by the embodiment of the present invention 1.
Fig. 2 is that the nitrogen physisorption of the multi-stage porous SAPO-11 molecular sieves synthesized by the embodiment of the present invention 1 is inhaled
Attached curve.
Fig. 3 is the SEM Electronic Speculum of the multi-stage porous SAPO-11 molecular sieves synthesized by the embodiment of the present invention 1
Photo.
Specific embodiment
Embodiment 1
To 10 grams of water are added in 50 milliliters of beakers, 2.0g crystal aluminum chlorides are added under magnetic agitation,
It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring,
Stirring 30 minutes, is then dropwise added dropwise 2 milliliters of expoxy propane, continues to stir 5 minutes.By mixture
In aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Above-mentioned precursor is taken to mix
During 1 gram of compound is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in,
The bottom of reactor adds 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, 2 are kept
My god, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.By final white
Powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL knots
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains
To the multi-stage porous SAPO-11 molecular sieves that duct is dredged.
Embodiment 2
To 5 grams of water, 5 grams of ethanol are added in 50 milliliters of beakers, 2.0g crystallization chlorinations are added under magnetic agitation
Aluminium, it is uniform that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.5 gram of positive silicic acid is added dropwise after stirring
Ethyl ester, stirs 30 minutes, and 2 milliliters of expoxy propane are then dropwise added dropwise, and continues to stir 5 minutes.Will
Mixture in aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Take above-mentioned
During 1 gram of precursor mixture is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron
In, add 1 gram of water, 1 gram of positive di-n-propylamine 200 DEG C to be warming up to after sealing, is protected in the bottom of reactor
Hold 2 days, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.Will be final
White powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere,
Obtain the multi-stage porous SAPO-11 molecular sieves of duct dredging.
Embodiment 3
To 10 ethanol are added in 50 milliliters of beakers, 2.0g crystal aluminum chlorides are added under magnetic agitation,
It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.4 gram of tetraethyl orthosilicate is added dropwise after stirring,
Stirring 30 minutes, is then dropwise added dropwise 3 milliliters of expoxy propane, continues to stir 5 minutes.By mixture
In aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Above-mentioned precursor is taken to mix
During 1 gram of compound is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in,
The bottom of reactor adds 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, 2 are kept
My god, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.By final white
Powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL knots
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains
To the multi-stage porous SAPO-11 molecular sieves that duct is dredged.
Embodiment 4
To 10 grams of water are added in 50 milliliters of beakers, 2.0g crystal aluminum chlorides are added under magnetic agitation, uniformly
The phosphoric acid that 2.0 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring, stir
Mix 30 minutes, 4 milliliters of expoxy propane are then dropwise added dropwise, continue to stir 5 minutes.By mixture in
Aging 12 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Take above-mentioned precursor mixing
During 1 gram of thing is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, anti-
The bottom of kettle is answered to add 1 gram of water, 0.5 gram of positive di-n-propylamine 200 DEG C to be warming up to after sealing, is kept for 2 days,
Then reactant mixture is cooled to room temperature, and is washed with deionized 3 times.By final white powder
It is placed in 120 DEG C of baking ovens and dries, tested through XRD, SEM, the white powder is with AEL structure
Multi-stage porous silicoaluminophosphamolecular molecular sieves.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains hole
The multi-stage porous SAPO-11 molecular sieves of road dredging.
Embodiment 5
To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation,
It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.6 gram of tetraethyl orthosilicate is added dropwise after stirring,
Stirring 30 minutes, is then dropwise added dropwise 5 milliliters of expoxy propane, continues to stir 5 minutes.By mixture
In aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Above-mentioned precursor is taken to mix
During 1 gram of compound is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in,
The bottom of reactor adds 1 gram of water, 0.6 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, 2 are kept
My god, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.By final white
Powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL knots
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains
To the multi-stage porous SAPO-11 molecular sieves that duct is dredged.
Embodiment 6
To 10 grams of ethanol are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation,
It is uniform that the phosphoric acid that 1.2 gram mass concentration are 85% is added dropwise, 0.4 gram of tetraethyl orthosilicate is added dropwise after stirring,
Stirring 30 minutes, is then dropwise added dropwise 2 milliliters of expoxy propane, continues to stir 5 minutes.By mixture
In aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Above-mentioned precursor is taken to mix
During 1 gram of compound is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in,
The bottom of reactor adds 1 gram of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, 2 are kept
My god, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.By final white
Powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL knots
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains
To the multi-stage porous SAPO-11 molecular sieves that duct is dredged.Embodiment 9
Embodiment 7
To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation, uniformly
The phosphoric acid that 1.8 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring, stir
Mix 30 minutes, 4 milliliters of expoxy propane are then dropwise added dropwise, continue to stir 5 minutes.By mixture in
Aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 120 degree.Take above-mentioned precursor mixing
During 1 gram of thing is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, anti-
The bottom of kettle is answered to add 1 gram of water, 0.5 gram of positive di-n-propylamine 200 DEG C to be warming up to after sealing, is kept for 2 days,
Then reactant mixture is cooled to room temperature, and is washed with deionized 3 times.By final white powder
It is placed in 120 DEG C of baking ovens and dries, tested through XRD, SEM, the white powder is with AEL structure
Multi-stage porous silicoaluminophosphamolecular molecular sieves.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains hole
The multi-stage porous SAPO-11 molecular sieves of road dredging.Embodiment 11
Embodiment 8
To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation,
It is even that the phosphoric acid that 1.5 gram mass concentration are 85% is added dropwise, 0.3 gram of tetraethyl orthosilicate is added dropwise after stirring,
Stirring 30 minutes, is then dropwise added dropwise 2 milliliters of expoxy propane, continues to stir 5 minutes.By mixture
In aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Above-mentioned precursor is taken to mix
During 1 gram of compound is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in,
The bottom of reactor adds 0.5 gram of water, 0.5 gram of positive di-n-propylamine that 180 DEG C are warming up to after sealing, 2 are kept
My god, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.By final white
Powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL knots
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains
To the multi-stage porous SAPO-11 molecular sieves that duct is dredged.
Embodiment 9
To 10 grams of water are added in 50 milliliters of beakers, 2.00g crystal aluminum chlorides are added under magnetic agitation, uniformly
The phosphoric acid that 1.2 gram mass concentration are 85% is added dropwise, 0.2 gram of tetraethyl orthosilicate is added dropwise after stirring, stir
Mix 30 minutes, 5 milliliters of expoxy propane are then dropwise added dropwise, continue to stir 5 minutes.By mixture in
Aging 24 hours at 40 DEG C, then in drying to obtain precursor mixture under 100 degree.Take above-mentioned precursor mixing
During 1 gram of thing is placed in standoff tetrafluoro pallet, and by pallet as stainless steel cauldron in, anti-
The bottom of kettle is answered to add 1.5 grams of water, 0.5 gram of positive di-n-propylamine that 200 DEG C are warming up to after sealing, 2 are kept
My god, reactant mixture is then cooled to room temperature, and be washed with deionized 3 times.By final white
Powder is placed in 120 DEG C of baking ovens and dries, and is tested through XRD, SEM, and the white powder is with AEL knots
The multi-stage porous silicoaluminophosphamolecular molecular sieves of structure.Products therefrom is calcined 24h through 570 DEG C under air atmosphere, obtains
To the multi-stage porous SAPO-11 molecular sieves that duct is dredged.
Claims (9)
1. a kind of method for preparing multi-stage porous SAPO-11 molecular sieves, it is characterised in that：With mesoporous phosphoric acid
Silica-alumina gel is presoma, with organic amine as template, by silicon phosphate under conditions of vapor auxiliary
Alumina gel synthesizes multi-stage porous SAPO-11 molecular sieves；Comprise the following steps：
1) preparation of precursor mixture：Phosphorus source, silicon source and silicon source are added in solvent, is stirred until homogeneous
After add epoxide, after continuing to be stirred until homogeneous, aging at a certain temperature and dry forerunner
Body mixture；
2) precursor mixture is placed in container, and is placed in crystallization system, in crystallization system
Bottom adds water and has organic amine；
3) heating crystallization, after crystallization terminates, separates solid product, and the solid for obtaining is multi-stage porous SAPO-11
Molecular sieve.
2. in accordance with the method for claim 1, it is characterised in that：Step 1) in precursor mixture
Silicon source：Silicon source：Phosphorus source：Epoxide：Solvent presses Al2O3：SiO2：P2O5：Epoxide：
The molar ratio of solvent meter is 1:0.01~1：0.1~5:0.01~50：5~200, aging temperature is
0~200 DEG C, drying temperature is 40~200 DEG C；Step 2) precursor mixture：Water：Organic amine rubs
Your ratio is 1:0.01~1000:0.1~50, wherein the mole of precursor mixture with phosphorus source mole
Gauge；Step 3) crystallization temperature be 80 DEG C~300 DEG C, crystallization time be more than or equal to 1 minute.
3. according to the method described in claim 1 or 2, it is characterised in that：Step 1) precursor mixing
Silicon source in thing：Silicon source：Phosphorus source：Epoxide：Solvent presses Al2O3：SiO2：P2O5：Epoxy compound
Thing：The mol ratio of solvent meter is 1:0.1~0.8：0.5~3:0.5~20：10~50, aging temperature
It it is 10~60 DEG C, drying temperature is 60~120 DEG C；Step 2) precursor mixture：Water：Organic amine
Molar ratio is 1:0.1~100:0.5~30, wherein the mole of precursor mixture with phosphorus source mole
Gauge；Step 3) crystallization temperature be 120~240 DEG C, crystallization time be 1~240h.
4. in accordance with the method for claim 1, it is characterised in that：Solvent be water, ethanol, propyl alcohol,
One or more in isopropanol and ethylene glycol；Phosphorus source is phosphoric acid, ammonium phosphate, monoammonium phosphate
With one or two or more kinds in ammonium dihydrogen phosphate, the phosphoric acid quality concentration is 50-85%；Silicon source is
One or two or more kinds in aluminium isopropoxide, crystal aluminum chloride, boehmite, aluminum sulfate；Silicon is former
It is one or two or more kinds in Ludox, waterglass, white carbon, tetraethyl orthosilicate；Epoxy compound
Thing be oxirane and expoxy propane in one or two；Organic amine is dimethylamine, diethylamine, two
One or two or more kinds in n-propylamine, diisopropylamine, n-butylamine.
5. in accordance with the method for claim 1, it is characterised in that：Crystallization system is stainless steel reaction
Kettle or microwave reactor.
6. in accordance with the method for claim 1, it is characterised in that：Product has the characteristics of in high yield,
Product yield is 40~100%.
7. in accordance with the method for claim 1, it is characterised in that：Prepared molecular sieve is fired
After removal organic formwork agent, the multi-stage porous silicoaluminophosphamolecular molecular sieves of duct dredging, the duct can be obtained
Dredge to be free of organic formwork agent in molecular sieve pore passage.
8. in accordance with the method for claim 7, it is characterised in that：Sintering temperature is 300~600 DEG C,
Roasting time is more than or equal to 1 hour.
9. the molecular sieve that prepared by any preparation method described in usage right requirement 1~7, it is characterised in that：
There is multi-stage porous SAPO-11 molecular sieves International Molecular to sieve the AEL structure that association confirms, while the molecule
Silicon source in sieve：Silicon source：Phosphorus source presses Al2O3:SiO2：P2O5Meter, molar ratio is 1:0.1~0.6：0.8~
1.2；Its X-ray diffraction spectrogram at least has diffraction maximum set forth below,
2 θ values expression diffraction maximum position, 2 θ/°：8.10±0.2,9.51±0.2,13.18±
0.2,13.65±0.2,15.71±0.2,16.23±0.2,19.03±0.2,20.38±0.2,21.08
±0.2,22.12±0.2,22.79±0.2,23.17±0.2,24.77±0.2,26.33±
0.2,28.70±0.2,29.50±0.2。
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| CN109896531A (en) * | 2019-04-21 | 2019-06-18 | 王干 | A kind of preparation method of SAPO-11 molecular sieve |
| CN112456513A (en) * | 2020-12-10 | 2021-03-09 | 聊城大学 | Open system solid phase synthesis AEL structure aluminum phosphate based molecular sieve, preparation method and application |
| CN114939434A (en) * | 2022-06-01 | 2022-08-26 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexane |
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| CN112456513B (en) * | 2020-12-10 | 2023-05-09 | 聊城大学 | Open system solid phase synthesis AEL structure aluminum phosphate based molecular sieve, preparation method and application |
| CN114939434A (en) * | 2022-06-01 | 2022-08-26 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexane |
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