CN104445269A - Molecular sieve SAPO-34 with low content of silicon and preparation method of molecular sieve - Google Patents
Molecular sieve SAPO-34 with low content of silicon and preparation method of molecular sieve Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 58
- 239000010703 silicon Substances 0.000 title claims abstract description 57
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 53
- 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 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 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 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 239000004411 aluminium Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000084 colloidal system Substances 0.000 claims description 16
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004964 aerogel Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- -1 isobutanol aluminum Chemical compound 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction 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
- 238000010189 synthetic method Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001308 synthesis 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
- C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
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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 provides a molecular sieve SAPO-34 with a low content of silicon and a preparation method of the molecular sieve and belongs to the technical field of synthesis and preparation of molecular sieves. The preparation method of the molecular sieve comprises the following steps: gelling, carrying out hydrothermal crystallization and carrying out post-treatment, wherein the raw materials comprise SiO2, Al2O3, P, R and H2O in a mole ratio of (0.01-0.15) to (0.3-1.5) to 3 to (0.5-8.0) to (30-150); a phosphorus source is a mixture of phosphorous acid and phosphoric acid; the mole ratio of H2PO4 to H3PO3 is 0.5-9; an organic amine template agent is triethylamine. The preparation method of the molecular sieve SAPO-34 with the low content of silicon is simple in step and convenient to operate; products with few impurities can be prepared at a low silicon charging ratio; the preparation method of the molecular sieve SAPO-34 with the low content of silicon is suitable for industrial expanded production.
Description
Technical field
The present invention relates to the synthesis and preparation technical field of molecular sieve, particularly relate to a kind of low silicon content molecular sieve SAPO-34 and preparation method thereof.
Background technology
Aluminium silicophosphate molecular sieve SAPO-34 skeleton is made up of Si, P, Al, O element, belongs to chabazite structure, and international zeolite association is by its called after CHA.Have the cage type channel system of octatomic ring opening, free diameter 0.43 nanometer, belongs to trigonal system, and unit cell dimension is a=b=1.37nm, c=1.48nm.Connect owing to there is Si-O-Al in the skeleton structure of SAPO-34, thus it is acid that this molecular sieve is produced.Their thermostability and hydrothermal stability are all higher, under high temperature and a large amount of water vapor existent condition, have absorption stability and skeleton stability.Just because of the small structure of its uniqueness and the acidity of suitable medium tenacity, make it in catalysis methanol/dme reaction for preparing light olefins (MTO), show very high activity and olefine selective.
European patent EP 0103117 discloses a kind of SAPO-34 Zeolite synthesis method, and one of its technical characterstic is the mixture of use tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and di-n-propylamine is template.Disclosed in US Patent No. 4440871, SAPO-34 synthetic method also adopts same template.The main deficiency of above method is that the price of template is relatively costly, is unfavorable for industrial production.Patent ZL92112230.6 reports a kind of method adopting phosphoric acid to synthesize SAPO-34 as template as the triethylamine of phosphorus source, less expensive.
In the molecular sieve that the synthetic method reported in above-mentioned document obtains, the content of silicon is higher, and the carrying out of some chemical reaction is directly bad by the molecular sieve effect of these high silicon contents, and the life-span of molecular sieve is short, and this just needs the aluminium silicophosphate molecular sieve producing low silicon content.But, carry out according to aforesaid method, after reducing the feed ratio in silicon source in raw material, very easily the impurity such as SAPO-5 are produced in the building-up process of SAPO-34, the product obtained is the mixture of all kinds molecular sieve, and is difficult to the SAPO-34 obtaining pure phase, is unfavorable for industrialization expanding production.
Summary of the invention
When the problem to be solved in the present invention is existing aluminium silicophosphate molecular sieve SAPO-34 synthesis, in raw material, the feed ratio in silicon source easily produces impurity after reducing, and is difficult to obtain pure phase SAPO-34 molecular sieve, is unfavorable for the amplification production of industry.
The object of the present invention is to provide a kind of low silicon content molecular sieve SAPO-34 preparation method.The preparation method of described low silicon content molecular sieve SAPO-34 comprises the following steps:
(1) plastic: silicon source, aluminium source, phosphorus source, organic amine template (R) and water are mixed and make synthesis colloid, temperature during plastic is 20 ~ 50 DEG C;
(2) hydrothermal crystallizing: after the synthesis colloid ultrasonication that step (1) is obtained, hydrothermal crystallizing 10 ~ 300h under 160 ~ 225 DEG C and autogenous pressure,
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, oven dry, obtain aluminium silicophosphate molecular sieve SAPO-34;
Wherein, in described raw material, silicon source is with SiO
2meter, aluminium source is with Al
2o
3meter, phosphorus source is in P, and molar ratio of material is: SiO
2: Al
2o
3: P:R:H
2o=0.01 ~ 0.15:0.3 ~ 1.5:3:0.5 ~ 8.0:30 ~ 150;
Described phosphorus source is the mixture of phosphoric acid and phosphorous acid, the mol ratio H of its material
3pO
4: H
3pO
3=0.5 ~ 9;
Described organic amine template is triethylamine.
Further, in described raw material, molar ratio of material is: SiO
2: Al
2o
3: P:R:H
2o=0.05 ~ 0.09:0.5 ~ 1.2:3:1.0 ~ 5.0:30 ~ 150.
Preferably, in described phosphorus source, the mol ratio of material is: H
3pO
4: H
3pO
3=1 ~ 5.
Further, the addition sequence of described phosphorus source, aluminium source, silicon source and organic amine template is: add aluminium source, phosphorus source, silicon source, organic amine template successively, or be followed successively by aluminium source, organic amine template, phosphorus source, silicon source, or be followed successively by phosphorus source, aluminium source, organic amine template, silicon source, or be followed successively by phosphorus source, silicon source, aluminium source, organic amine template.
Further, described aluminium source is one or more in pseudo-boehmite, aluminum isopropylate, isobutanol aluminum, aluminium hydroxide, aluminum oxide and aluminium salt, and silicon source is one or more in silica gel, silicon sol, the aerogel of silicon, white carbon black, tetraethoxy.
Preferably, in step (2), the temperature of hydrothermal crystallizing is 190 ~ 200 DEG C, and the time is 20 ~ 50h, and bake out temperature is 60-80 DEG C.
Preferably, in described step (2), ultrasonic wave is 20 ~ 35kHz, treatment time 1 ~ 4h.
Second object of the present invention is to provide a kind of low silicon content molecular sieve SAPO-34, and it is prepared from by above-mentioned preparation method.
The advantage that the present invention has and positively effect are: the preparation method of low silicon content molecular sieve SAPO-34 provided by the invention, step is simple, simple operation, adopt the mixture of phosphoric acid and phosphorous acid as phosphorus source, triethylamine as template, under lower silicon source feed ratio, the aluminium silicophosphate molecular sieve SAPO-34 degree of crystallinity be prepared from is high, even mutually, substantially free of impurities SAPO-5, is suitable for the expanding production of industry.The template adopted in the present invention is cheap, is beneficial to industrial use.Optimize in the present invention and use phosphoric acid and phosphorous acid as phosphorus source, and optimize its mol ratio, decrease the impurity SAPO-5 produced in synthesis.After synthesis colloid, supersound process is carried out to it further in the present invention, and screening is except suitable frequency and time, is beneficial to the carrying out of colloid crystallization.Present invention also offers comparatively preferred material order of addition, provide preferable temperature and the time of hydrothermal crystallizing, prepare the aluminium silicophosphate molecular sieve SAPO-34 that catalytic performance is higher, in its synthesis, impurity reduces, and the product degree of crystallinity obtained is high, mutually even.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram (XRD) of the low silicon content molecular sieve SAPO-34 of preparation in the present embodiment 1.
Fig. 2 is the opticmicroscope figure of the low silicon content molecular sieve SAPO-34 of preparation in the present embodiment 1.
Embodiment
For a better understanding of the present invention, below in conjunction with specific embodiments and the drawings, the present invention is conducted further description.
Raw material in following examples is common commercially available prod, wherein: the volumetric molar concentration of phosphoric acid is 15mol/l, SiO in silicon sol
2content be 5.9mol/l, SiO in white carbon black
2content be 90wt%, the middle Al of pseudo-boehmite
2o
3content be 67.25wt%.
Embodiment 1
A preparation method of low silicon content molecular sieve SAPO-34, comprises the following steps:
(1) plastic: with 500ml water dissolution 264g phosphorous acid, 200ml phosphoric acid is dripped in stirring, this mixed acid solution is mixed with 16.9ml silicon sol, afterwards it mixed with the solution of 500ml water with 212.3g pseudo-boehmite and stir rapidly, add 202.4g triethylamine while stirring, stir 1h, after add 500ml water, mix to obtain synthesis colloid, gelling temperature is 25 DEG C.
(2) hydrothermal crystallizing: move in stainless steel cauldron after the ultrasonic 1h of synthesis colloid 20kHz that step (1) is obtained, hydrothermal crystallizing 30h under 190 DEG C and autogenous pressure.
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, 60 DEG C of oven dry, obtain aluminium silicophosphate molecular sieve SAPO-34.
The aluminium silicophosphate molecular sieve SAPO-34 prepared as seen from Figure 1 presents its characteristic diffraction peak, and there is obvious bimodal appearance at 2 θ angles with 31 ° of vicinity near 26 °, and have larger intensity, show that gained sample has very high degree of crystallinity.In FIG, almost do not have near the characteristic peak 7.5 ° of SAPO-5, prove that its impurity SAPO-5 content is extremely low.
Fig. 2 is the opticmicroscope figure of 40 times made, aluminium silicophosphate molecular sieve SAPO-34 object lens, known gained molecular sieve is cubic, is typical SAPO-34 molecular sieve shape.
Embodiment 2
A preparation method of low silicon content molecular sieve SAPO-34, comprises the following steps:
(1) plastic: with 500ml water dissolution 82g phosphorous acid, drip 133.3ml phosphoric acid in stirring, obtain mixed acid solution.Mixture A is obtained after being mixed with mixed acid solution with the mixing solutions of 100ml water by 4g white carbon black.200g pseudo-boehmite powder is mixed to obtain mixture B with 200ml water.Joined by mixture A afterwards in mixture B and also stir rapidly, add 202.4g triethylamine and 500ml water after 40min while stirring, stirring 1h must synthesize colloid, and gelling temperature is 30 DEG C.
(2) hydrothermal crystallizing: move in stainless steel cauldron after the ultrasonic 2h of synthesis colloid 30kHz that step (1) is obtained, hydrothermal crystallizing 24h under 192 DEG C and autogenous pressure.
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, 70 DEG C of oven dry, obtain aluminium silicophosphate molecular sieve SAPO-34.
Embodiment 3
A preparation method of low silicon content molecular sieve SAPO-34, comprises the following steps:
(1) plastic: with 600ml water dissolution 61.5g phosphorous acid, drip 150ml phosphoric acid afterwards, this mixed acid aqueous solution is joined in 364.3g aluminum isopropylate pressed powder and stir 120min rapidly, add 303.6g triethylamine while stirring, add water 1000ml, finally add 4.7g white carbon black, be stirred to evenly and continue to stir 2h, 35 DEG C must be synthesized colloid.
(2) hydrothermal crystallizing: move in stainless steel cauldron after the ultrasonic 3h of synthesis colloid 25kHz that step (1) is obtained, hydrothermal crystallizing 36h under 196 DEG C and autogenous pressure.
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, 75 DEG C of oven dry, obtain aluminium silicophosphate molecular sieve SAPO-34.
Embodiment 4
A preparation method of low silicon content molecular sieve SAPO-34, comprises the following steps:
(1) plastic: slowly add after 500ml water and 151.7g pseudo-boehmite are stirred 404.8g triethylamine and 500ml water stir all with must mixture A.With 1L water dissolution 49.2g phosphorous acid, drip 160ml phosphoric acid afterwards, this mixed acid aqueous solution is joined in mixture A, rapid stirring 90min, adds 16.7g tetraethoxy while stirring, adds water 160ml afterwards, be stirred to evenly, 42 DEG C of plastics, obtain synthesis colloid.
(2) hydrothermal crystallizing: move in stainless steel cauldron after the ultrasonic 2.5h of synthesis colloid 35kHz that step (1) is obtained, hydrothermal crystallizing 45h under 198 DEG C and autogenous pressure.
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, 65 DEG C of oven dry, obtain aluminium silicophosphate molecular sieve SAPO-34.
Embodiment 5
A preparation method of low silicon content molecular sieve SAPO-34, comprises the following steps:
(1) plastic: with 1L water dissolution 41g phosphorous acid, drip 166.7ml phosphoric acid afterwards, the silicon sol of this mixed acid solution and 15.3ml and 430ml water are mixed, pour 182g pseudo-boehmite pressed powder again into, rapid stirring 120min, add 506g triethylamine and water 1L while stirring, stir 240min and must synthesize colloid after evenly, gelling temperature is 48 DEG C.
(2) hydrothermal crystallizing: move in stainless steel cauldron after the ultrasonic 4h of synthesis colloid 20kHz that step (1) is obtained, hydrothermal crystallizing 48h under 200 DEG C and autogenous pressure.。
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, 80 DEG C of oven dry, obtain aluminium silicophosphate molecular sieve SAPO-34.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the scope of the invention change and improve, and all should still belong within this patent covering scope.
Claims (8)
1. a preparation method of low silicon content molecular sieve SAPO-34, is characterized in that: comprise the following steps:
(1) plastic: silicon source, aluminium source, phosphorus source, organic amine template (R) and water are mixed and make synthesis colloid, temperature during plastic is 20 ~ 50 DEG C;
(2) hydrothermal crystallizing: after the synthesis colloid ultrasonication that step (1) is obtained, hydrothermal crystallizing 10 ~ 300h under 160 ~ 225 DEG C and autogenous pressure,
(3) aftertreatment: by the product collection after hydrothermal crystallizing in step (2), washing, oven dry, obtain low silicon content molecular sieve SAPO-34;
Wherein, in described raw material, silicon source is with SiO
2meter, aluminium source is with Al
2o
3meter, phosphorus source is in P, and molar ratio of material is: SiO
2: Al
2o
3: P:R:H
2o=0.01 ~ 0.15:0.3 ~ 1.5:3:0.5 ~ 8.0:30 ~ 150;
Described phosphorus source is the mixture of phosphoric acid and phosphorous acid, the mol ratio H of its material
3pO
4: H
3pO
3=0.5 ~ 9;
Described organic amine template is triethylamine.
2. the preparation method of low silicon content molecular sieve SAPO-34 according to claim 1, is characterized in that: in described raw material, molar ratio of material is: SiO
2: Al
2o
3: P:R:H
2o=0.05 ~ 0.09:0.5 ~ 1.2:3:1.0 ~ 5.0:30 ~ 150.
3. the preparation method of low silicon content molecular sieve SAPO-34 according to claim 2, is characterized in that: in described phosphorus source, the mol ratio of material is: H
3pO
4: H
3pO
3=1 ~ 5.
4. the preparation method of low silicon content molecular sieve SAPO-34 according to claim 2, it is characterized in that: the addition sequence of described phosphorus source, aluminium source, silicon source and organic amine template is: be followed successively by aluminium source, phosphorus source, silicon source, organic amine template, or be followed successively by aluminium source, organic amine template, phosphorus source, silicon source, or be followed successively by phosphorus source, aluminium source, organic amine template, silicon source, or be followed successively by phosphorus source, silicon source, aluminium source, organic amine template.
5. according to the preparation method of the arbitrary described low silicon content molecular sieve SAPO-34 of claim 1-4, it is characterized in that: described aluminium source is one or more in pseudo-boehmite, aluminum isopropylate, isobutanol aluminum, aluminium hydroxide, aluminum oxide and aluminium salt, silicon source is one or more in silica gel, silicon sol, the aerogel of silicon, white carbon black, tetraethoxy.
6. according to the preparation method of the arbitrary described low silicon content molecular sieve SAPO-34 of claim 1-4, it is characterized in that: in step (2), the temperature of hydrothermal crystallizing is 190 ~ 200 DEG C, and the time is 20 ~ 50h, and bake out temperature is 60 ~ 80 DEG C.
7., according to the preparation method of the arbitrary described low silicon content molecular sieve SAPO-34 of claim 1-4, it is characterized in that: in described step (2), ultrasonic wave is 20 ~ 35kHz, treatment time 1 ~ 4h.
8. a low silicon content molecular sieve SAPO-34, is characterized in that: be prepared from by the preparation method of the low silicon content molecular sieve SAPO-34 as described in as arbitrary in claim 1-7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542547A (en) * | 2016-08-03 | 2017-03-29 | 刘希尧 | A kind of preparation method of 34 molecular sieves of SAPO of high activity low silicon content |
| CN107128949A (en) * | 2017-05-27 | 2017-09-05 | 江苏有容催化技术研究所有限公司 | A kind of method of the synthesis molecular sieves of SAPO 34 |
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| WO2003106341A1 (en) * | 2002-06-12 | 2003-12-24 | Exxonmobil Chemical Patents Inc. | Synthesis of aluminophosphates and silicoaluminophosphates |
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN103130241A (en) * | 2013-03-21 | 2013-06-05 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN103641131A (en) * | 2013-12-10 | 2014-03-19 | 吉林大学 | Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003106341A1 (en) * | 2002-06-12 | 2003-12-24 | Exxonmobil Chemical Patents Inc. | Synthesis of aluminophosphates and silicoaluminophosphates |
| CN102336413A (en) * | 2010-11-29 | 2012-02-01 | 中国科学院大连化学物理研究所 | Synthesis method of low-silicon SAPO-34 molecular sieves |
| CN103130241A (en) * | 2013-03-21 | 2013-06-05 | 上海绿强新材料有限公司 | Synthesis method of low-silicon nano SAPO-34 molecular sieve |
| CN103641131A (en) * | 2013-12-10 | 2014-03-19 | 吉林大学 | Slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542547A (en) * | 2016-08-03 | 2017-03-29 | 刘希尧 | A kind of preparation method of 34 molecular sieves of SAPO of high activity low silicon content |
| CN107128949A (en) * | 2017-05-27 | 2017-09-05 | 江苏有容催化技术研究所有限公司 | A kind of method of the synthesis molecular sieves of SAPO 34 |
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