CN1693202A - Preparation method of SAPO-34 molecular sieve - Google Patents
Preparation method of SAPO-34 molecular sieve Download PDFInfo
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- CN1693202A CN1693202A CN200510038863.9A CN200510038863A CN1693202A CN 1693202 A CN1693202 A CN 1693202A CN 200510038863 A CN200510038863 A CN 200510038863A CN 1693202 A CN1693202 A CN 1693202A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- 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 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 150000001412 amines Chemical class 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003292 glue Substances 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 238000007796 conventional method Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 54
- 239000007791 liquid phase Chemical group 0.000 claims description 25
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 24
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 229960005181 morphine Drugs 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 239000012687 aluminium precursor Substances 0.000 claims 1
- 239000012688 phosphorus precursor Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 6
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 241000566146 Asio Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a preparation method of an SAPO-34 molecular sieve, in particular to a method for preparing the SAPO-34 molecular sieve by a gas phase method. Adding deionized water into a container with a stirrer, then respectively adding precursor compounds of aluminum, phosphorus and silicon and organic amine into the container according to a certain proportion and sequence, adding another substance after the former substance is uniformly mixed, and evaporating water in an oven at 30-100 ℃ to obtain dry glue after the substances are uniformly mixed; placing the dry glue on the upper part of a gas phase reaction kettle, adding a mixture of organic amine and water at the bottom of the reaction kettle, and reacting for 24-72 hours at the temperature of 150-; and after the reaction is finished, cooling the reaction kettle in a natural state, and finally washing, drying and roasting the sample by a conventional method to obtain the SAPO-34 molecular sieve. The synthesis range of the silicon-aluminum ratio and the phosphorus-aluminum ratio of the prepared SAPO-34 molecular sieve is larger, and the crystallinity is higher than that of a common gas phase method.
Description
Technical field:
The present invention relates to a kind of preparation method of SAPO-34 molecular sieve, relate in particular to the method that a kind of vapor phase process prepares the SAPO-34 molecular sieve.
Background technology:
U.S. Union Carbide Corp had developed a series of silicoaluminophosphamolecular molecular sieves in 1984, and wherein the SAPO-34 molecular sieve has similar Chabazite-type structure, belongs to pore zeolite, can be used as sorbent material, catalyzer and support of the catalyst.Shown good catalytic activity in methane system alkene (MTO) reaction, selectivity of light olefin is up to more than 90%, and the selectivity of therein ethylene can reach more than 50%, does not almost have the above product of C5.Traditional method for preparing molecular sieve is selected hydrothermal method (USP4440871 for use, CN1037334C, CN1038125C, CN1048428C, CN1088483A) preparation, Hydrothermal Preparation molecular sieve process more complicated needs to use a large amount of organic amine template, and need isolate zeolite product at last from mother liquor.
Vapor phase process is as a kind of method of preparation molecular sieve, and at zeolite molecular sieve, particularly there has been deep research ZSM-5 molecular sieve aspect, but aspect phosphate aluminium molecular sieve synthetic, present report is also few.So-called vapor phase process is meant in building-up process, at first the synthetic precursor liquid of molecular sieve is prepared into dried glue under certain condition, then dried glue is placed reactor top, add the mixed solution of a certain amount of organic amine and water as template in the reactor bottom simultaneously, dried glue does not contact with liquid phase part, react for some time at a certain temperature at last, just can obtain zeolite product.Vapor phase process can significantly reduce the usage quantity of organic formwork agent; Saved the isolating numerous and diverse step of product and mother liquor; Can not produce a large amount of waste liquids, very friendly to environment; Be convenient to carry out continuous production; Organic formwork agent such as can reuse at advantage.Also there is report to use vapor phase process to prepare SAPO molecular sieve, Chemical Communications at present as CN1363519A, 2003,2232-2233 uses vapor phase process to prepare the SAPO-34 molecular sieve, only use the organic amine template at liquid phase part in the method for above-mentioned two bibliographical informations, its degree of crystallinity is relatively low; And the synthetic scope of silica alumina ratio, phosphorus aluminum ratio that is fit to preparation SAPO-34 molecular sieve is less, so institute's synthetic molecular sieve catalytic performance is restricted.
Summary of the invention:
Technical problem to be solved by this invention is to overcome method for preparing molecular sieve process more complicated, need to use a large amount of organic amine template, the synthetic scope of silica alumina ratio, phosphorus aluminum ratio that is fit to preparation SAPO-34 molecular sieve is less, deficiencies such as degree of crystallinity is relatively low and proposed a kind ofly to introduce the organic amine template during dried glue in preparation, and it is big that the phosphorus aluminum ratio scope becomes, and obtains the degree of crystallinity SAPO-34 molecular sieve preparation method higher than general vapor phase process.
Technical scheme of the present invention: a kind of preparation method of SAPO-34 molecular sieve may further comprise the steps successively:
A, in being housed, the container of agitator adds deionized water, respectively precursor compound, the organic amine of aluminium, phosphorus, silicon is sequentially added in the container then, by the time add another kind of material again after a kind of material mixes before, the mol ratio of each material in the final solution is: aSiO
2: Al
2O
3: b P
2O
5: cH
2O (deionized water): the d organic amine, wherein the scope of a is 0.10-1.5, and the scope of b is 0.10-1.5, and the scope of c is 0-300, and the scope of d is 0.01-4.0;
After B, each material mixed, evaporate to dryness moisture content obtained dried glue in 30-100 ℃ baking oven;
C, dried glue is placed the top of gas phase reaction kettle, the mixture that the reactor bottom adds organic amine and water reacted 24-72 hour down at 150-200 ℃;
D, reaction finish the afterreaction still cools off under state of nature, at last to sample wash according to a conventional method, drying and roasting, obtain the SAPO-34 molecular sieve.
Wherein the presoma of phosphorus is that mass percent is 85% phosphoric acid; The presoma of aluminium is aluminum isopropylate or pseudo-boehmite; The presoma of silicon is that mass percent is silicon sol or the gas-phase silica of 25-30%; Organic amine is triethylamine, di-n-propylamine, Diisopropylamine, morphine quinoline, tetraethyl ammonium hydroxide or Isopropylamine; The presoma of preferred aluminium is an aluminum isopropylate; The presoma of silicon is that mass percent is the silicon sol of 25-30%; Organic amine is triethylamine, morphine quinoline, tetraethyl ammonium hydroxide.Organic amine and liquid phase part organic amine are organic amine of the same race or are organic amine not of the same race in the dried glue, and organic amine and liquid phase part organic amine are organic amine not of the same race in the preferred dried glue.
The scope of a is preferably 0.6-1.3, and the scope of b is preferably 0.6-1.3, and the scope of c is preferably 0-120, and the scope of d is preferably 0.05-2.0.The mol ratio of liquid phase part water and organic amine is 1.0-200: 1.0; Be preferably 10-100: 1.0.
When c is 0, at first that the precursor compound thorough mixing of the precursor compound silicon sol of silicon and aluminium is even, and then the precursor compound and the organic amine of adding phosphorus, be not add deionized water in the step (A), be not introduce extra water in the synthetic precursor liquid of molecular sieve, and can omit step (B).
Beneficial effect:
1, in dried glue and liquid phase part use organic amine as the template synthesis of molecular sieve, the gained molecular sieve crystallinity is much higher when not containing organic amine in the dried glue, and when in the dried glue and liquid phase part when using not organic amine of the same race, degree of crystallinity is very high, and its catalytic activity also will improve greatly.
2, vapor phase process prepares silica alumina ratio (0.10-1.5) and synthetic a wider range of phosphorus aluminum ratio (0.10-1.5) of SAPO-34 molecular sieve; Can prepare the SAPO-34 molecular sieve of different catalytic performances.
3, do not introduce extra water in the synthetic precursor liquid of molecular sieve, avoided evaporate to dryness moisture content to form the step of dried this time consumption and energy consumption of glue, make that the vapor phase process synthesis of molecular sieve is simpler.
4, organic amine template amount ratio is few when synthetic with hydrothermal method, greatly reduces the synthetic cost of molecular sieve.
Description of drawings:
Fig. 1 is the XRD figure of SAPO-34 molecular sieve
Embodiment:
Comparative Examples 1
Solution one: the 15.37g mass percent is that 85% phosphoric acid joins in the 18.0g water, mixes the back and slowly adds 9.20g and intend thin water aluminium (Al
2O
3Mass percent is 66.8%), add 10.0g water then, stir; Solution two: the 4.09g white carbon black joins in the 15.0g water, adds 11.62g morphine quinoline then, and thorough mixing is even.Solution two is added drop-wise in the solution one while stirring, add 24.0g water again, fully mix, ageing 24h under the room temperature then, then at 200 ℃ of following hydro-thermal Synthetic 2 4h, product after filtration, after the washing, drying, be indicated as SAPO-34 molecular sieve (see figure 1) through XRD analysis is stipulated its degree of crystallinity 100%.
Comparative Examples 2
The 5.0g aluminum isopropylate is added in the 10.65g deionized water, after high degree of agitation is even, the adding mass percent is 85% phosphoric acid 2.82g, continue to stir for some time, be 30% silicon sol (Jiangyin League of Nations chemical industry) to wherein adding the .1.96g mass percent while stirring then, the ratio of each component is: 0.8SiO
2: Al
2O
3: 1.0P
2O
5: 60H
2O, evaporate to dryness moisture content forms dried glue; Liquid phase part is the mixture (mol ratio is 10: 1.0) of water and triethylamine, and 170 ℃ of following gas-phase reactions 48 hours, the SAPO-34 molecular sieve crystallinity that obtains at last was 62%.
Embodiment 1
The 5.0g aluminum isopropylate is added in the 13.95g deionized water, after high degree of agitation is even, the adding mass percent is 85% phosphoric acid 2.82g, continue to stir for some time, be 30% silicon sol (Jiangyin League of Nations chemical industry) to wherein adding the 3.06g mass percent while stirring then, add the 1.54g triethylamine at last.The ratio of each component is:
1.25SiO
2: Al
2O
3: 1.0P
2O
5: 75H
2O: 1.25Nt
3After N (triethylamine) liquid to be synthesized mixes fully, be moved into and form dried glue in 40 ℃ of baking ovens behind the moisture content evaporate to dryness, dried glue grinding powder, place the reactor top of inner liner polytetrafluoroethylene then, add the mixture of water and morphine quinoline (mol ratio is 50: 1.0) simultaneously in the reactor bottom.Sealing was placed in 170 ℃ of baking ovens gas-phase reaction 48 hours, and reaction finishes the back and cools off under state of nature.Take out sample at last, to sample wash, drying and roasting just can obtain molecular sieve.
Sample characterizes through XRD, has the crystalline form identical with Fig. 1, and its degree of crystallinity is 124%.
Embodiment 2
With the 3.06g mass percent is that 30% silicon sol joins in the 5.0g aluminum isopropylate, and mechanical stirring mixes it, adds the 1.76g mass percent then and be 85% phosphoric acid, thorough mixing evenly after, add the 1.54g triethylamine at last.The ratio of each component is:
1.25SiO
2: Al
2O
3: 1.0P
2O
5: 1.25Et
3The synthetic presoma of the molecular sieve of N (triethylamine) gained need not to heat evaporate to dryness moisture content, directly places the reactor top of inner liner polytetrafluoroethylene, adds the mixture of water and morphine quinoline (mol ratio is 50: 1.0) simultaneously in the reactor bottom.Sealing is placed in 170 ℃ of baking ovens reacted 48 hours, and reaction finishes the back and cools off under state of nature.Take out sample at last, to sample wash, drying and roasting just can obtain molecular sieve.
Sample characterizes through XRD, has the crystalline form identical with Fig. 1, and its degree of crystallinity is 121%.
Embodiment 3
According to the preparation method and the step of example 1, but liquid phase part organic amine kind when changing gas-phase reaction, liquid phase part is the mixture (mol ratio is 10: 1.0) of water and triethylamine, the SAPO-34 molecular sieve crystallinity that obtains at last is 85%.
Embodiment 4
According to the preparation method and the step of example 1, but liquid phase part organic amine kind when changing gas-phase reaction, liquid phase part is the mixture (mol ratio is 10: 1.0) of water and Diisopropylamine, the SAPO-34 molecular sieve crystallinity that obtains at last is 82%.
According to the preparation method and the step of example 2, but liquid phase part organic amine kind when changing gas-phase reaction, liquid phase part is the mixture (mol ratio is 10: 1.0) of water and triethylamine, the SAPO-34 molecular sieve crystallinity that obtains at last is 98%.
Embodiment 6
According to the preparation method and the step of example 1, but add the morphine quinoline as the organic amine template when the dried glue of preparation, it is template (mol ratio is 50: 1.0) that liquid phase part makes water and triethylamine, and the SAPO-34 molecular sieve crystallinity that obtains at last is 102%.
Embodiment 7
According to the preparation method and the step of example 2, but when the dried glue of preparation, add tetraethyl ammonium hydroxide, and the reaction precursor fluid component is: 1.25SiO as the organic amine template
2: Al
2O
3: 1.0P
2O
5: the 0.05TEAOH tetraethyl ammonium hydroxide.It is template (mol ratio is 50: 1.0) that liquid phase part makes water and triethylamine, and the SAPO-34 molecular sieve crystallinity that obtains at last is 117%.
Embodiment 8
According to the preparation method and the step of example 1, but add the morphine quinoline as the organic amine template when the dried glue of preparation, liquid phase part still is the mixture (mol ratio 50: 1.0) of water and morphine quinoline, and the SAPO-34 molecular sieve crystallinity that obtains at last is 94%.
Embodiment 9
According to the preparation method and the step of example 2, but add the morphine quinoline as the organic amine template when the dried glue of preparation, it is template (mol ratio is 10: 1.0) that liquid phase part makes water and triethylamine, and the SAPO-34 molecular sieve crystallinity that obtains at last is 118%.
According to the preparation method and the step of example 2, but add Diisopropylamine as the organic amine template when the dried glue of preparation, it is template (mol ratio is 10: 1.0) that liquid phase part makes water and triethylamine, and the SAPO-34 molecular sieve crystallinity that obtains at last is 102%.
Embodiment 11
According to the preparation method and the step of example 2, but add di-n-propylamine as the organic amine template when the dried glue of preparation, it is template (mol ratio is 10: 1.0) that liquid phase part makes water and triethylamine, and the SAPO-34 molecular sieve crystallinity that obtains at last is 92%.
Embodiment 12
According to the preparation method and the step of example 2, but add Isopropylamine as the organic amine template when the dried glue of preparation, it is template (mol ratio is 10: 1.0) that liquid phase part makes water and morphine quinoline, and the SAPO-34 molecular sieve crystallinity that obtains at last is 121%.
Embodiment 13
According to the preparation method and the step of example 9, it is template (mol ratio is 100: 1.0) that liquid phase part makes water and triethylamine, and the SAPO-34 molecular sieve crystallinity that obtains at last is 90%.
Embodiment 14
According to the preparation method and the step of example 1, but change the consumption that synthesizes silicon sol in the liquid, its initial mole proportioning is: 0.5SiO
2: Al
2O
3: 1.0P
2O
5: 75H
2O: 1.25Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 105%.
According to the preparation method and the step of example 1, but change the consumption that synthesizes silicon sol in the liquid, its initial mole proportioning is: 0.2SiO
2: Al
2O
3: 1.0P
2O
5: 75H
2O: 1.25Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 65%.
Embodiment 16
According to the preparation method and the step of example 1, but change the consumption that synthesizes phosphoric acid in the liquid, its initial mole proportioning is: 1.25SiO
2: Al
2O
3: 0.4P
2O
5: 75H
2O: 1.25Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 97%.
Embodiment 17
According to the preparation method and the step of example 1, but change the consumption that synthesizes water in the liquid, its initial mole proportioning is: 1.25SiO
2: Al
2O
3: 1.0P
2O
5: 200H
2O: 1.25Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 85%.
Embodiment 18
According to the preparation method and the step of example 1, but change the consumption that synthesizes triethylamine in the liquid, its initial mole proportioning is: 1.25SiO
2: Al
2O
3: 1.0P
2O
5: 75H
2O: 0.02Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 80%.
Embodiment 19
According to the preparation method and the step of example 1, but with intending thin water aluminium substitution aluminum isopropylate.Its initial mole proportioning is: 1.25SiO
2: Al
2O
3: 1.0P
2O
5: 75H
2O: 1.25Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 86%.
According to the preparation method and the step of example 1, but replace silicon sol with white carbon black.Its initial mole proportioning is: 1.25SiO
2: Al
2O
3: 1.0P
2O
5: 75H
2O: 1.25Et
3N, the SAPO-34 molecular sieve crystallinity that obtains at last is 94%.
Claims (7)
1, a kind of preparation method of SAPO-34 molecular sieve may further comprise the steps successively:
A, in being housed, the container of agitator adds deionized water, respectively precursor compound, the organic amine of aluminium, phosphorus, silicon is sequentially added in the container then, by the time add another kind of material again after a kind of material mixes before, the mol ratio of each material in the final solution is:
A SiO
2: Al
2O
3: b P
2O
5: c H
2O: the d organic amine, wherein the scope of a is 0.10-1.5, and the scope of b is 0.10-1.5, and the scope of c is 0-300, and the scope of d is 0.01-4.0;
After B, each material mixed, evaporate to dryness moisture content obtained dried glue in 30-100 ℃ baking oven;
C, dried glue is placed the top of gas phase reaction kettle, the mixture that the reactor bottom adds organic amine and water reacted 24-72 hour down at 150-200 ℃;
D, reaction finish the afterreaction still cools off under state of nature, at last to sample wash according to a conventional method, drying and roasting, obtain the SAPO-34 molecular sieve.
2, preparation method according to claim 1, the presoma that it is characterized in that phosphorus is that mass percent is 85% phosphoric acid; The presoma of aluminium is aluminum isopropylate or pseudo-boehmite; The presoma of silicon is that mass percent is silicon sol or the gas-phase silica of 25-30%; Organic amine is triethylamine, di-n-propylamine, Diisopropylamine, morphine quinoline, tetraethyl ammonium hydroxide or Isopropylamine.
3, preparation method according to claim 1, the presoma that it is characterized in that aluminium is an aluminum isopropylate; The presoma of silicon is that mass percent is the silicon sol of 25-30%; Organic amine is triethylamine, morphine quinoline, tetraethyl ammonium hydroxide.
4, preparation method according to claim 1 is characterized in that organic amine and liquid phase part organic amine are organic amine of the same race or are organic amine not of the same race that organic amine and liquid phase part organic amine are organic amine not of the same race in the preferred dried glue in the dried glue.
5, preparation method according to claim 1, the scope that it is characterized in that a is 0.6-1.3, and the scope of b is 0.6-1.3, and the scope of c is 0-120, and the scope of d is 0.05-2.0.
6, preparation method according to claim 1, the mol ratio that it is characterized in that liquid phase part water and organic amine is 1.0-200: 1.0; Preferred 10-100: 1.0.
7, preparation method according to claim 1, it is characterized in that when c is 0, at first that the precursor compound silicon sol and the aluminium precursor compound thorough mixing of silicon is even, and then adding phosphorus precursor compound and organic amine, and do not add deionized water in the step (A), and can omit step (B).
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