CN108545758A - The method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve in strong basicity system - Google Patents
The method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve in strong basicity system Download PDFInfo
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- CN108545758A CN108545758A CN201810310028.3A CN201810310028A CN108545758A CN 108545758 A CN108545758 A CN 108545758A CN 201810310028 A CN201810310028 A CN 201810310028A CN 108545758 A CN108545758 A CN 108545758A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 80
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 80
- 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 80
- 239000004411 aluminium Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 348
- 230000008025 crystallization Effects 0.000 claims abstract description 347
- 238000006243 chemical reaction Methods 0.000 claims abstract description 203
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 170
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 86
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 86
- 229910001868 water Inorganic materials 0.000 claims abstract description 80
- 238000003756 stirring Methods 0.000 claims abstract description 61
- 238000001816 cooling Methods 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000009415 formwork Methods 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 118
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 70
- 238000007605 air drying Methods 0.000 claims description 59
- 230000035484 reaction time Effects 0.000 claims description 58
- 229910052681 coesite Inorganic materials 0.000 claims description 42
- 229910052906 cristobalite Inorganic materials 0.000 claims description 42
- 229910052682 stishovite Inorganic materials 0.000 claims description 42
- 229910052905 tridymite Inorganic materials 0.000 claims description 42
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 25
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 claims description 7
- 229960003263 cyclopentamine Drugs 0.000 claims description 7
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 57
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000009972 noncorrosive effect Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 126
- 238000002360 preparation method Methods 0.000 description 57
- 229910052710 silicon Inorganic materials 0.000 description 57
- 239000010703 silicon Substances 0.000 description 57
- 239000012153 distilled water Substances 0.000 description 56
- 238000005303 weighing Methods 0.000 description 52
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 49
- 229910017119 AlPO Inorganic materials 0.000 description 24
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 239000000908 ammonium hydroxide Substances 0.000 description 14
- PFCBHFDNVFQUJI-UHFFFAOYSA-N 3-methylbut-2-en-1-amine Chemical compound CC(C)=CCN PFCBHFDNVFQUJI-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 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
- 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
- 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
- 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
Landscapes
- 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 present invention relates to the technologies of preparing of molecular sieve, it is desirable to provide a method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve in strong basicity system.Including：First phosphorus silicon source AlPO4, organic formwork agent R and water are added in reaction kettle, are uniformly mixed；Then silica is added, starts crystallization after stirring evenly；After cooling is completed in reaction, washing to neutrality, drying roasts to obtain phosphate aluminium molecular sieve or aluminium silicophosphate molecular sieve.The phosphorus source that the present invention uses be aluminum phosphate rather than traditional crystallization used in phosphoric acid, non-corrosive or toxicity, raw material is easy to get.The molecular sieve of synthesis has good alkali resistance, the not easy in inactivation in MTO reactions.Synthesis step simplifies, and yield and one-pot utilization rate are all enhanced.Production cost can be greatly reduced, energy-saving and emission-reduction have huge prospects for commercial application.It can be widely applied to the synthesis of a variety of aluminium silicophosphate molecular sieves or phosphate aluminium molecular sieve.Product maintains good crystallinity and purity, also has higher specific surface area.
Description
Technical field
The invention belongs to the technologies of preparing of molecular sieve, more particularly to synthesizing P-Al molecular sieve or silicon phosphorus in strong basicity system
The method of aluminum molecular screen.
Background technology
The beginning of the eighties in 19th century, U.S. combinating carbide company (U.C.C) develop after phosphate aluminium molecular sieve (AlPO-n)
A kind of novel molecular sieve material, aluminium silicophosphate molecular sieve (SAPO-n).The skeleton of SAPO-n is by SiO2、AlO2 -、PO2 +Three kinds of four sides
Body basic unit is constituted so that being in the skeleton of the AlPO-n molecular sieves of electroneutral originally has tradable charge, forms class
It is similar to the Bronsted acidity of Si-Al molecular sieve, while the thermostabilization with AlPO-n molecular sieves and hydrothermal stability again.Thus,
SAPO-n molecular sieves have been widely used in catalysis industry field because of its excellent physico-chemical property.
Since molecular sieve research and industry are closely bound up, the exploration of new Zeolite synthesis route is closed as researchers
The hot spot of note.The characteristics of earliest Zeolite synthesis route synthesizes for hydro-thermal method, the route is using a large amount of water as solvent
It is synthesized.And need to use using phosphoric acid as phosphorus source, in commercial Application, it is not only be easy to cause environmental pollution, is also unfavorable for
Industrial operation.
Large-scale application is still hydro-thermal method route in industrial synthetic route at present, and colloidal sol is required in synthesis condition
PH value is neutral or faintly acid in system.If aluminium phosphate molecular sieve or silicon phosphorus aluminium molecule can be made under alkaline system
Sieve, it will be an important breakthrough.
Invention content
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide one kind in strong basicity system
The method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve.
To solve technical problem, solution of the invention is：
A kind of method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve under alkaline system is provided, is included the following steps：
(1) Al: P: H is pressed2O∶R∶SiO2Molar ratio be 1: 1: 15~90: 0.03~7.0: 0~0.5, respectively measure phosphorus aluminium
Source AlPO4, organic formwork agent R, water and silica；First by phosphorus silicon source AlPO4, organic formwork agent R and water be added in reaction kettle,
It is uniformly mixed；Then silica is added, starts crystallization after stirring evenly；Controlling reaction temperature is 180~220
DEG C, the reaction time is for 24 hours~5d, and the pH value of reaction system keeps 12~14；
(2) after crystallization completes cooling, reaction product is taken out；It is first washed with deionized to neutrality, then at 80 DEG C
Under air drying, obtain molecular screen primary powder；
(3) molecular screen primary powder is roasted to 4 hours in 600 DEG C of air to get phosphate aluminium molecular sieve or aluminium silicophosphate molecular sieve.
In the present invention, the organic formwork agent R is organic ammonium salt or organic amine, is the mixed of following any one or a few
Close object：Tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetramethylammonium hydroxide, di-n-propylamine, triethylamine, N, N, N- front threes
Base, 1- adamantane ammonium hydroxide (TMAdaOH), cyclopentamine, N, N, N, N- tetramethyls -1,6- hexamethylene diamine, N, N,-diisopropyl second
Amine, diethanol amine or triethanolamine.
In the present invention, the organic formwork agent is any one following：Mass fraction is 20%~35% tetraethyl
Ammonium hydroxide aqueous solution, mass fraction are 20%~40% tetrapropylammonium hydroxide solutions or tetramethylammonium hydroxide
Five water crystallization solids.
Further include that CuSO is added into reaction system in the step (1) in the present invention4·5H2O controls its addition
Amount makes Al: Cu molar ratio be 1: 0.05~0.2.
Inventive principle describes：
In the building-up process of general phosphate aluminium molecular sieve, phosphoric acid can be used；And phosphoric acid is middle strong acid, during heating with
The progress of reaction, gradually dissociates Bronsted acid, influence in reaction process or reaction after the completion of system pH value, cause system at
Neutral or faintly acid system.PH value in the reaction system of the present invention is to be closed with general phosphate aluminium molecular sieve under strong basicity system
It is in neutrality in architectonical or faintly acid is different.In the building-up process of the present invention, any acidic materials, all raw materials are not added
It is neutral or strong basicity.In heating building-up process, Bronsted acid will not be stable in the presence of in solution under strong basicity system, no
PH in solution can be had an impact.The molecular sieve synthesized under strongly alkaline conditions has good alkali resistance, in MTO reactions
Not easy in inactivation, have potential application the present invention for some important catalysis reactions has in practical chemical production field
Significance.
Compared with prior art, the beneficial effects of the invention are as follows：
1, the phosphorus source that uses of the present invention be aluminum phosphate rather than traditional crystallization used in phosphoric acid, it is non-corrosive or malicious
Property, raw material is easy to get.
2, the molecular sieve that the present invention synthesizes under strongly alkaline conditions has good alkali resistance, not volatile in MTO reactions
It is living.
3, synthetic route of the invention relates only to the mixing of primary raw materials, the more traditional side of synthesis step before crystallization
Method greatly simplifies, and yield and one-pot utilization rate are all enhanced.It can be greatly reduced production cost, energy-saving and emission-reduction,
There is huge prospects for commercial application.
4, synthetic method proposed by the present invention can be widely used in a variety of aluminium silicophosphate molecular sieves or phosphate aluminium molecular sieve
Synthesis.Obtained product not only maintains good crystallinity and purity, also has many advantages, such as higher specific surface area.Product pair
The present invention is had potential application in some important catalysis reactions to be of great significance in practical chemical production field.
Description of the drawings
Fig. 1 is AlPO made from specific embodiment 54The XRD spectra of -18 molecular sieves.
Fig. 2 is AlPO made from specific embodiment 54The SEM pictures (high power) of -18 molecular sieves.
Fig. 3 is AlPO made from specific embodiment 54The SEM pictures (low power) of -18 molecular sieves.
Fig. 4 is AlPO made from specific embodiment 54The nitrogen adsorption isotherm of -18 molecular sieves.
Fig. 5 is the XRD spectra of SAPO-34 molecular sieves made from specific embodiment 8.
Fig. 6 is the SEM pictures (high power) of SAPO-34 molecular sieves made from specific embodiment 8.
Fig. 7 is the SEM pictures (low power) of SAPO-34 molecular sieves made from specific embodiment 8.
Fig. 8 is the XRD spectra of SAPO-44 molecular sieves made from specific embodiment 15.
Fig. 9 is the SEM pictures (high power) of SAPO-44 molecular sieves made from specific embodiment 15.
Figure 10 is the SEM pictures (low power) of SAPO-44 molecular sieves made from specific embodiment 15.
Figure 11 is the XRD spectra of SAPO-56 molecular sieves made from specific embodiment 20.
Figure 12 is the SEM pictures (high power) of SAPO-56 molecular sieves made from specific embodiment 20.
Figure 13 is the SEM pictures (low power) of SAPO-56 molecular sieves made from specific embodiment 20.
Figure 14 is the nitrogen adsorption isotherm of SAPO-56 molecular sieves made from specific embodiment 20.
Figure 15 is the XRD spectra of SAPO-37 molecular sieves made from specific embodiment 26.
Figure 16 is the SEM pictures (high power) of SAPO-37 molecular sieves made from specific embodiment 26.
Figure 17 is the SEM pictures (low power) of SAPO-37 molecular sieves made from specific embodiment 26.
Figure 18 is the nitrogen adsorption isotherm of SAPO-37 molecular sieves made from specific embodiment 26.
Figure 19 is AlPO made from specific embodiment 314The XRD spectra of -5 molecular sieves.
Figure 20 is the XRD spectra of SAPO-5 molecular sieves made from specific embodiment 36.
Figure 21 is AlPO made from specific embodiment 454The XRD spectra of -11 molecular sieves.
Figure 22 is the XRD spectra of SAPO-11 molecular sieves made from specific embodiment 49.
Figure 23 is the XRD spectra of Cu-SAPO-34 molecular sieves made from specific embodiment 57.
Specific implementation mode：
The following examples can make the professional technician of this profession that the present invention be more fully understood, but not with any side
The formula limitation present invention.
Embodiment 1：AlPO4The preparation of -18 samples
(1) by silicon and aluminum source AlPO4, 20%TEAOH (tetraethyl ammonium hydroxide) aqueous solution weighing pour into beaker, be stirred
2h is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 200 DEG C, reaction time 2d,
PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: TEAOH 1: 1: 30:
3.5。
(2) crystallization product is obtained after the completion of crystallization, crystallization product is cooled down at room temperature, can also be used
Cooling water rushes crystallization product and accelerates cooling rate, is then washed crystallization product to neutrality with deionized water, 80
Air drying at DEG C, obtains molecular screen primary powder.
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-18
Molecular sieve.
Embodiment 2：AlPO4The preparation of -18 samples
(1) by silicon and aluminum source AlPO4, 35%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, stir
It is fitted into reaction kettle after uniformly and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 2d, PH=14；
When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: TEAOH 1: 1: 70: 0.5.
(2) crystallization product is obtained after the completion of crystallization, crystallization product is cooled down at room temperature, can also be used
Cooling water rushes crystallization product and accelerates cooling rate, is then washed crystallization product to neutrality with deionized water, 80
Air drying at DEG C, obtains molecular screen primary powder.
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-18
Molecular sieve.
Embodiment 3：AlPO4The preparation of -18 samples
(1) by silicon and aluminum source AlPO4, 20%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, stir
It is fitted into reaction kettle after uniformly and carries out crystallization, the reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=13；
When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: TEAOH 1: 1: 70: 0.5.
(2) crystallization product is obtained after the completion of crystallization, crystallization product is cooled down at room temperature, can also be used
Cooling water rushes crystallization product and accelerates cooling rate, is then washed crystallization product to neutrality with deionized water, 80
Air drying at DEG C, obtains molecular screen primary powder.
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-18
Molecular sieve.
Embodiment 4：AlPO4The preparation of -18 samples
(1) by silicon and aluminum source AlPO4, 35%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, stir
It is fitted into reaction kettle after uniformly and carries out crystallization, the reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=for 24 hours
13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: TEAOH 1: 1: 70: 0.5.
(2) crystallization product is obtained after the completion of crystallization, crystallization product is cooled down at room temperature, can also be used
Cooling water rushes crystallization product and accelerates cooling rate, is then washed crystallization product to neutrality with deionized water, 80
Air drying at DEG C, obtains molecular screen primary powder.
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-18
Molecular sieve.
Embodiment 5：AlPO4The preparation of -18 samples
(1) by silicon and aluminum source AlPO4, 30%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, stir
It is fitted into reaction kettle after uniformly and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；
When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: TEAOH 1: 1: 50: 2.0.
(2) crystallization product is obtained after the completion of crystallization, crystallization product is cooled down at room temperature, can also be used
Cooling water rushes crystallization product and accelerates cooling rate, is then washed crystallization product to neutrality with deionized water, 80
Air drying at DEG C, obtains molecular screen primary powder.
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-18
Molecular sieve.
Embodiment 6：The preparation of SAPO-34 samples
(1) by silicon and aluminum source AlPO4, 20%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, then add
Entering a small amount of silica, is fitted into after stirring evenly in reaction kettle and carries out crystallization, the reaction temperature of crystallization is 200 DEG C,
Reaction time is 2d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
TEAOH∶SiO2=1: 1: 40: 7.0: 0.02.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-34 points in 600 DEG C of air
Son sieve.
Embodiment 7：The preparation of SAPO-34 samples
(1) by silicon and aluminum source AlPO4, 35%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, then add
Enter a certain amount of silica, be fitted into after stirring evenly in reaction kettle and carry out crystallization, the reaction temperature of crystallization is 200
DEG C, reaction time 2d, PH=12；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
TEAOH∶SiO2=1: 1: 90: 1.5: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-34 points in 600 DEG C of air
Son sieve.
Embodiment 8：The preparation of SAPO-34 samples
(1) by silicon and aluminum source AlPO4, 30%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, then add
Enter a certain amount of silica, be fitted into after stirring evenly in reaction kettle and carry out crystallization, the reaction temperature of crystallization is 200
DEG C, reaction time 3d, PH=14；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
TEAOH∶SiO2=1: 1: 75: 4.0: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-34 points in 600 DEG C of air
Son sieve.
Embodiment 9：The preparation of SAPO-34 samples
(1) by silicon and aluminum source AlPO4, 20%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, then add
Enter a certain amount of silica, be fitted into after stirring evenly in reaction kettle and carry out crystallization, the reaction temperature of crystallization is 180
DEG C, reaction time 5d, PH=12；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
TEAOH∶SiO2=1: 1: 90: 1.5: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-34 points in 600 DEG C of air
Son sieve.
Embodiment 10：The preparation of SAPO-34 samples
(1) by silicon and aluminum source AlPO4, 35%TEAOH aqueous solutions and distilled water weighing pour into beaker, are stirred 2h, then add
Enter a certain amount of silica, be fitted into after stirring evenly in reaction kettle and carry out crystallization, the reaction temperature of crystallization is 220
DEG C, the reaction time is PH=14 for 24 hours；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
TEAOH∶SiO2=1: 1: 40: 7.0: 0.02；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-34 points in 600 DEG C of air
Son sieve.
Embodiment 11：The preparation of SAPO-44 samples
(1) by silicon and aluminum source AlPO4, cyclopentamine (C5H11N) and beaker is poured into distilled water weighing, is stirred 2h, adds
A small amount of silica is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 200 DEG C, instead
It is 3d, PH=14 between seasonable；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶C5H11N∶
SiO2=1: 1: 15: 1.0: 0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-44 points in 600 DEG C of air
Son sieve
Embodiment 12：The preparation of SAPO-44 samples
(1) by silicon and aluminum source AlPO4, cyclopentamine (C5H11N) and beaker is poured into distilled water weighing, is stirred 2h, adds
A certain amount of silica is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 200
DEG C, reaction time 3d, PH=14；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
C5H11N∶SiO2=1: 1: 50: 4.0: 0.50；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-44 points in 600 DEG C of air
Son sieve.
Embodiment 13：The preparation of SAPO-44 samples
(1) by silicon and aluminum source AlPO4, cyclopentamine (C5H11N) and beaker is poured into distilled water weighing, is stirred 2h, adds
A certain amount of silica is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 180
DEG C, reaction time 5d, PH=14；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
C5H11N∶SiO2=1: 1: 50: 4.0: 0.50；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-44 points in 600 DEG C of air
Son sieve.
Embodiment 14：The preparation of SAPO-44 samples
(1) by silicon and aluminum source AlPO4, cyclopentamine (C5H11N) and beaker is poured into distilled water weighing, is stirred 2h, adds
A certain amount of silica is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 220
DEG C, the reaction time is PH=14 for 24 hours；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
C5H11N∶SiO2=1: 1: 15: 1.0: 0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-44 points in 600 DEG C of air
Son sieve.
Embodiment 15：The preparation of SAPO-44 samples
(1) by silicon and aluminum source AlPO4, cyclopentamine (C5H11N) and beaker is poured into distilled water weighing, is stirred 2h, adds
A certain amount of silica is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 200
DEG C, reaction time 3d, PH=14；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶
C5H11N∶SiO2=1: 1: 30: 2.5: 0.25；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-44 points in 600 DEG C of air
Son sieve.
Embodiment 16：The preparation of SAPO-56 samples
(1) by silicon and aluminum source AlPO4, N, N, N, N- tetramethyl -1,6- hexamethylene diamines (C10H24N2) and distilled water weighing pour into burning
Cup, is stirred 2h, adds a small amount of silica, be fitted into after stirring evenly in reaction kettle and carry out crystallization, crystallization
Reaction temperature be 200 DEG C, reaction time 3d, PH=13；When crystallization, the Component molar of the reaction raw materials of addition matches
Meet, Al: P: H2O∶C10H24N2∶SiO2=1: 1: 15: 0.75: 0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-56 points in 600 DEG C of air
Son sieve.
Embodiment 17：The preparation of SAPO-56 samples
1) by silicon and aluminum source AlPO4, 3.1g N, N, N, N- tetramethyl -1,6- hexamethylene diamines (C10H24N2) and the weighing of 5g distilled water
Beaker is poured into, 2h is stirred, adds a certain amount of silica, it is anti-that progress crystallization in reaction kettle is fitted into after stirring evenly
It answers, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；When crystallization, the reaction raw materials of addition
Component molar proportioning meets, and Al: P: H2O∶C10H24N2∶SiO2=1: 1: 50: 3.0: 0.50；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-56 points in 600 DEG C of air
Son sieve.
Embodiment 18：The preparation of SAPO-56 samples
1) by silicon and aluminum source AlPO4, 3.1g N, N, N, N- tetramethyl -1,6- hexamethylene diamines (C10H24N2) and the weighing of 5g distilled water
Beaker is poured into, 2h is stirred, adds a certain amount of silica, it is anti-that progress crystallization in reaction kettle is fitted into after stirring evenly
It answers, the reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=14；When crystallization, the reaction raw materials of addition
Component molar proportioning meets, and Al: P: H2O∶C10H24N2∶SiO2=1: 1: 50: 3.0: 0.50；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-56 points in 600 DEG C of air
Son sieve.
Embodiment 19：The preparation of SAPO-56 samples
1) by silicon and aluminum source AlPO4, 3.1g N, N, N, N- tetramethyl -1,6- hexamethylene diamines (C10H24N2) and the weighing of 5g distilled water
Beaker is poured into, 2h is stirred, adds a certain amount of silica, it is anti-that progress crystallization in reaction kettle is fitted into after stirring evenly
It answers, the reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=14 for 24 hours；When crystallization, the reaction raw materials of addition
Component molar proportioning meets, and Al: P: H2O∶C10H24N2∶SiO2=1: 1: 15: 0.75: 0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-56 points in 600 DEG C of air
Son sieve.
Embodiment 20：The preparation of SAPO-56 samples
1) by silicon and aluminum source AlPO4, 3.1g N, N, N, N- tetramethyl -1,6- hexamethylene diamines (C10H24N2) and the weighing of 5g distilled water
Beaker is poured into, 2h is stirred, adds a certain amount of silica, it is anti-that progress crystallization in reaction kettle is fitted into after stirring evenly
It answers, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；When crystallization, the reaction raw materials of addition
Component molar proportioning meets, and Al: P: H2O∶C10H24N2∶SiO2=1: 1: 30: 2.0: 0.25；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-56 points in 600 DEG C of air
Son sieve.
Embodiment 21：The preparation of SAPO-37 samples
(1) by silicon and aluminum source AlPO4, five water crystallization object of 20% tetrapropylammonium hydroxide (TPAOH) and ammonium hydroxide
(TMAOH·5H2O) and beaker is poured into distilled water weighing, is stirred 2h, a small amount of silica is added, after stirring evenly
It is fitted into reaction kettle and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；Crystallization is anti-
At once, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 15: 1.0:
0.01∶0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-37 points in 600 DEG C of air
Son sieve.
Embodiment 22：The preparation of SAPO-37 samples
1) by silicon and aluminum source AlPO4, five water of 30% tetrapropylammonium hydroxide (TPAOH) and a certain amount of ammonium hydroxide
Beaker is poured into crystal (TMAOH5H2O) and distilled water weighing, is stirred 2h, adds a small amount of silica, and stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 15:
1.0∶0.15∶0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-37 points in 600 DEG C of air
Son sieve.
Embodiment 23：The preparation of SAPO-37 samples
1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 80:
4.0∶0.01∶0.50；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-37 points in 600 DEG C of air
Son sieve.
Embodiment 24：The preparation of SAPO-37 samples
1) by silicon and aluminum source AlPO4, 20% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=14；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 80:
4.0∶0.01∶0.50；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-37 points in 600 DEG C of air
Son sieve.
Embodiment 25：The preparation of SAPO-37 samples
1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=14 for 24 hours；
When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 15:
1.0∶0.15∶0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-37 points in 600 DEG C of air
Son sieve.
Embodiment 26：The preparation of SAPO-37 samples
1) by silicon and aluminum source AlPO4, 30% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 42:
2.5∶0.08∶0.25；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-37 points in 600 DEG C of air
Son sieve.
Embodiment 27：AlPO4The preparation of -5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, stirring is
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: DPA=1: 1: 15: 1.0；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4- 5 points
Son sieve.
Embodiment 28：AlPO4The preparation of -5 samples
(1) by silicon and aluminum source AlPO4, triethylamine (TPA) and distilled water weighing pour into beaker, are stirred 2h, stir evenly
It is fitted into afterwards in reaction kettle and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；Crystallization
When reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: DPA=1: 1: 80: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4- 5 points
Son sieve.
Embodiment 29：AlPO4The preparation of -5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, stirring is
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=13；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: DPA=1: 1: 15: 1.0；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4- 5 points
Son sieve.
Embodiment 30：AlPO4The preparation of -5 samples
(1) by silicon and aluminum source AlPO4, triethylamine (TPA) and distilled water weighing pour into beaker, are stirred 2h, stir evenly
It is fitted into afterwards in reaction kettle and carries out crystallization, the reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=13 for 24 hours；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: DPA=1: 1: 80: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4- 5 points
Son sieve.
Embodiment 31：AlPO4The preparation of -5 samples
(1) by silicon and aluminum source AlPO4, triethylamine (TPA) and distilled water weighing pour into beaker, are stirred 2h, stir evenly
It is fitted into afterwards in reaction kettle and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；Crystallization
When reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O: DPA=1: 1: 42: 0.75；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4- 5 points
Son sieve.
Embodiment 32：The preparation of SAPO-5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, add
A small amount of silica is fitted into reaction kettle after stirring evenly and carries out crystallization, and the reaction temperature of crystallization is 200 DEG C,
Reaction time is 3d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶DPA∶
SiO2=1: 1: 80: 0.5: 0.1；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-5 points in 600 DEG C of air
Son sieve.
Embodiment 33：The preparation of SAPO-5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, stirring is
A small amount of silica is added after even, is fitted into reaction kettle and is carried out crystallization, the reaction temperature of crystallization is 200 DEG C,
Reaction time is 3d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶DPA∶
SiO2=1: 1: 15: 1.0: 0.5；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-5 points in 600 DEG C of air
Son sieve.
Embodiment 34：The preparation of SAPO-5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, stirring is
A small amount of silica is added after even, is fitted into reaction kettle and is carried out crystallization, the reaction temperature of crystallization is 180 DEG C,
Reaction time is 5d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶DPA∶
SiO2=1: 1: 80: 0.5: 0.1；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-5 points in 600 DEG C of air
Son sieve.
Embodiment 35：The preparation of SAPO-5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, stirring is
A small amount of silica is added after even, is fitted into reaction kettle and is carried out crystallization, the reaction temperature of crystallization is 220 DEG C,
Reaction time is PH=13 for 24 hours；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶DPA
∶SiO2=1: 1: 15: 1.0: 0.5；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-5 points in 600 DEG C of air
Son sieve.
Embodiment 36：The preparation of SAPO-5 samples
(1) by silicon and aluminum source AlPO4, di-n-propylamine (DPA) and distilled water weighing pour into beaker, are stirred 2h, stirring is
A small amount of silica is added after even, is fitted into reaction kettle and is carried out crystallization, the reaction temperature of crystallization is 200 DEG C,
Reaction time is 3d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶DPA∶
SiO2=1: 1: 40: 0.75: 0.3；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-5 points in 600 DEG C of air
Son sieve.
Embodiment 37：AlPO4The preparation of -31 samples
(1) by silicon and aluminum source AlPO4, 20% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, is fitted into after stirring evenly in reaction kettle and carries out crystalline substance
Change reaction, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；When crystallization, the reaction of addition is former
The Component molar proportioning of material meets, and Al: P: H2O: TPAOH: TMAOH=1: 1: 20: 0.25: 0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-31
Molecular sieve.
Embodiment 38：AlPO4The preparation of -31 samples
(1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, is fitted into after stirring evenly in reaction kettle and carries out crystalline substance
Change reaction, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；When crystallization, the reaction of addition is former
The Component molar proportioning of material meets, and Al: P: H2O: TPAOH: TMAOH=1: 1: 15: 0.05: 0.01；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-31
Molecular sieve.
Embodiment 39：AlPO4The preparation of -31 samples
(1) by silicon and aluminum source AlPO4, 20% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, is fitted into after stirring evenly in reaction kettle and carries out crystalline substance
Change reaction, the reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=13；When crystallization, the reaction of addition is former
The Component molar proportioning of material meets, and Al: P: H2O: TPAOH: TMAOH=1: 1: 15: 0.02: 0.03；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-31
Molecular sieve.
Embodiment 40：AlPO4The preparation of -31 samples
(1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, is fitted into after stirring evenly in reaction kettle and carries out crystalline substance
Change reaction, the reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=13 for 24 hours；When crystallization, the reaction of addition is former
The Component molar proportioning of material meets, and Al: P: H2O: TPAOH: TMAOH=1: 1: 15: 0.01: 0.02；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-31
Molecular sieve.
Embodiment 41：The preparation of SAPO-31 samples
(1) by silicon and aluminum source AlPO4, 30% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a small amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 20:
0.03∶0.03∶0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-31 points in 600 DEG C of air
Son sieve.
Embodiment 42：The preparation of SAPO-31 samples
(1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a small amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=13；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 20:
0.25∶0.01∶0.05；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-31 points in 600 DEG C of air
Son sieve.
Embodiment 43：The preparation of SAPO-31 samples
(1) by silicon and aluminum source AlPO4, 20% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a small amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=13；It is brilliant
When changing reaction, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 20:
0.25∶0.04∶0.03；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-31 points in 600 DEG C of air
Son sieve.
Embodiment 44：The preparation of SAPO-31 samples
(1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a small amount of five water knot of ammonium hydroxide
Brilliant object (TMAOH5H2O) and beaker is poured into distilled water weighing, is stirred 2h, adds a small amount of silica, stirring is equal
It is fitted into reaction kettle after even and carries out crystallization, the reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=13 for 24 hours；
When crystallization, the Component molar proportioning of the reaction raw materials of addition meets, and Al: P: H2O∶TPAOH∶TMAOH∶SiO2=1: 1: 20:
0.25∶0.05∶0.5；
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-31 points in 600 DEG C of air
Son sieve.
Embodiment 45：AlPO4The preparation of -11 samples
(1) by silicon and aluminum source AlPO4, 20% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Distilled water weighing pour into beaker, be stirred 2h, be fitted into after stirring evenly in reaction kettle and carry out crystallization, crystallization it is anti-
It is 200 DEG C to answer temperature, reaction time 3d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition is full
Foot, Al: P: H2O: TPAOH: DPA=1: 1: 40: 0.15: 0.05.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-11
Molecular sieve.
Embodiment 46：AlPO4The preparation of -11 samples
(1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Distilled water weighing pour into beaker, be stirred 2h, be fitted into after stirring evenly in reaction kettle and carry out crystallization, crystallization it is anti-
It is 200 DEG C to answer temperature, reaction time 3d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition is full
Foot, Al: P: H2O: TPAOH: DPA=1: 1: 60: 0.45: 0.25.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-11
Molecular sieve.
Embodiment 47：AlPO4The preparation of -11 samples
(1) by silicon and aluminum source AlPO4, 30% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Distilled water weighing pour into beaker, be stirred 2h, be fitted into after stirring evenly in reaction kettle and carry out crystallization, crystallization it is anti-
It is 220 DEG C to answer temperature, and the reaction time is PH=13 for 24 hours；When crystallization, the Component molar proportioning of the reaction raw materials of addition is full
Foot, Al: P: H2O: TPAOH: DPA=1: 1: 50: 0.3: 0.15.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-11
Molecular sieve.
Embodiment 48：AlPO4The preparation of -11 samples
(1) by silicon and aluminum source AlPO4, 30% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Distilled water weighing pour into beaker, be stirred 2h, be fitted into after stirring evenly in reaction kettle and carry out crystallization, crystallization it is anti-
It is 180 DEG C to answer temperature, reaction time 5d, PH=13；When crystallization, the Component molar proportioning of the reaction raw materials of addition is full
Foot, Al: P: H2O: TPAOH: DPA=1: 1: 50: 0.3: 0.15.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to AlPO in 600 DEG C of air4-11
Molecular sieve.
Embodiment 49：The preparation of SAPO-11 samples
(1) by silicon and aluminum source AlPO4, 30% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, is fitted into reaction kettle and carries out after stirring evenly
The reaction temperature of crystallization, crystallization is 200 DEG C, reaction time 3d, PH=13；When crystallization, the reaction of addition
The Component molar proportioning of raw material meets, and Al: P: H2O∶TPAOH∶DPA∶SiO2=1: 1: 40: 0.45: 0.25: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-11 points in 600 DEG C of air
Son sieve.
Embodiment 50：The preparation of SAPO-11 samples
(1) by silicon and aluminum source AlPO4, 30% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, is fitted into reaction kettle and carries out after stirring evenly
The reaction temperature of crystallization, crystallization is 200 DEG C, reaction time 3d, PH=13；When crystallization, the reaction of addition
The Component molar proportioning of raw material meets, and Al: P: H2O∶TPAOH∶DPA∶SiO2=1: 1: 60: 0.15: 0.05: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-11 points in 600 DEG C of air
Son sieve.
Embodiment 51：The preparation of SAPO-11 samples
(1) by silicon and aluminum source AlPO4, 20% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, is fitted into reaction kettle and carries out after stirring evenly
The reaction temperature of crystallization, crystallization is 220 DEG C, and the reaction time is PH=13 for 24 hours；When crystallization, the reaction of addition
The Component molar proportioning of raw material meets, and Al: P: H2O∶TPAOH∶DPA∶SiO2=1: 1: 50: 0.3: 0.15: 0.3.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-11 points in 600 DEG C of air
Son sieve.
Embodiment 52：The preparation of SAPO-11 samples
(1) by silicon and aluminum source AlPO4, 40% tetrapropylammonium hydroxide (TPAOH) and a certain amount of di-n-propylamine (DPA) and
Beaker is poured into distilled water weighing, is stirred 2h, adds a large amount of silica, is fitted into reaction kettle and carries out after stirring evenly
The reaction temperature of crystallization, crystallization is 180 DEG C, reaction time 5d, PH=13；When crystallization, the reaction of addition
The Component molar proportioning of raw material meets, and Al: P: H2O∶TPAOH∶DPA∶SiO2=1: 1: 50: 0.3: 0.15: 0.3.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to SAPO-11 points in 600 DEG C of air
Son sieve.
Embodiment 53：The preparation of Cu-SAPO-34 samples
(1) by silicon and aluminum source AlPO4, tetraethylenepentamine (TEPA) and a certain amount of CuSO4·5H2O and distilled water weigh
Enter beaker, be stirred 2h, add a small amount of silica, is fitted into after stirring evenly in reaction kettle and carries out crystallization, it is brilliant
The reaction temperature for changing reaction is 200 DEG C, reaction time 3d, PH=14；When crystallization, the reaction raw materials of addition at centimorgan
You meet proportioning, and Al: P: H2O∶Cu∶TEPA∶SiO2=1: 1: 20: 0.05: 0.5: 0.1.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to Cu-SAPO- in 600 DEG C of air
34 molecular sieves.
Embodiment 54：The preparation of Cu-SAPO-34 samples
(1) by silicon and aluminum source AlPO4, tetraethylenepentamine (TEPA) and a certain amount of CuSO4·5H2O and distilled water weigh
Enter beaker, be stirred 2h, add a certain amount of silica, is fitted into after stirring evenly in reaction kettle and carries out crystallization,
The reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；When crystallization, the ingredient of the reaction raw materials of addition
Mol ratio meets, and Al: P: H2O∶Cu∶TEPA∶SiO2=1: 1: 50: 0.2: 3.0: 0.5.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to Cu-SAPO- in 600 DEG C of air
34 molecular sieves.
Embodiment 55：The preparation of Cu-SAPO-34 samples
(1) by silicon and aluminum source AlPO4, tetraethylenepentamine (TEPA) and a certain amount of CuSO4·5H2O and distilled water weigh
Enter beaker, be stirred 2h, add a certain amount of silica, is fitted into after stirring evenly in reaction kettle and carries out crystallization,
The reaction temperature of crystallization is 220 DEG C, and the reaction time is PH=14 for 24 hours；When crystallization, the reaction raw materials of addition at
Mol ratio is divided to meet, Al: P: H2O∶Cu∶TEPA∶SiO2=1: 1: 35: 0.13: 1.8: 0.3.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to Cu-SAPO- in 600 DEG C of air
34 molecular sieves.
Embodiment 56：The preparation of Cu-SAPO-34 samples
(1) by silicon and aluminum source AlPO4, tetraethylenepentamine (TEPA) and a certain amount of CuSO4·5H2O and distilled water weigh
Enter beaker, be stirred 2h, add a certain amount of silica, is fitted into after stirring evenly in reaction kettle and carries out crystallization,
The reaction temperature of crystallization is 180 DEG C, reaction time 5d, PH=14；When crystallization, the ingredient of the reaction raw materials of addition
Mol ratio meets, and Al: P: H2O∶Cu∶TEPA∶SiO2=1: 1: 35: 0.13: 1.8: 0.3.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to Cu-SAPO- in 600 DEG C of air
34 molecular sieves.
Embodiment 57：The preparation of Cu-SAPO-34 samples
(1) by silicon and aluminum source AlPO4, tetraethylenepentamine (TEPA) and a certain amount of CuSO4·5H2O and distilled water weigh
Enter beaker, be stirred 2h, add a certain amount of silica, is fitted into after stirring evenly in reaction kettle and carries out crystallization,
The reaction temperature of crystallization is 200 DEG C, reaction time 3d, PH=14；When crystallization, the ingredient of the reaction raw materials of addition
Mol ratio meets, and Al: P: H2O∶Cu∶TEPA∶SiO2=1: 1: 35: 0.13: 1.8: 0.3.
(2) crystallization product is obtained after the completion of crystallization, then cooling crystallization product is washed with deionized
To neutrality, the air drying at 80 DEG C obtains molecular screen primary powder；
(3) molecular screen primary powder that will be obtained in step (2) roasts 4 hours to get to Cu-SAPO- in 600 DEG C of air
34 molecular sieves.
The above is only several case study on implementation of the present invention, not does limitation in any form to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, however, it is not intended to limit the invention, any skill for being familiar with this profession
Art personnel, without departing from the scope of the present invention, when structure and technology contents using the disclosure above make it is a little
Change or be modified to the equivalence enforcement cases of equivalent variations.But every content without departing from technical solution of the present invention, foundation
The technical spirit of the present invention still belongs to the present invention to any simple modification, equivalent change and modification made by the above case study on implementation
In technical proposal scope.
Claims (4)
1. a kind of method of synthesizing P-Al molecular sieve or aluminium silicophosphate molecular sieve under alkaline system, which is characterized in that including following
Step：
(1) Al: P: H is pressed2O∶R∶SiO2Molar ratio be 1: 1: 15~90: 0.03~7.0: 0~0.5, respectively measure phosphorus silicon source
AlPO4, water, organic formwork agent R and silica；First by phosphorus silicon source AlPO4, organic formwork agent R and water be added in reaction kettle, stir
It mixes uniformly mixed；Then silica is added, starts crystallization after stirring evenly；Controlling reaction temperature is 180~220 DEG C,
Reaction time is for 24 hours~5d, and the pH value of reaction system keeps 12~14；
(2) after crystallization completes cooling, reaction product is taken out；It is first washed with deionized to neutrality, then at 80 DEG C
Air drying obtains molecular screen primary powder；
(3) molecular screen primary powder is roasted to 4 hours in 600 DEG C of air to get phosphate aluminium molecular sieve or aluminium silicophosphate molecular sieve.
2. according to the method described in claim 1, it is characterized in that, the organic formwork agent R be organic ammonium salt or organic amine, be
Any one or a few following mixtures：Tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetramethylammonium hydroxide, two
N-propylamine, triethylamine, N, N, N- trimethyls, 1- adamantane ammonium hydroxide, cyclopentamine, N, N, N, N- tetramethyls -1,6- hexamethylene diamine,
N, N ,-diisopropylethylamine, diethanol amine or triethanolamine.
3. according to the method described in claim 1, it is characterized in that, the organic formwork agent is any one following：Quality
The tetrapropylammonium hydroxide water that tetraethyl ammonium hydroxide aqueous solution that score is 20%~35%, mass fraction are 20%~40%
Five water crystallization solids of solution or tetramethylammonium hydroxide.
Further include adding into reaction system 4. according to the method described in claim 1, it is characterized in that, in the step (1)
Add CuSO4·5H2O, controlling its additive amount makes Al: Cu molar ratio be 1: 0.05~0.2.
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| CN111422882A (en) * | 2019-01-09 | 2020-07-17 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol |
| CN111422843A (en) * | 2019-01-09 | 2020-07-17 | 中国石油化工股份有限公司 | Synthesis method of molecular sieve |
| CN114289062A (en) * | 2021-11-10 | 2022-04-08 | 浙江恒逸石化研究院有限公司 | Alkaline synthesized aluminium phosphate molecular sieve alkylation catalyst and application thereof |
| CN115231591A (en) * | 2021-04-22 | 2022-10-25 | 中国石油化工股份有限公司 | Pure-phase small-crystal-grain SAPO-44 molecular sieve and preparation method and application thereof |
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| CN111422882A (en) * | 2019-01-09 | 2020-07-17 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol |
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