CN106629759B - A kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves - Google Patents
A kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 45
- 230000008025 crystallization Effects 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 230000003213 activating effect Effects 0.000 claims abstract description 14
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229940043279 diisopropylamine Drugs 0.000 claims description 8
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical group CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 claims description 3
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 claims description 3
- 229910002796 Si–Al Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 230000004907 flux Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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
-
- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves, step are：（1）It by reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, is then uniformly mixed among mortar, and 10 ~ 20min of hand lapping；（2）Predecessor after grinding is placed in small-sized reaction kettle and carries out activating pretreatment, 8 ~ 12h of constant temperature under 80 DEG C of environment, it is 160 ~ 200 DEG C then to adjust temperature, starts crystallization, and crystallization time is 10 ~ 20h；（3）Crystallization terminates cooled to room temperature, uses deionized water and acetone centrifuge washing successively, and until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；（4）By step（3）The molecular screen primary powder of acquisition roasts at 550 600 DEG C, roasts 3 ~ 5h, obtains AEL type silicoaluminophosphamolecular molecular sieves powder.
Description
Technical field
The present invention relates to the synthetic technologys of silicoaluminophosphamolecular molecular sieves, belong to new catalytic material synthesis, method for preparing catalyst
Field.
Background technology
Silicoaluminophosphamolecular molecular sieves（SAPO-n）Material has very important status in catalysis industry field, for a long time,
People are dedicated to the research in silicoaluminophosphamolecular molecular sieves synthetic route, it is desirable to find while not influencing its catalytic performance, energy
Enough simple and effectives and the new way for inexpensively synthesizing such material.
The a member of AEL types silicoaluminophosphamolecular molecular sieves as SAPO-n molecular sieves has one-dimensional ten-ring pore passage structure,
The acidic site of its appropriateness makes it show splendid catalytic performance in hygrogenating isomerization reaction.
Traditional AEL types silicoaluminophosphamolecular molecular sieves are prepared using water/solvent-thermal process method, this method has synthetic material pure
The advantages that degree is higher, grain size is easy to control, but it inevitably generates the waste unfavorable to environment, and crystallization process using solvent
The middle high-voltage problem come using water equal solvent vaporization zone also enables compound experiment have some potential safety problems.There is researcher to utilize ion
Liquid carries out the synthesis of silicoaluminophosphamolecular molecular sieves, although high-voltage problem can be solved successfully, this kind of synthetic method molecular sieve
Narrow scope of application, and ionic liquid is at high price causes relative cost excessively high.
In recent years, under the situation that clean environment and Environmental security are taken seriously further, to make AEL type silicoaluminophosphate point
Son sieve preferably plays its catalysis advantage, then it is very urgent to explore a kind of high-efficiency synthesis method of low cost.
Invention content
The object of the present invention is to provide a kind of synthetic methods of AEL types silicoaluminophosphamolecular molecular sieves.
The present invention is a kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves, so that reactant is uniformly mixed using grinding means
It closes, in the case where additionally not adding water and other liquid fluxs, merely with the self-contained a small amount of water of reactant, realizes low mould
The synthesis of the AEL type silicoaluminophosphamolecular molecular sieves of silicon atom same order elements, step are when plate agent dosage：
（1）By reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, then
It is uniformly mixed among mortar, and 10 ~ 20min of hand lapping；
（2）Predecessor after grinding is placed in small-sized reaction kettle and carries out activating pretreatment, the constant temperature 8 under 80 DEG C of environment
~ 12h, it is 160 ~ 200 DEG C then to adjust temperature, starts crystallization, and crystallization time is 10 ~ 20h；
（3）Crystallization terminates cooled to room temperature, uses deionized water and acetone centrifuge washing successively, until upper layer
Until liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；
（4）By step（3）The molecular screen primary powder of acquisition roasts at 550-600 DEG C, roasts 3 ~ 5h, obtains AEL type phosphoric acid
Si-Al molecular sieve powder；
Source of aluminium is aluminium isopropoxide, with Al2O3Meter；Phosphorus source is phosphoric acid or phosphorous acid, with P2O5Meter；Fluorine source is hydrofluoric acid
Or ammonium fluoride, in terms of F；Template is di-n-propylamine or diisopropylamine；Silicon source is aerosil, nano silicon dioxide or silicon
Colloidal sol, with SiO2Meter；
It is described reaction original mixture specific molar ratio be：Al2O3:P2O5:F:SiO2:DPA/DIPA is：1:（0.8~
1.2）:1:（0.1~0.4）:（0.1~0.3）.
The present invention has following advantage compared with the method for other synthesis AEL type silicoaluminophosphamolecular molecular sieves：Crystallization can be made
Preferable AEL types silicoaluminophosphamolecular molecular sieves are spent, step is safe and simple, and template dosage is less, and utilization rate is high, to make system
Standby of low cost, prospects for commercial application is bright and clear.
Description of the drawings
Fig. 1 is the XRD spectra of the sample powder synthesized by the embodiment of the present invention 1, and Fig. 2 is synthesized by the embodiment of the present invention 1
Sample powder SEM spectrograms, Fig. 3 be the embodiment of the present invention 2 synthesized by sample powder XRD spectra.
Specific implementation mode
The present invention is a kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves, so that reactant is uniformly mixed using grinding means
It closes, in the case where additionally not adding water and other liquid fluxs, merely with the self-contained a small amount of water of reactant, realizes low mould
The synthesis of the AEL type silicoaluminophosphamolecular molecular sieves of silicon atom same order elements, step are when plate agent dosage：
（1）By reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, then
It is uniformly mixed among mortar, and 10 ~ 20min of hand lapping；
（2）Predecessor after grinding is placed in small-sized reaction kettle and carries out activating pretreatment, the constant temperature 8 under 80 DEG C of environment
~ 12h, it is 160 ~ 200 DEG C then to adjust temperature, starts crystallization, and crystallization time is 10 ~ 20h；
（3）Crystallization terminates cooled to room temperature, uses deionized water and acetone centrifuge washing successively, until upper layer
Until liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；
（4）By step（3）The molecular screen primary powder of acquisition roasts at 550-600 DEG C, roasts 3 ~ 5h, obtains AEL type phosphoric acid
Si-Al molecular sieve powder；
Source of aluminium is aluminium isopropoxide, with Al2O3Meter；Phosphorus source is phosphoric acid or phosphorous acid, with P2O5Meter；Fluorine source is hydrofluoric acid
Or ammonium fluoride, in terms of F；Template is di-n-propylamine or diisopropylamine；Silicon source is aerosil, nano silicon dioxide or silicon
Colloidal sol, with SiO2Meter；
It is described reaction original mixture specific molar ratio be：Al2O3:P2O5:F:SiO2:DPA/DIPA is：1:（0.8~
1.2）:1:（0.1~0.4）:（0.1~0.3）.
Above-described synthetic method, synthesis AEL types silicoaluminophosphamolecular molecular sieves are through inductively coupled plasma atomic emissions
Spectroscopic methodology is tested, and silicon content is distributed within the scope of 3wt% ~ 10wt%.
Above-described synthetic method, synthesis AEL types silicoaluminophosphamolecular molecular sieves are in the process without extraly introducing water and its
Its solvent, and crystallization carries out under the conditions of low template dosage.
The present invention will be further described for embodiment below, but operation is embodied and is not limited in embodiment.
Embodiment 1：
By reaction raw materials aluminium isopropoxide, phosphoric acid, hydrofluoric acid, di-n-propylamine and aerosil proportionally 1Al2O3:
1P2O5:1F:0.4SiO2:0.2DPA accurate weighings, are uniformly mixed among mortar, and hand lapping 20min；After grinding
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, carries out activating pretreatment, the constant temperature 8h under 80 DEG C of environment；It adjusts
Temperature is 180 DEG C, starts crystallization, crystallization time 12h；Crystallization terminates cooled to room temperature, uses deionization successively
Water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecular sieve
Original powder roasts at 550 DEG C, roasts 3h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 7.21wt%.
Embodiment 2：
By reaction raw materials aluminium isopropoxide, phosphoric acid, hydrofluoric acid, diisopropylamine and nano silicon dioxide proportionally 1Al2O3:
1P2O5:1F:0.2SiO2:0.2DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 20min；After grinding
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, carries out activating pretreatment, the constant temperature 8h under 80 DEG C of environment；It adjusts
Temperature is 180 DEG C, starts crystallization, crystallization time 12h；Crystallization terminates cooled to room temperature, uses deionization successively
Water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecular sieve
Original powder roasts at 550 DEG C, roasts 3h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 4.56wt%.
Embodiment 3：
By reaction raw materials aluminium isopropoxide, phosphorous acid, hydrofluoric acid, diisopropylamine and nano silicon dioxide proportionally 1Al2O3:
1.2P2O5:1F:0.4SiO2:0.3DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 10min；It will be ground
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, afterwards carries out activating pretreatment, the constant temperature 8h under 80 DEG C of environment；It adjusts
It is 180 DEG C to save temperature, starts crystallization, crystallization time 12h；Crystallization terminates cooled to room temperature, successively using go from
Sub- water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecule
Sieve original powder roasts at 600 DEG C, roasts 5h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 9.14wt%.
Embodiment 4：
By reaction raw materials aluminium isopropoxide, phosphoric acid, hydrofluoric acid, di-n-propylamine and Ludox proportionally 1Al2O3:0.8P2O5:
1F: 0.1SiO2:0.1DPA accurate weighings, are uniformly mixed among mortar, and hand lapping 10min；It will be presented after grinding
The predecessor of solid powdery, which is placed in small-sized reaction kettle, carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；Adjust temperature
It is 200 DEG C, starts crystallization, crystallization time 20h；Crystallization terminates cooled to room temperature, successively use deionized water and
Acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecular screen primary powder
It is roasted at 550 DEG C, roasts 5h, obtain the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 3.27wt%.
Embodiment 5：
By reaction raw materials aluminium isopropoxide, phosphoric acid, hydrofluoric acid, di-n-propylamine and aerosil proportionally 1Al2O3:
1P2O5:1F:0.4SiO2:0.3DPA accurate weighings, are uniformly mixed among mortar, and hand lapping 15min；After grinding
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, carries out activating pretreatment, the constant temperature 10h under 80 DEG C of environment；It adjusts
Temperature is 200 DEG C, starts crystallization, crystallization time 20h；Crystallization terminates cooled to room temperature, uses deionization successively
Water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecular sieve
Original powder roasts at 550 DEG C, roasts 5h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 8.43wt%.
Embodiment 6：
By reaction raw materials aluminium isopropoxide, phosphoric acid, ammonium fluoride, diisopropylamine and aerosil proportionally 1Al2O3:
0.8P2O5:1F:0.2SiO2:0.2DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 15min；It will be ground
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, afterwards carries out activating pretreatment, the constant temperature 10h under 80 DEG C of environment；It adjusts
It is 180 DEG C to save temperature, starts crystallization, crystallization time 12h；Crystallization terminates cooled to room temperature, successively using go from
Sub- water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecule
Sieve original powder roasts at 550 DEG C, roasts 4h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 3.86wt%.
Embodiment 7：
By reaction raw materials aluminium isopropoxide, phosphorous acid, ammonium fluoride, diisopropylamine and Ludox proportionally 1Al2O3:
1.2P2O5:1F:0.4SiO2:0.3DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 20min；It will be ground
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, afterwards carries out activating pretreatment, the constant temperature 10h under 80 DEG C of environment；It adjusts
It is 180 DEG C to save temperature, starts crystallization, crystallization time 20h；Crystallization terminates cooled to room temperature, successively using go from
Sub- water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecule
Sieve original powder roasts at 550 DEG C, roasts 4h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 8.81wt%.
Embodiment 8：
By reaction raw materials aluminium isopropoxide, phosphorous acid, ammonium fluoride, di-n-propylamine and aerosil proportionally 1Al2O3:
1.2P2O5:1F:0.2SiO2:0.2DPA accurate weighings, are uniformly mixed among mortar, and hand lapping 15min；It will be ground
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, afterwards carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；It adjusts
It is 180 DEG C to save temperature, starts crystallization, crystallization time 12h；Crystallization terminates cooled to room temperature, successively using go from
Sub- water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecule
Sieve original powder roasts at 550 DEG C, roasts 4h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 4.37wt%.
Embodiment 9：
By reaction raw materials aluminium isopropoxide, phosphoric acid, ammonium fluoride, diisopropylamine and Ludox proportionally 1Al2O3:0.8P2O5:
1F: 0.4SiO2:0.3DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 10min；To be in after grinding
The predecessor of existing solid powdery, which is placed in small-sized reaction kettle, carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；Adjust temperature
Degree is 180 DEG C, starts crystallization, crystallization time 20h；Crystallization terminates cooled to room temperature, uses deionized water successively
With acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecular screen primary
Powder roasts at 550 DEG C, roasts 4h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 5.84wt%.
Embodiment 10：
By reaction raw materials aluminium isopropoxide, phosphorous acid, ammonium fluoride, di-n-propylamine and nano silicon dioxide proportionally 1Al2O3:
0.8P2O5:1F:0.1SiO2:0.3DPA accurate weighings, are uniformly mixed among mortar, and hand lapping 10min；It will be ground
The predecessor of presentation solid powdery, which is placed in small-sized reaction kettle, afterwards carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；It adjusts
It is 200 DEG C to save temperature, starts crystallization, crystallization time 20h；Crystallization terminates cooled to room temperature, successively using go from
Sub- water and acetone centrifuge washing, until upper liquid is clarified, dry 150min, obtains molecular screen primary powder at 110 DEG C；Molecule
Sieve original powder roasts at 550 DEG C, roasts 4h, obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 3.70wt%.
Claims (2)
1. a kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves, it is characterised in that：Reactant is set uniformly to mix using grinding means
It closes, in the case where additionally not adding water and other liquid fluxs, merely with the self-contained a small amount of water of reactant, realizes low mould
The synthesis of the AEL type silicoaluminophosphamolecular molecular sieves of silicon atom same order elements, step are when plate agent dosage：
（1）By reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, then uniformly
It is mixed among mortar, and 10 ~ 20min of hand lapping；
（2）Predecessor after grinding is placed in small-sized reaction kettle and carries out activating pretreatment, under 80 DEG C of environment constant temperature 8 ~
12h, it is 160 ~ 200 DEG C then to adjust temperature, starts crystallization, and crystallization time is 10 ~ 20h；
（3）Crystallization terminates cooled to room temperature, uses deionized water and acetone centrifuge washing successively, until upper liquid is clear
Until clear, dry 150min, obtains molecular screen primary powder at 110 DEG C；
（4）By step（3）The molecular screen primary powder of acquisition roasts at 550-600 DEG C, roasts 3 ~ 5h, obtains AEL type silicoaluminophosphate
Molecular sieve powder；
Source of aluminium is aluminium isopropoxide, with Al2O3Meter；Phosphorus source is phosphoric acid or phosphorous acid, with P2O5Meter；Fluorine source is hydrofluoric acid or fluorination
Ammonium, in terms of F；Template is di-n-propylamine or diisopropylamine；Silicon source be aerosil, nano silicon dioxide or Ludox,
With SiO2Meter；
It is described reaction original mixture specific molar ratio be：Al2O3:P2O5:F:SiO2:DPA/DIPA is：1:（0.8~1.2）:
1:（0.1~0.4）:（0.1~0.3）.
2. the synthetic method of AEL types silicoaluminophosphamolecular molecular sieves according to claim 1, it is characterised in that：Synthesize AEL type phosphorus
Sour Si-Al molecular sieve is tested through inductively coupled plasma atomic emission spectrometry, and silicon content is distributed in 3wt% ~ 10wt%
In range.
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| CN103864088A (en) * | 2014-03-07 | 2014-06-18 | 浙江大学 | Method for synthesizing molecular sieve by solid phase grinding |
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