CN100360405C - LTA and FAU molecular screen nanocrystalline preparation method - Google Patents
LTA and FAU molecular screen nanocrystalline preparation method Download PDFInfo
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- CN100360405C CN100360405C CNB200510016886XA CN200510016886A CN100360405C CN 100360405 C CN100360405 C CN 100360405C CN B200510016886X A CNB200510016886X A CN B200510016886XA CN 200510016886 A CN200510016886 A CN 200510016886A CN 100360405 C CN100360405 C CN 100360405C
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- 238000002360 preparation method Methods 0.000 title claims description 34
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004411 aluminium Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000003068 static effect Effects 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 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 7
- 239000000843 powder Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 230000001476 alcoholic effect Effects 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
- 238000005119 centrifugation Methods 0.000 claims description 2
- KZNVCIMXFKZCHP-UHFFFAOYSA-L disodium;chloride;fluoride Chemical compound [F-].[Na+].[Na+].[Cl-] KZNVCIMXFKZCHP-UHFFFAOYSA-L 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002159 nanocrystal Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 230000001089 mineralizing effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000007787 solid Substances 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910021536 Zeolite Inorganic materials 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
- 239000000463 material Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 organic bases Tetramethylammonium hydroxide Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
Abstract
The present invention relates to a method for preparing LTA and FAU molecular sieve nano crystal, which comprises: aluminium sources or silicon sources are added to mineralizing agents and tetramethylammonium hydroxide (TMAOH) to prepare solutions; the silicon sources or the aluminium sources are added and evenly stirred, and then react for 1 to 30 days at room temperature to 100 DEG C under a static state or stir; finally, the LTA and FAJJ molecular sieve nanometer crystal is obtained by washing and drying through crystallization, centrifugal separation or filtration. The LTA molecular sieve nano crystal is synthesized within the range of proportioning SiO2: Al2O3: (TMA) O2: Na: H2O or alcohol = 0.8 to 3.0: 1: 0 to 20: 0 to 7.5: 50 to 5000, and the FAU molecular sieve nano crystal is synthesized within the range of proportioning SiO2: Al2O3: (TMA) O2: Na: H2O or alcohol = 3.4: 0.5 to 1.8: 0 to 20: 0 to 7.5: 50 to 5000.
Description
Technical field
The invention belongs to the preparation method of the relevant molecular screen material of domain of inorganic chemistry, be specifically related to the preparation method of a kind of LTA and FAU molecular screen nanocrystalline.
Background technology
Fields such as FAU is widely used in catalysis with the LTA molecular sieve, separates, ion-exchange, the existing preparation technology obtains product and mostly is granularity greatly at the above body phase material of 1 μ m, the molecular sieve of this granularity can not effectively be brought into play its distinctive duct feature, particularly in the application of catalysis and ion-exchange field.When molecular sieve was applied to catalytic field and ion-exchange field, expectation possesses following feature: 1) bigger external surface area can obtain more active centre; 2) diffusion that reduces to help reactant and product of particle size makes the efficient of catalyzer higher, the easier generation of ion-exchange; 3) have more opening of the channel, reactant be difficult for to stop up the duct, helps prolonging the catalyst runs cycle, makes more abundant that ion-exchange carries out in the duct.
Chinese patent 96102487.9 has been reported a kind of preparation method of fine-crystal model A zeolite, by add the directed agents that oneself prepares in building-up process, obtains the A type zeolite of mean particle size less than 1 μ m, and the calcium adsorptive power of this product is not less than 320mg CaCO
3/ g anhydrous zeolite.This method preparation process is simple, easily realizes large-scale commercial production, but the product that obtains only is the body phase material less than 1 μ m, though the calcium adsorptive power is better, the granularity of zeolite is still very big, does not reach below the 100nm.
Chinese patent 200310111435.5 has been reported a kind of preparation method of nano type A molecular sieve, by introducing ultrasonic wave and microwave combined effect, the nanocrystal of generation can't be grown up, thereby obtained the A type molecular sieve of 0.1～100nm.Adopt this method to prepare nano molecular sieve, it is fast to have speed, advantages such as productive rate height, but realize relatively difficulty of large-scale commercial production.
The preparation method of LTA provided by the present invention and FAU molecular screen nanocrystalline, by introducing the organic bases Tetramethylammonium hydroxide and adding mineralizer, the crystalline mean sizes is reduced to below the 100nm, and by can regulating and control the granularity of product as required to the selection of silicon source, aluminium source reaction conditions, and obtain the nano material of homogeneous grain diameter.
Summary of the invention
It is the following FAU of 100nm and the preparation method of LTA molecular screen nanocrystalline that purpose of the present invention just is to provide a kind of crystalline mean sizes.
Concrete synthesis step is:
1. aluminium source (or silicon source) added mineralizer and Tetramethylammonium hydroxide (TMAOH), make solution;
2. add silicon source (or aluminium source), after stirring, room temperature to 100 ℃ static state or stirring were reacted 1-30 days down;
3. centrifugation or filtration after the crystallization, the washing drying obtains LTA and FAU molecular screen nanocrystalline.
Added the organic amine Tetramethylammonium hydroxide as template in the nanocrystalline process of synthesis of molecular sieve.Silicon source in the above-mentioned steps is one or more in tetraethoxy (TEOS), butyl silicate, methyl silicate, white carbon black, silica gel, silicon sol, the water glass.The aluminium source is one or more in aluminium powder, aluminium hydroxide, aluminum isopropylate, aluminum chloride, the sodium metaaluminate.
Solution in the above-mentioned steps can be the aqueous solution, alcoholic solution (ethanol, methyl alcohol, ethylene glycol, propyl alcohol) or alcohol solution.When the aluminium source was aluminium powder, aluminium powder was added in the solution of mineralizer, Tetramethylammonium hydroxide and water after the stirring and dissolving, with the membrane filtration of 0.2 μ m.Mineralizer is a sodium salt, comprises SODIUMNITRATE, sodium sulfate, sodium-chlor, Sodium Fluoride or sodium hydroxide.
The proportioning that the reaction soln that above-mentioned steps (2) obtains is formed is (0.8-3.0) SiO
2: 1Al
2O
3: (0.1-20) (TMA) O
2: (0-7.5) Na: (50-5000) H
2During O (or alcohol), obtain the LTA molecular screen nanocrystalline, the proportioning of composition is 3.4SiO
2: (0.5-1.8) Al
2O
3: (0.1-20) (TMA) O
2: (0-7.5) Na: (50-5000) H
2Obtain the FAU molecular screen nanocrystalline during O (or alcohol).
The product of gained, the silica alumina ratio of LTA molecular screen nanocrystalline are 1.0-2.6, and the silica alumina ratio of FAU molecular screen nanocrystalline is 2.7-4.6.
Characteristics of the present invention are: by introducing Tetramethylammonium hydroxide, the crystalline mean sizes is reduced to below the 100nm.Partly or entirely provide alkalimetal ion by sodium salt, the basicity in the reaction mixture is partly or entirely controlled by the amount of TMAOH, and sodium salt promotes the molecular sieve nucleation and improves productive rate owing to change the ion constant of solution and influence the crystalline pattern.
Present method synthetic LTA and FAU are nanocrystalline in catalyzer, sorbent material and ion-exchanger superior performance, because its crystalline size is even, pattern is regular, in others such as Subjective and Objective material, optics etc. good application can both be arranged.
Description of drawings
Following example will be described further the aspect of this synthetic LTA and FAU nano molecular sieve, and the part photo in the example is listed in the Figure of description.
Fig. 1: the XRD figure spectrum of product A 1;
Fig. 2: the XRD figure spectrum of product A 11;
Fig. 3: the TEM photo of product A 6;
Fig. 4: the TEM photo of product A 4;
Fig. 5: the TEM photo of product A 13;
Fig. 6: the TEM photo of product A 15.
Embodiment
Come enumeration technical characterstic of the present invention below in conjunction with specific embodiment.
Embodiment one
A kind of preparation method of A type molecular sieve nanocrystal, the proportioning of reaction solution is: 3SiO
2: 1.0Al
2O
3: 1.5 (TMA) O
2: 0.007NaCl: 276H
2O.At first with Al powder+NaCl+TMAOH stirring and dissolving, with the membrane filtration of 0.2 μ m.TEOS drips above-mentioned solution, after stirring, continues under agitation aging two days.Above-mentioned reaction soln is packed in the 150ml acrylic plastering bottle, puts into 100 ℃ of baking ovens, static reaction 15 days.Crystallization fully after, solid sample separated on 8000 rev/mins of whizzers in centrifugal 40 minutes, separated with whizzer with deionized water, ultrasonic washing repeatedly then, near 7, last solid sample is 80 ℃ of dryings 4 hours down up to the PH of separated water.Obtain product A 1, granular size is 80nm.
Embodiment two
A kind of preparation method of A type molecular sieve nanocrystal, this example except the proportioning of reaction solution is: 2.8SiO
2: 1.0Al
2O
3: 5.5 (TMA) O
2: 0.057NaCl: 600H
2Outside the O, other obtains product A 2 with embodiment one, and granular size is 100nm.
Embodiment three
A kind of preparation method of A type molecular sieve nanocrystal, present embodiment is except reaction raw materials changes aluminum isopropylate into, and all the other are all with embodiment one.Obtain product A 3, granular size is 100nm.
Embodiment four
A kind of preparation method of A type molecular sieve nanocrystal, present embodiment is except reaction raw materials changes white carbon black into, and all the other are all with embodiment one.Obtain product A 4, granular size is 90nm.
Embodiment five
A kind of preparation method of A type molecular sieve nanocrystal is except the reaction solution proportioning is 3.65SiO
2: Al
2O
3: 1.23 (TMA) O
2: 0.43Na
2O: 249H
2Outside the O, other obtains product A 5 with embodiment one, and granular size is 80nm.
Embodiment six
A kind of preparation method of A type molecular sieve nanocrystal is except the reaction solution proportioning is 11.27SiO
2: 1.82Al
2O
3: 13.5 (TMA) O
2: 0.3Na
2O: 700H
2Outside the O, other obtains product A 6 with embodiment one, and granular size is 90nm.
Embodiment seven
A kind of preparation method of A type molecular sieve nanocrystal is except the reaction solution proportioning is 5.2SiO
2: Al
2O
3: 8.3 (TMA) O
2: 0.23Na
2O: 400H
2Outside the O, other obtains product A 7 with embodiment one, and granular size is 130nm.
Embodiment eight
A kind of preparation method of A type molecular sieve nanocrystal, the proportioning of reaction solution is: 0.3Na
2O: 11.25SiO
2: 1.8Al
2O
3: 13.4 (TMA)
2O: 700H
2O.0.75 gram aluminum isopropylate, 5.00 gram TMAOH5H
2The sodium hydroxide solution of O, 0.6 gram 1M adds 7.0 gram water, stirs to clarification, adds the solution of 2.25 gram silicon sol and 2.0 gram water, continues to stir one day 100 ℃ of crystallization one day.Other subsequent disposal is with embodiment one.Obtain product A 8, granular size is 50nm.
Embodiment nine
A kind of preparation method of A type molecular sieve nanocrystal, present embodiment except the reaction solution proportioning is: 3.0SiO
2: 1.0Al
2O
3: 1.5 (TMA) O
2: 0.2NaNO
3: 276H
2Outside the O, all the other are all with embodiment one.Obtain product A 9, granular size is 60nm.
Embodiment ten
A kind of preparation method of A type molecular sieve nanocrystal, the proportioning of reaction solution is: 3SiO
2: 1.0Al
2O
3: 1.5 (TMA) O
2: 0.007Na: 276 ethanol.Aluminum isopropylate+NaCl+TMAOH+ ethanol stirring and dissolving at first is with the membrane filtration of 0.2 μ m.The ethanolic soln of TEOS drips above-mentioned solution, after stirring, continues under agitation aging two days.Above-mentioned reaction soln is packed in the 50ml teflon-lined stainless steel reaction, puts into 65 ℃ of baking ovens, static reaction 10 days.Crystallization fully after, solid sample separated on 8000 rev/mins of whizzers in centrifugal 40 minutes, separated with whizzer with deionized water, ultrasonic washing repeatedly then, near 7, last solid sample is 100 ℃ of dryings 4 hours down up to the PH of separated water.Obtain product A 10, granular size is 65nm.
Embodiment 11
A kind of preparation method of FAU type molecular screen nanocrystalline, present embodiment except the reaction solution proportioning is: 3.4SiO
2: 1.7Al
2O
3: 2.3 (TMA) O
2: 0.34Na
2SO
4: 1000H
2Outside the O, other obtains product A 11 with embodiment one, and granular size is 80nm.
Embodiment 12
A kind of preparation method of FAU type molecular screen nanocrystalline, 3.4SiO
2: 1.0Al
2O
3: 2.3 (TMA) O
2: 0.1NaNO
3: 300H
2O, at first aluminum isopropylate+NaNO
3+ TMAOH stirring and dissolving, 30% silicon sol drips above-mentioned solution, after stirring, continues under agitation aged at room temperature seven days.After the crystallization, solid sample separated on 10000 rev/mins of whizzers in centrifugal 40 minutes, separated with whizzer with deionized water, ultrasonic washing repeatedly then, and near 7, last solid sample is 80 ℃ of dryings 4 hours down up to the PH of separated water.Obtain product A 12, granular size is 60nm.
Embodiment 13
A kind of preparation method of FAU type molecular screen nanocrystalline, the proportioning of reaction solution is: 0.15Na
2O: 5.5 (TMA)
2O: 2.3Al
2O
3: 10SiO
2: 570H
2O.TMAOH5H
2O joins the aqueous solution of aluminum isopropylate, stirs to clarification, adds silicon sol (30%), continue to stir 30 minutes, the teflon-lined reactor of packing into, 100 ℃ 2 days.Other subsequent disposal is with embodiment one.Obtain product A 13, granular size is 80nm.
Embodiment 14
A kind of preparation method of FAU type molecular screen nanocrystalline, except the silicon source changes into the TEOS, other is identical with embodiment ten.Obtain product A 14, granular size is 60nm.
A kind of preparation method of FAU type molecular screen nanocrystalline, present embodiment except the reaction solution proportioning is: 3.54SiO
2: Al
2O
3: 2.46 (TMA) O
2: 0.04Na
2O: 370H
2Outside the O, other obtains product A 15 with embodiment one, and granular size is 80nm.
Embodiment 16
A kind of preparation method of FAU type molecular screen nanocrystalline, present embodiment except the reaction solution proportioning is: 3.63SiO
2: 1.7Al
2O
3: 1.576 (TMA) O
2: 0.045Na
2O: 250H
2Outside the O, other obtains product A 16 with embodiment one, and granular size is 80nm.
Embodiment 17
A kind of preparation method of FAU type molecular screen nanocrystalline, present embodiment except the reaction solution proportioning is: 10SiO
2: 2.4Al
2O
3: 5.5 (TMA) O
2: 0.16Na
2O: 550H
2Outside the O, other obtains product A 17 with embodiment one, and granular size is 60nm.
Embodiment 18
A kind of preparation method of FAU type molecular screen nanocrystalline, present embodiment except the reaction solution proportioning is: 3.4SiO
2: Al
2O
3: 2.46 (TMA) O
2: 0.32Na
2O: 380H
2O: outside the 13.6EtOH, other obtains product A 18 with embodiment one, and granular size is 85nm.
Claims (6)
1, the preparation method of a kind of LTA or FAU molecular screen nanocrystalline the steps include:
(1) aluminium source or silicon source are added mineralizer and Tetramethylammonium hydroxide, make water, alcohol or alcohol solution;
(2) add silicon source or aluminium source, after stirring, room temperature to 100 ℃ static state or stirring were reacted 1-30 days down;
(3) centrifugation or filtration after the crystallization, washing is dry, and forming proportioning in reaction soln is (0.8-3.0) SiO
2: 1Al
2O
3: (0.1-20) (TMA) O
2: (0-7.5) Na: (50-5000) H
2When O or alcohol, obtain the LTA molecular screen nanocrystalline; Forming proportioning in reaction soln is 3.4SiO
2: (0.5-1.8) Al
2O
3: (0.1-20) (TMA) O
2: (0-7.5) Na: (50-5000) H
2When O or alcohol, obtain the FAU molecular screen nanocrystalline.
2, the preparation method of LTA as claimed in claim 1 or FAU molecular screen nanocrystalline is characterized in that: the silicon source is one or more in tetraethoxy, butyl silicate, methyl silicate, white carbon black, silica gel, silicon sol, the water glass.
3, the preparation method of LTA as claimed in claim 1 or FAU molecular screen nanocrystalline is characterized in that: the aluminium source is one or more in aluminium powder, aluminium hydroxide, aluminum isopropylate, aluminum chloride, the sodium metaaluminate; When the aluminium source was aluminium powder, aluminium powder was added in the solution of mineralizer, Tetramethylammonium hydroxide and water after the stirring and dissolving, with the membrane filtration of 0.2 μ m.
4, the preparation method of LTA as claimed in claim 1 or FAU molecular screen nanocrystalline is characterized in that: alcoholic solution is ethanol, methyl alcohol, ethylene glycol or propyl alcohol.
5, the preparation method of LTA as claimed in claim 1 or FAU molecular screen nanocrystalline is characterized in that: mineralizer is a sodium salt.
6, the preparation method of LTA as claimed in claim 5 or FAU molecular screen nanocrystalline is characterized in that: mineralizer is SODIUMNITRATE, sodium sulfate, sodium-chlor, Sodium Fluoride or sodium hydroxide.
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| CN101318107B (en) * | 2008-05-20 | 2011-07-13 | 吉林大学 | Preparation method for pure silicon beta molecular sieve film |
| CN102992343A (en) * | 2012-12-09 | 2013-03-27 | 浙江大学 | Method for synthesizing zeolite molecular sieve via solid phase method without organic template |
| CN106698459B (en) * | 2017-01-16 | 2019-01-08 | 中国石油大学(华东) | A method of post-processing amorphous precursors prepare nano-sized zeolites molecular sieve |
| CN109833918B (en) * | 2017-11-28 | 2022-01-25 | 中国石油天然气股份有限公司 | Preparation method of carrier silica gel |
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| CN1160600A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Process of producing fine-grain Model. A zeolite |
| CN1397495A (en) * | 2002-06-28 | 2003-02-19 | 吉林大学 | Nanocrystal molecular sieve and its preparing process |
| CN1544327A (en) * | 2003-11-20 | 2004-11-10 | 江西师范大学 | Nanometer A type molecular sieve preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1160600A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Process of producing fine-grain Model. A zeolite |
| CN1397495A (en) * | 2002-06-28 | 2003-02-19 | 吉林大学 | Nanocrystal molecular sieve and its preparing process |
| CN1544327A (en) * | 2003-11-20 | 2004-11-10 | 江西师范大学 | Nanometer A type molecular sieve preparation method |
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