CN106629759A - Synthetic method of AEL type silicoaluminophosphate molecular sieve - Google Patents
Synthetic method of AEL type silicoaluminophosphate molecular sieve Download PDFInfo
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- CN106629759A CN106629759A CN201710000437.9A CN201710000437A CN106629759A CN 106629759 A CN106629759 A CN 106629759A CN 201710000437 A CN201710000437 A CN 201710000437A CN 106629759 A CN106629759 A CN 106629759A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 42
- 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 42
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 44
- 230000008025 crystallization Effects 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 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 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 230000003213 activating effect Effects 0.000 claims description 13
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 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
- 239000000377 silicon dioxide Substances 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
- 229910002796 Si–Al Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 241000269350 Anura Species 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 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
- 239000004411 aluminium 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
- 239000000376 reactant Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000006228 supernatant Substances 0.000 abstract 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 5
- 150000002576 ketones Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003292 glue Substances 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
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method 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
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
The invention discloses a synthetic method of an AEL type silicoaluminophosphate molecular sieve. The synthetic method comprises the following steps: (1) accurately weighing an aluminum source, a phosphorous source, a fluorine source, a template reagent and a silicon source serving as reaction raw materials in a specific molar ratio, uniformly mixing the aluminum source, the phosphorous source, the fluorine source, the template reagent and the silicon source in a mortar, and manually grinding for 10 to 20 minutes; (2) placing the ground precursor in a small-sized reaction kettle to perform an activation pretreatment, preserving heat at the temperature of 80 DEG C for 8 to 12 hours, adjusting the temperature to 160 to 200 DEG C, and starting to crystalize for 10 to 20 hours; (3) naturally cooling to the room temperature after finishing the crystallization reaction, performing centrifugal washing by using deionized water and acetone in sequence until supernatant is clear, and drying at the temperature of 110 DEG C for 150 minutes to obtain molecular sieve raw powder; (4) sintering the molecular sieve raw powder obtained in the step (3) at the temperature of 550 to 600 DEG C for 3 to 5 hours to obtain AEL type silicoaluminophosphate molecular sieve powder.
Description
Technical field
The present invention relates to the synthetic technology of silicoaluminophosphamolecular molecular sieves, belongs 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 devoted to the research in silicoaluminophosphamolecular molecular sieves synthetic route, it is desirable to find while its catalytic performance is not affected, energy
Enough new ways that is simple and effective and inexpensively synthesizing such material.
AEL types silicoaluminophosphamolecular molecular sieves as SAPO-n molecular sieves a member, with one-dimensional ten annulus pore passage structure,
Its appropriate acidic site causes it that splendid catalytic performance is shown in hygrogenating isomerization reaction.
Traditional AEL types silicoaluminophosphamolecular molecular sieves are prepared using water/solvent-thermal process method, and this method has synthetic material pure
The advantages of degree is higher, particle diameter is easy to control, but it utilizes solvent to generate to environmentally undesirable garbage unavoidably, and crystallization process
Used in water equal solvent vaporization zone come high-voltage problem also make compound experiment have certain potential safety hazard.There is researcher to utilize ion
Liquid is carrying out the synthesis of silicoaluminophosphamolecular molecular sieves, although can successfully solve high-voltage problem, but this kind of synthetic method molecular sieve
The scope of application is narrower, and ionic liquid price is high causes relative cost too high.
In recent years, under the situation that clean environment and Environmental security are taken seriously further, to make AEL types SAPO point
Son sieve preferably plays its catalysis advantage, then explore a kind of high-efficiency synthesis method of low cost very urgent.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves.
The present invention is a kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves, reactant is uniformly mixed using grinding means
Close, in the case of without water and other liquid fluxs, realize the AEL type phosphorus of silicon atom isomorphous substitution during low template consumption
The synthesis of sour Si-Al molecular sieve, its step is：
（1）By reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, then uniformly
Among being mixed in mortar, and 10 ~ 20min of hand lapping；
（2）Predecessor after grinding is placed in small-sized reactor 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 to naturally cool to room temperature, successively using deionized water and acetone centrifuge washing, until upper liquid is clear
Till clear, 150min is dried at 110 DEG C, obtains molecular screen primary powder；
（4）By step（3）The molecular screen primary powder of acquisition roasting at 550-600 DEG C, 3 ~ 5h of roasting obtains AEL type SAPOs
Molecular sieve powder；
Source of aluminium is aluminum isopropylate., with Al2O3Meter；Phosphorus source is phosphoric acid or phosphorous acid, with P2O5Meter；Fluorine source is Fluohydric acid. or fluorine
Change ammonium, in terms of F；Template is di-n-propylamine or diisopropylamine；Silicon source is that aerosil, nano silicon or silicon are molten
Glue, 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 possesses following advantage compared with the method for other synthesis AEL type silicoaluminophosphamolecular molecular sieves：Crystallization can be obtained
Preferable AEL types silicoaluminophosphamolecular molecular sieves are spent, building-up process is anhydrous and solvent is participated in, and step is safe and simple, and template is used
Amount is less, and utilization rate is high, so that preparation cost is cheap, 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 embodiment
The present invention is a kind of synthetic method of AEL types silicoaluminophosphamolecular molecular sieves, reactant is uniformly mixed using grinding means
Close, in the case of without water and other liquid fluxs, realize the AEL type phosphorus of silicon atom isomorphous substitution during low template consumption
The synthesis of sour Si-Al molecular sieve, its step is：
（1）By reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, then uniformly
Among being mixed in mortar, and 10 ~ 20min of hand lapping；
（2）Predecessor after grinding is placed in small-sized reactor 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 to naturally cool to room temperature, successively using deionized water and acetone centrifuge washing, until upper liquid is clear
Till clear, 150min is dried at 110 DEG C, obtains molecular screen primary powder；
（4）By step（3）The molecular screen primary powder of acquisition roasting at 550-600 DEG C, 3 ~ 5h of roasting obtains AEL type SAPOs
Molecular sieve powder；
Source of aluminium is aluminum isopropylate., with Al2O3Meter；Phosphorus source is phosphoric acid or phosphorous acid, with P2O5Meter；Fluorine source is Fluohydric acid. or fluorine
Change ammonium, in terms of F；Template is di-n-propylamine or diisopropylamine；Silicon source is that aerosil, nano silicon or silicon are molten
Glue, 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, synthesizes AEL type silicoaluminophosphamolecular molecular sieves Jing inductively coupled plasma atomic emissions
Spectrographic method is tested, and its silicon content is distributed in the range of 3wt% ~ 10wt%.
Above-described synthetic method, synthesizes drawing without water and other solvents during AEL type silicoaluminophosphamolecular molecular sieves
Enter, and crystallization is carried out under the conditions of low template consumption.
The present invention will be further described for below example, but be embodied as operation and be not limited in embodiment.
Embodiment 1：
By reaction raw materials aluminum isopropylate., phosphoric acid, Fluohydric 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；To be presented solid after grinding
The predecessor of body powder is placed in small-sized reactor carries out activating pretreatment, the constant temperature 8h under 80 DEG C of environment；Adjusting temperature is
180 DEG C, start crystallization, crystallization time is 12h；Crystallization terminates to naturally cool to room temperature, successively using deionized water and third
Ketone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min is dried, and obtains molecular screen primary powder；Molecular screen primary powder exists
Roasting at 550 DEG C, roasting 3h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 7.21wt%.
Embodiment 2：
By reaction raw materials aluminum isopropylate., phosphoric acid, Fluohydric acid., diisopropylamine and nano silicon proportionally 1Al2O3:1P2O5:
1F:0.2SiO2:0.2DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 20min；To present after grinding
The predecessor of solid powdery is placed in small-sized reactor carries out activating pretreatment, the constant temperature 8h under 80 DEG C of environment；Adjust temperature
For 180 DEG C, start crystallization, crystallization time is 12h；Crystallization terminates to naturally cool to room temperature, successively using deionized water and
Acetone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min is dried, and obtains molecular screen primary powder；Molecular screen primary powder
The roasting at 550 DEG C, roasting 3h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 4.56wt%.
Embodiment 3：
By reaction raw materials aluminum isopropylate., phosphorous acid, Fluohydric acid., diisopropylamine and nano silicon proportionally 1Al2O3:
1.2P2O5:1F:0.4SiO2:0.3DIPA accurate weighings, are uniformly mixed among mortar, and hand lapping 10min；It will be ground
Afterwards the predecessor of presentation solid powdery is placed in small-sized reactor and carries out activating pretreatment, the constant temperature 8h under 80 DEG C of environment；Adjust
Section temperature is 180 DEG C, starts crystallization, and crystallization time is 12h；Crystallization terminates to naturally cool to room temperature, successively using go from
Sub- water and acetone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min are dried, and obtain molecular screen primary powder；Molecule
The former powder roasting at 600 DEG C of sieve, roasting 5h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 9.14wt%.
Embodiment 4：
By reaction raw materials aluminum isopropylate., phosphoric acid, Fluohydric 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；Solid will be presented after grinding
The predecessor of powder is placed in small-sized reactor carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；Adjusting temperature is
200 DEG C, start crystallization, crystallization time is 20h；Crystallization terminates to naturally cool to room temperature, successively using deionized water and third
Ketone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min is dried, and obtains molecular screen primary powder；Molecular screen primary powder exists
Roasting at 550 DEG C, roasting 5h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 3.27wt%.
Embodiment 5：
By reaction raw materials aluminum isopropylate., phosphoric acid, Fluohydric 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；To be presented solid after grinding
The predecessor of body powder is placed in small-sized reactor carries out activating pretreatment, the constant temperature 10h under 80 DEG C of environment；Adjusting temperature is
200 DEG C, start crystallization, crystallization time is 20h；Crystallization terminates to naturally cool to room temperature, successively using deionized water and third
Ketone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min is dried, and obtains molecular screen primary powder；Molecular screen primary powder exists
Roasting at 550 DEG C, roasting 5h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 8.43wt%.
Embodiment 6：
By reaction raw materials aluminum isopropylate., 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
Afterwards the predecessor of presentation solid powdery is placed in small-sized reactor and carries out activating pretreatment, the constant temperature 10h under 80 DEG C of environment；Adjust
Section temperature is 180 DEG C, starts crystallization, and crystallization time is 12h；Crystallization terminates to naturally cool to room temperature, successively using go from
Sub- water and acetone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min are dried, and obtain molecular screen primary powder；Molecule
The former powder roasting at 550 DEG C of sieve, roasting 4h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 3.86wt%.
Embodiment 7：
By reaction raw materials aluminum isopropylate., 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；To present after grinding
The predecessor of solid powdery is placed in small-sized reactor carries out activating pretreatment, the constant temperature 10h under 80 DEG C of environment；Adjust temperature
For 180 DEG C, start crystallization, crystallization time is 20h；Crystallization terminates to naturally cool to room temperature, successively using deionized water and
Acetone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min is dried, and obtains molecular screen primary powder；Molecular screen primary powder
The roasting at 550 DEG C, roasting 4h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 8.81wt%.
Embodiment 8：
By reaction raw materials aluminum isopropylate., 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
Afterwards the predecessor of presentation solid powdery is placed in small-sized reactor and carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；Adjust
Section temperature is 180 DEG C, starts crystallization, and crystallization time is 12h；Crystallization terminates to naturally cool to room temperature, successively using go from
Sub- water and acetone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min are dried, and obtain molecular screen primary powder；Molecule
The former powder roasting at 550 DEG C of sieve, roasting 4h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 4.37wt%.
Embodiment 9：
By reaction raw materials aluminum isopropylate., 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 presented solid after grinding
The predecessor of body powder is placed in small-sized reactor carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；Adjusting temperature is
180 DEG C, start crystallization, crystallization time is 20h；Crystallization terminates to naturally cool to room temperature, successively using deionized water and third
Ketone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min is dried, and obtains molecular screen primary powder；Molecular screen primary powder exists
Roasting at 550 DEG C, roasting 4h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 5.84wt%.
Embodiment 10：
By reaction raw materials aluminum isopropylate., phosphorous acid, ammonium fluoride, di-n-propylamine and nano silicon proportionally 1Al2O3:
0.8P2O5:1F:0.1SiO2:0.3DPA accurate weighings, are uniformly mixed among mortar, and hand lapping 10min；It will be ground
Afterwards the predecessor of presentation solid powdery is placed in small-sized reactor and carries out activating pretreatment, the constant temperature 12h under 80 DEG C of environment；Adjust
Section temperature is 200 DEG C, starts crystallization, and crystallization time is 20h；Crystallization terminates to naturally cool to room temperature, successively using go from
Sub- water and acetone centrifuge washing, till upper liquid is clarified, at 110 DEG C 150min are dried, and obtain molecular screen primary powder；Molecule
The former powder roasting at 550 DEG C of sieve, roasting 4h obtains the AEL type silicoaluminophosphamolecular molecular sieves that silicone content is 3.70wt%.
Claims (3)
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
Close, in the case of without water and other liquid fluxs, realize the AEL type phosphorus of silicon atom isomorphous substitution during low template consumption
The synthesis of sour Si-Al molecular sieve, its step is：
（1）By reaction raw materials silicon source, phosphorus source, Fluorine source, template and silicon source according to specific molar ratio accurate weighing, then uniformly
Among being mixed in mortar, and 10 ~ 20min of hand lapping；
（2）Predecessor after grinding is placed in small-sized reactor 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 to naturally cool to room temperature, successively using deionized water and acetone centrifuge washing, until upper liquid is clear
Till clear, 150min is dried at 110 DEG C, obtains molecular screen primary powder；
（4）By step（3）The molecular screen primary powder of acquisition roasting at 550-600 DEG C, 3 ~ 5h of roasting obtains AEL type SAPOs
Molecular sieve powder；
Source of aluminium is aluminum isopropylate., with Al2O3Meter；Phosphorus source is phosphoric acid or phosphorous acid, with P2O5Meter；Fluorine source is Fluohydric acid. or fluorination
Ammonium, in terms of F；Template is di-n-propylamine or diisopropylamine；Silicon source be aerosil, nano silicon 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：Synthesis AEL type phosphorus
Sour Si-Al molecular sieve Jing ICP-AESs test, its silicon content is distributed in 3wt% ~ 10wt%
In the range of.
3. the synthetic method of AEL types silicoaluminophosphamolecular molecular sieves according to claim 1, it is characterised in that：Synthesis AEL type phosphorus
Introducing without water He other solvents during sour Si-Al molecular sieve, and crystallization enters under the conditions of low template consumption
OK.
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