CN106044794A - Preparation method of laminar SAPO-34 molecular sieve - Google Patents
Preparation method of laminar SAPO-34 molecular sieve Download PDFInfo
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- CN106044794A CN106044794A CN201610389108.3A CN201610389108A CN106044794A CN 106044794 A CN106044794 A CN 106044794A CN 201610389108 A CN201610389108 A CN 201610389108A CN 106044794 A CN106044794 A CN 106044794A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- 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 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 46
- 230000008025 crystallization Effects 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 14
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 13
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 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 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a laminar SAPO-34 molecular sieve. The method comprises the following steps: gel a is obtained by uniformly mixing a phosphorus source, an aluminum source, a template agent, a silicon source and a solvent, and an accelerant solution is obtained by stirring and crystallizing the gel a; gel b is obtained by uniformly mixing the phosphorus source, the aluminum source, the silicon source, the template agent and water; the accelerant solution is added to the gel b, an obtained mixture is subjected to hydrothermal crystallization, centrifugal separation, washing, drying and roasting, and the laminar SAPO-34 molecular sieve is obtained. The SAPO-34 molecular sieve prepared with the method has laminar morphology and high degree of crystallinity, has shorter diffusion path on a section when applied to a reaction for preparing alkene from methanol, has excellent diffusion performance, and can prolong the service life of a catalyst and increase the yield of ethylene and propylene. The preparation method has the advantages that on one hand, the use amount of the template agent is reduced and the production cost is reduced accordingly, on the other hand, the crystallization time is shortened, and energy consumption is reduced.
Description
Technical field
The present invention relates to the preparation method of SAPO molecular sieve, the preparation of a kind of flaggy shape SAPO-34 molecular sieve
Method.
Background technology
SAPO-34 molecular sieve has suitable acid, less aperture and the hydrothermal stability of excellence, at methanol-to-olefins
Reaction shows selectivity of light olefin and the methanol conversion of excellence, thus the optimal catalysis being seen as in MTO technique
Agent, but current SAPO-34 molecular sieve is easily generated serious carbon distribution, blocking duct when MTO reacts, thus cause catalyst
Inactivation, research shows that particle diameter is less than the SAPO-34 molecular sieve of 0.4 micron and has the longest life-span and higher in MTO reacts
Diene selective, and almost without induction period, but the synthesis of the SAPO-34 molecular sieve that current particle diameter is less than 0.4 micron
Process is complicated, relatively costly, separates difficulty, and the requirement to equipment is high, is unfavorable for industrialized production.
Lamellated SAPO-34 molecular sieve is shorter at cross section the evolving path, and the low-carbon (LC) hydro carbons of generation can diffuse out rapidly
Go, alleviate the generation of carbon distribution, thus there is longer catalytic life and higher diene selective；Other two diffusion roads simultaneously
Footpath is longer, has the feature of big crystal grain, it is easy to separates, is suitable for large-scale production, but current Lamellated SAPO-34 molecule
The synthetic method template sieved is expensive, and the production cycle is long, is easily generated environmental pollution, therefore needs a kind of simple efficient, warp of exploitation badly
Help profitable, be suitable to industrial flaggy shape SAPO-34 molecular sieve.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide the preparation method of a kind of flaggy shape SAPO-34 molecular sieve.
The present invention for achieving the above object, is achieved through the following technical solutions:
The preparation method of a kind of flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. phosphorus source, aluminum source, template, silicon source and solvent mix homogeneously are obtained gel a, then gel a is joined reactor
In, at 60 ~ 165 DEG C, stirring crystallization 1 ~ 24 hour, temperature of reaction kettle is down to 20 ~ 30 DEG C after terminating by crystallization, is promoted agent
Solution；Solvent: P in described gel a2O5:Al2O3: template: SiO2Mol ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:1 ~ 3:
0.02~1；Described solvent is one or both in ethanol or water；
2. phosphorus source, aluminum source, silicon source, template and water mix homogeneously are obtained gel b, H in described gel b2O:P2O5:Al2O3:
Template: SiO2Mol ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:0.1 ~ 4:0.01 ~ 1；
3. the accelerator solution of step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by gained gel c
Join in crystallizing kettle, be warming up to 100 ~ 170 DEG C, react 6 ~ 30 hours, be continuously heating to 170 ~ 220 DEG C, hydrothermal crystallizing 10 ~ 96
Hour, obtain crystallization product；The quality of described accelerator solution accounts for the 0.1% ~ 20% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 500 ~ 600 DEG C of Muffle kiln roastings 4 ~ 6 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape
SAPO-34 molecular sieve.
Preferably, step aluminum source 1. and 2. is boehmite, aluminum isopropylate. or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon
Source is tetraethyl orthosilicate, Ludox or white carbon；Template be tetraethyl ammonium hydroxide, 2-aminopropane., triethylamine, diethylamine,
One or both in quinoline or DIPEA.
Preferably, 1. step stirs crystallization 20 hours at 95 DEG C.
Preferably, step 3. in the quality of accelerator solution account for gel b quality 10%.
Preferably, step 1. in solvent be that water and ethanol are according to the ratio mixing gained that mol ratio is 1:1.
The preparation method of further preferred flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. phosphorus source, aluminum source, template, silicon source and solvent mix homogeneously are obtained gel a, then gel a is joined reactor
In, at 95 DEG C, stirring crystallization 20 hours, temperature of reaction kettle is down to 25 DEG C after terminating by crystallization, is promoted agent solution；Described
Solvent in gel a: P2O5:Al2O3: template: SiO2Mol ratio be 80:1:1:2:0.5；Phosphorus source is phosphoric acid, described aluminum
Source is aluminium hydroxide, and described template is tetraethyl ammonium hydroxide；Silicon source is tetraethyl orthosilicate, described solvent be second alcohol and water by
According to the ratio mixing gained that mol ratio is 1:1；
2. phosphorus source, aluminum source, silicon source, template and water mix homogeneously are obtained gel b, H in described gel b2O:P2O5:Al2O3:
Template: SiO2Mol ratio be 80:1:1:3:0.5；Phosphorus source is phosphoric acid, and source of aluminium is aluminium hydroxide, described template
Agent is tetraethyl ammonium hydroxide；Silicon source is tetraethyl orthosilicate；
3. the accelerator solution of step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by gained gel c
Join in crystallizing kettle, be warming up to 150 DEG C, react 20 hours, be continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours, obtain crystallization
Product；The quality of described accelerator solution accounts for the 10% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 550 DEG C of Muffle kiln roastings 5 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve.
The present invention has the advantage that compared to existing technology
The SAPO-34 molecular sieve using preparation method gained of the present invention has flaggy shape pattern, and degree of crystallinity is high, for methanol system
During the reaction of standby alkene shorter at cross section the evolving path, there is excellent diffusion, it is possible to extend the life-span of catalyst, improve
Ethylene and the yield of propylene；The preparation method yield of the present invention is high, owing to other two the evolving paths are longer, has big crystal grain
Feature, is more easily than separation relative to nano level small particle size SAPO-34 molecular sieve, is therefore applicable to industrial extensive life
Produce；The preparation method of the present invention prepares flaggy shape SAPO-34 molecular sieve, wherein accelerator by adding homemade accelerator solution
Solution not only has the characteristic of crystal seed, and can guide the growth of molecular sieve in crystallization process；Additionally accelerator solution is straight
Connect in the synthesis participating in molecular sieve as a kind of liquid charging stock, it is to avoid waste liquid that solid-liquid separation is brought and energy consumption problem；This
On the one hand the preparation method of invention reduces the consumption of template, thus reduces production cost, when on the other hand shortening crystallization
Between, reduce energy consumption.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the flaggy shape SAPO-34 molecular screen primary powder sample of embodiment 1 ~ 4 gained；
Fig. 2 is the SEM figure of the flaggy shape SAPO-34 molecular screen primary powder sample of embodiment 1 gained；
Fig. 3 is the SEM figure of the flaggy shape SAPO-34 molecular screen primary powder sample of embodiment 2 gained；
Fig. 4 is the SEM figure of the flaggy shape SAPO-34 molecular screen primary powder sample of embodiment 3 gained；
Fig. 5 is the SEM figure of the flaggy shape SAPO-34 molecular screen primary powder sample of embodiment 4 gained.
Detailed description of the invention
It is an object of the invention to provide a kind of heat-resisting water-resistant type high strength polyurethane adhesive and preparation method thereof, by with
Lower technical scheme realizes:
The preparation method of a kind of flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. phosphorus source, aluminum source, template, silicon source and solvent mix homogeneously are obtained gel a, then gel a is joined reactor
In, at 60 ~ 165 DEG C, stirring crystallization 1 ~ 24 hour, temperature of reaction kettle is down to 20 ~ 30 DEG C after terminating by crystallization, is promoted agent
Solution；Solvent: P in described gel a2O5:Al2O3: template: SiO2Mol ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:1 ~ 3:
0.02~1；Described solvent is one or both in ethanol or water；
2. phosphorus source, aluminum source, silicon source, template and water mix homogeneously are obtained gel b, H in described gel b2O:P2O5:Al2O3:
Template: SiO2Mol ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:0.1 ~ 4:0.01 ~ 1；
3. the accelerator solution of step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by gained gel c
Join in crystallizing kettle, be warming up to 100 ~ 170 DEG C, react 6 ~ 30 hours, be continuously heating to 170 ~ 220 DEG C, hydrothermal crystallizing 10 ~ 96
Hour, obtain crystallization product；The quality of described accelerator solution accounts for the 0.1% ~ 20% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 500 ~ 600 DEG C of Muffle kiln roastings 4 ~ 6 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape
SAPO-34 molecular sieve.
Preferably, step aluminum source 1. and 2. is boehmite, aluminum isopropylate. or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon
Source is tetraethyl orthosilicate, Ludox or white carbon；Template be tetraethyl ammonium hydroxide, 2-aminopropane., triethylamine, diethylamine,
One or both in quinoline or DIPEA.
Preferably, 1. step stirs crystallization 20 hours at 95 DEG C.
Preferably, step 3. in the quality of accelerator solution account for gel b quality 10%.
Preferably, step 1. in solvent be that water and ethanol are according to the ratio mixing gained that mol ratio is 1:1.
The preparation method of further preferred flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. phosphorus source, aluminum source, template, silicon source and solvent mix homogeneously are obtained gel a, then gel a is joined reactor
In, at 95 DEG C, stirring crystallization 20 hours, temperature of reaction kettle is down to 25 DEG C after terminating by crystallization, is promoted agent solution；Described
Solvent in gel a: P2O5:Al2O3: template: SiO2Mol ratio be 80:1:1:2:0.5；Phosphorus source is phosphoric acid, described aluminum
Source is aluminium hydroxide, and described template is tetraethyl ammonium hydroxide；Silicon source is tetraethyl orthosilicate, described solvent be second alcohol and water by
According to the ratio mixing gained that mol ratio is 1:1；
2. phosphorus source, aluminum source, silicon source, template and water mix homogeneously are obtained gel b, H in described gel b2O:P2O5:Al2O3:
Template: SiO2Mol ratio be 80:1:1:3:0.5；Phosphorus source is phosphoric acid, and source of aluminium is aluminium hydroxide, described template
Agent is tetraethyl ammonium hydroxide；Silicon source is tetraethyl orthosilicate；
3. the accelerator solution of step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by gained gel c
Join in crystallizing kettle, be warming up to 150 DEG C, react 20 hours, be continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours, obtain crystallization
Product；The quality of described accelerator solution accounts for the 10% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 550 DEG C of Muffle kiln roastings 5 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve.
Below in conjunction with specific embodiment, the invention will be further described.
Al in boehmite used in the embodiment of the present invention 1 ~ 42O3Mass fraction 76%, the matter of tetraethyl ammonium hydroxide
Amount mark is 35%, and the mass fraction of phosphoric acid is 85%, and the mass fraction of Ludox is 25%.
Embodiment 1
The preparation method of a kind of flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. 11.5kg phosphoric acid, 6.7kg boehmite, 42kg tetraethyl ammonium hydroxide, 0.156kg Ludox and 36kg water are mixed
Closing and uniformly obtain gel a, then join in reactor by gel a, stir crystallization 1 hour at 60 DEG C, crystallization will after terminating
Temperature of reaction kettle is down to 20 ~ 30 DEG C, is promoted agent solution；
2. 115kg phosphoric acid, 67kg boehmite, 4.2kg tetraethyl ammonium hydroxide, 0.78kg Ludox and 360kg water are mixed
Close and uniformly obtain gel b；
3. the accelerator solution of 0.523kg step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by institute
Obtain gel c and join in crystallizing kettle, be warming up to 100 DEG C, react 6 hours, be continuously heating to 170 DEG C, hydrothermal crystallizing 96 hours,
To crystallization product；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 500 DEG C of Muffle kiln roastings 4 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve, numbering S-1.
Embodiment 2
The preparation method of a kind of flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. by 54.78kg phosphoric acid, 97.92kg aluminum isopropylate., 21.24kg 2-aminopropane., 9.36kg white carbon, 496.8kg ethanol and
21.6kg water mix homogeneously obtains gel a, then joins in reactor by gel a, stirs crystallization 24 hours at 165 DEG C,
Temperature of reaction kettle is down to 30 DEG C after terminating by crystallization, is promoted agent solution；；
2. 456kg phosphoric acid, 816kg aluminum isopropylate., 236kg 2-aminopropane., 78kg white carbon and 1800kg water mix homogeneously are obtained
Gel b；
3. the accelerator solution of 663.6kg step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by institute
Obtain gel c and join in crystallizing kettle, be warming up to 170 DEG C, react 30 hours, be continuously heating to 220 DEG C, hydrothermal crystallizing 96 hours,
Obtain crystallization product；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 600 DEG C of Muffle kiln roastings 6 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve, numbering S-2.
Embodiment 3
The preparation method of a kind of flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. by 22.8kg phosphoric acid, 15.6kg aluminium hydroxide, 8.7kg morpholine, 7.3kg diethylamine, 8.32kg tetraethyl orthosilicate and
230kg ethanol mix homogeneously obtains gel a, then joins in reactor by gel a, stirs crystallization 10 hours at 95 DEG C,
Temperature of reaction kettle is down to 24 DEG C after terminating by crystallization, is promoted agent solution；
2. by 136.9kg phosphoric acid, 124.8kg aluminium hydroxide, 130.5kg morpholine, 109.5kg diethylamine, 20.8kg positive silicic acid second
Ester and 720kg water mix homogeneously obtain gel b；
3. the accelerator solution of 61.1kg step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by institute
Obtain gel c and join in crystallizing kettle, be warming up to 150 DEG C, react 10 hours, be continuously heating to 180 DEG C, hydrothermal crystallizing 20 hours,
Obtain crystallization product；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 520 DEG C of Muffle kiln roastings 3 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve, numbering S-3.
Embodiment 4
The preparation method of a kind of flaggy shape SAPO-34 molecular sieve, comprises the steps:
1. by 22.8kg phosphoric acid, 15.6kg aluminium hydroxide, 84kg tetraethyl ammonium hydroxide, 10.4kg tetraethyl orthosilicate, 184kg second
Alcohol and 72kg water mix homogeneously obtain gel a, then join in reactor by gel a, stir crystallization 20 hours at 95 DEG C,
Temperature of reaction kettle is down to 25 DEG C after terminating by crystallization, is promoted agent solution；
2. by 228kg phosphoric acid, 156kg aluminium hydroxide, 1260kg tetraethyl ammonium hydroxide, 104kg tetraethyl orthosilicate and 1440kg
Water mix homogeneously obtains gel b；
3. the accelerator solution of 233.5kg step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by institute
Obtain gel c and join in crystallizing kettle, be warming up to 150 DEG C, react 20 hours, be continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours,
Obtain crystallization product；The quality of described accelerator solution accounts for the 10% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 550 DEG C of Muffle kiln roastings 5 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve, numbering S-4.
The XRD spectra of the flaggy shape SAPO-34 molecular screen primary powder sample of embodiment 1 ~ 4 gained is as it is shown in figure 1, SEM picture
As shown in Fig. 2 ~ 5.The SAPO-34 molecular sieve that be may indicate that embodiment 1 ~ 4 gained by the result of Fig. 1 ~ 5 is pure phase, flaggy shape,
Structure is CHA topological structure, and grain size is each about 1.8 × 1.8 × 0.4 μm.
The flaggy shape SAPO-34 molecular sieve of embodiment 1 ~ 4 gained carries out tabletting, is crushed to 40 ~ 60 mesh.Take 1.0g sample dress
Enter fixed bed reactors, carry out MTO performance test.Test condition is: catalyst activates 1 hour at 500 DEG C, is cooled to 450
℃.Methanol charging is loaded into by nitrogen, and stream of nitrogen gas is 30ml/min, and methanol water content is 60%, and air speed is 1.5h-1.Gas phase is produced
Thing is detected by extra large glad GC-950 type gas chromatograph (fid detector).Chromatographic column be PLOT Q capillary column (30m ×
0.32mm × 10 μm).Analysis result is shown in Table 1.As can be seen from Table 1, the flaggy shape SAPO-34 molecular sieve of embodiment 1 ~ 4 gained
It is respectively provided with longer life-span (methanol conversion is more than 99.9%) and higher ethylene, propene yield, and ethylene and propylene
Selectivity reaches more than 94%.
Table 1: the MTO reaction test result of sample
。
Claims (6)
1. the preparation method of a flaggy shape SAPO-34 molecular sieve, it is characterised in that: comprise the steps:
1. phosphorus source, aluminum source, template, silicon source and solvent mix homogeneously are obtained gel a, then gel a is joined reactor
In, at 60 ~ 165 DEG C, stirring crystallization 1 ~ 24 hour, temperature of reaction kettle is down to 20 ~ 30 DEG C after terminating by crystallization, is promoted agent
Solution；Solvent: P in described gel a2O5:Al2O3: template: SiO2Mol ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:1 ~ 3:
0.02~1；Described solvent is one or both in ethanol or water；
2. phosphorus source, aluminum source, silicon source, template and water mix homogeneously are obtained gel b, H in described gel b2O:P2O5:Al2O3: mould
Plate agent: SiO2Mol ratio be 20 ~ 100:0.5 ~ 2:0.5 ~ 2:0.1 ~ 4:0.01 ~ 1；
3. the accelerator solution of step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by gained gel c
Join in crystallizing kettle, be warming up to 100 ~ 170 DEG C, react 6 ~ 30 hours, be continuously heating to 170 ~ 220 DEG C, hydrothermal crystallizing 10 ~ 96
Hour, obtain crystallization product；The quality of described accelerator solution accounts for the 0.1% ~ 20% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 500 ~ 600 DEG C of Muffle kiln roastings 4 ~ 6 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape
SAPO-34 molecular sieve.
The preparation method of flaggy shape SAPO-34 molecular sieve the most according to claim 1, it is characterised in that: 1. and 2. step
Aluminum source be boehmite, aluminum isopropylate. or aluminium hydroxide；Phosphorus source is phosphoric acid；Silicon source is tetraethyl orthosilicate, Ludox or white
White carbon black；Template is in tetraethyl ammonium hydroxide, 2-aminopropane., triethylamine, diethylamine, morpholine or DIPEA
Plant or two kinds.
The preparation method of flaggy shape SAPO-34 molecular sieve the most according to claim 1, it is characterised in that: step is 1. 95
Crystallization is stirred 20 hours at DEG C.
The preparation method of flaggy shape SAPO-34 molecular sieve the most according to claim 1, it is characterised in that: step is 3. middle to be promoted
Enter that the quality of agent solution accounts for the quality of gel b 10%.
The preparation method of flaggy shape SAPO-34 molecular sieve the most according to claim 1, it is characterised in that: step 1. in
Solvent is that water and ethanol are according to the ratio mixing gained that mol ratio is 1:1.
The preparation method of flaggy shape SAPO-34 molecular sieve the most according to claim 1, it is characterised in that: include walking as follows
Rapid:
1. phosphorus source, aluminum source, template, silicon source and solvent mix homogeneously are obtained gel a, then gel a is joined reactor
In, at 95 DEG C, stirring crystallization 20 hours, temperature of reaction kettle is down to 25 DEG C after terminating by crystallization, is promoted agent solution；Described
Solvent in gel a: P2O5:Al2O3: template: SiO2Mol ratio be 80:1:1:2:0.5；Phosphorus source is phosphoric acid, described aluminum
Source is aluminium hydroxide, and described template is tetraethyl ammonium hydroxide；Silicon source is tetraethyl orthosilicate, described solvent be second alcohol and water by
According to the ratio mixing gained that mol ratio is 1:1；
2. phosphorus source, aluminum source, silicon source, template and water mix homogeneously are obtained gel b, H in described gel b2O:P2O5:Al2O3: mould
Plate agent: SiO2Mol ratio be 80:1:1:3:0.5；Phosphorus source is phosphoric acid, and source of aluminium is aluminium hydroxide, described template
For tetraethyl ammonium hydroxide；Silicon source is tetraethyl orthosilicate；
3. the accelerator solution of step 1. gained is joined in the gel b of step 2. gained, obtain gel c, by gained gel c
Join in crystallizing kettle, be warming up to 150 DEG C, react 20 hours, be continuously heating to 190 DEG C, hydrothermal crystallizing 20 hours, obtain crystallization
Product；The quality of described accelerator solution accounts for the 10% of the quality of gel b；
4. being performing centrifugal separation on by step 3. gained crystallization product, filter cake is through washing, being dried to obtain flaggy shape SAPO-34 molecular screen primary
Powder, is placed in 550 DEG C of Muffle kiln roastings 5 hours by sheets thus obtained stratiform SAPO-34 molecular screen primary powder, obtains flaggy shape SAPO-34
Molecular sieve.
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| CN108706609A (en) * | 2018-06-07 | 2018-10-26 | 深圳科冠华太新材料技术有限公司 | A kind of preparation method of nanometer of SAPO-34 molecular sieve |
| CN111013650A (en) * | 2019-12-25 | 2020-04-17 | 山东江岳科技开发股份有限公司 | SAPO-34 molecular sieve thin-layer catalyst and preparation method thereof |
| CN114426295A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | AFX type molecular sieve and synthetic method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525141A (en) * | 2009-04-03 | 2009-09-09 | 成都惠恩精细化工有限责任公司 | Method for preparing SAPO-34 molecular sieve |
| CN102464338A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method for silicoaluminophosphate (SAPO)-34 molecular sieve with small crystal particle |
| CN104445266A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of small-grain-size SAPO-34 molecular sieve |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101525141A (en) * | 2009-04-03 | 2009-09-09 | 成都惠恩精细化工有限责任公司 | Method for preparing SAPO-34 molecular sieve |
| CN102464338A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method for silicoaluminophosphate (SAPO)-34 molecular sieve with small crystal particle |
| CN104445266A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of small-grain-size SAPO-34 molecular sieve |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108706609A (en) * | 2018-06-07 | 2018-10-26 | 深圳科冠华太新材料技术有限公司 | A kind of preparation method of nanometer of SAPO-34 molecular sieve |
| CN108706609B (en) * | 2018-06-07 | 2021-07-30 | 深圳科冠华太新材料技术有限公司 | Preparation method of nano SAPO-34molecular sieve |
| CN111013650A (en) * | 2019-12-25 | 2020-04-17 | 山东江岳科技开发股份有限公司 | SAPO-34 molecular sieve thin-layer catalyst and preparation method thereof |
| CN114426295A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | AFX type molecular sieve and synthetic method and application thereof |
| CN114426295B (en) * | 2020-09-27 | 2023-08-29 | 中国石油化工股份有限公司 | AFX type molecular sieve and synthetic method and application thereof |
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