CN104941451A - Method for synthesizing NaA molecular sieve membrane by employing mesoporous zeolite crystal - Google Patents
Method for synthesizing NaA molecular sieve membrane by employing mesoporous zeolite crystal Download PDFInfo
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- CN104941451A CN104941451A CN201510284313.9A CN201510284313A CN104941451A CN 104941451 A CN104941451 A CN 104941451A CN 201510284313 A CN201510284313 A CN 201510284313A CN 104941451 A CN104941451 A CN 104941451A
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Abstract
The invention discloses a method for synthesizing a NaA molecular sieve membrane by employing mesoporous zeolite crystal, which is characterized in that the zeolite molecular sieve membrane is prepared by taking nano crystal stripped by the micron-sized mesoporous NaA zeolite as seed crystal. According to the invention, the mesoporous NaA zeolite crystal is crushed and configured to a water dispersion liquid, then separated to remove micron-sized particles, the nano crystal dispersion liquid is obtained, the nano crystal dispersion liquid can be taken as a seed crystal liquid for coating the surface of the hollow fiber with crystal, the synthesized film is compact, and the separating performance is excellent. The nano NaA zeolite crystal can be obtained by crushing micron-sized mesoporous NaA zeolite crystal, the method is simple, the yield is high, the nano crystal dispersion liquid can be used for preparing the NaA zeolite molecular sieve membrane, compared with the traditional zeolite crystal of which nano crystal can not be simply stripped, the NaA molecular sieve membrane has great advantage.
Description
Technical field
The present invention relates to a kind of method of synthesis zeolite film, be specifically related to a kind of method being made crystal seed synthesis NaA type molecular screen membrane by the mesoporous NaA zeolite of micron order.
Background technology
Zeolite molecular sieve film has good mechanical strength and chemical stability, and homogeneous pore passage structure, is widely used in the numerous areas such as separation, catalysis, electrode and optical material.Wherein, NaA zeolite molecular sieve has very strong hydrophily, is therefore widely deployed in organics dehydration field.
Pottery (aluminium oxide) doughnut corrosion-and high-temp-resistant, wall is thin and have high loading density (film surface area/volume ratio > 1000m
2/ m
3), become the novel carriers of synthesis zeolite rete.Research shows, the thin-walled of doughnut and high porosity make rete have higher infiltration evaporation flux.The preparation of NaA zeolite molecular sieve adopts crystal seed secondary growth method usually.Nanocrystal does crystal seed and is conducive to the zeolite molecular sieve rete that synthesis is fine and close continuously on aluminium oxide doughnut carrier.[the Ind.Eng.Chem.Res.2011 such as Shao, 50:9718 – 9726] research find dip-coating crystalline size be 90nm crystal seed liquid can the preparation of aluminium oxide doughnut carrier surface diauxic growth have high separability can NaA zeolite molecular sieve, and reproducible.In fact, zeolite nanocrystal is widely used in the synthesis of zeolite molecular sieve film as crystal seed, effectively can control the thicknesses of layers in diauxic growth and film layer structure, thus improve the separating property of film.
The nanocrystal of zeolite generally uses the synthesis liquid of clarification (low concentration) to synthesize under hydrothermal conditions, and often adds the size that structure directing agent (template) reduces crystal.But some problems can be produced like this: the synthesis liquid-crystalization speed of (1) low concentration is slow, and productive rate is lower, and yield is lower after the operations such as centrifuge washing repeatedly; (2) reaction terminate after, a large amount of raw materials has neither part nor lot in reaction, comprise expensive, to the disadvantageous structure directing agent of environment; (3) organic formwork agent can be embedded in crystal structure when synthesizing, affect the application of nanocrystal, therefore general in air or oxygen high-temperature roasting remove organic formwork agent, but roasting can reduce the degree of crystallinity of nanocrystal and cause irreversible reunion.
In order to overcome the above problems, a lot of seminar is studied in nanocrystal synthesis.Yang etc. [Microporous Mesoporous Mater.2009,117:33-40] adopt the Pt (NH of 0.003M
3)
4cl
2as the NaA zeolite crystal of crystallization director synthesis nano.[the Chem.Commun.2000 such as Wang, 23:2333-2334] adopt organic polymer to solve Sintering Problem in nanocrystal roasting process, also adopt [J.Am.Chem.Soc.2009,125:9928-9929] methyl cellulose hydrogel controls the growth of zeolite crystal, synthesizes the NaX zeolite crystal of NaA and 120nm of 165nm under the condition of Template-free method.
Therefore, need the mode of easier acquisition nanocrystal, for the zeolite molecular sieve rete that synthesis is fine and close continuously.
Summary of the invention
The object of the invention is to overcome complicated process prepared by nanocrystal, provide a kind of mode of simple and effective acquisition nanocrystal newly, prepare NaA molecular sieve membrane at carrier surface.Concrete the invention provides a kind of method adopting mesoporous zeolite Opacity in lens NaA molecular sieve membrane.
Operation scheme of the present invention is as follows:
A kind of step of the method for mesoporous zeolite Opacity in lens NaA molecular sieve membrane that adopts is as follows:
A. the preparation of crystal seed liquid
Crystal seed aqueous dispersions is mixed with by after mesoporous for micron order NaA zeolite crystal grinding, its mass fraction is 0.1%-5%, then this dispersion liquid is carried out centrifugation removing micron-sized crystals, the rotating speed of centrifugation is 500-5000rpm, centrifugation time is 5-60min, crystal seed aqueous dispersions after removing micron-sized crystals, is called crystal seed liquid;
B. the preparation of crystal seed layer
Crystal seed layer adopts dip-coating-abrasive tumbling legal system standby, first carrier is dipped vertically into 5-30s in crystal seed liquid, after proposition, carrier is put into baking oven, then taken out by dried carrier, is rotated by carrier, carries out abrasive tumbling from the bottom to top on one side, obtains seeding carrier;
C. the preparation of rete
Adopt hydrothermal synthesis method to prepare rete, the aluminium source of having dissolved dropwise is added the silicon source in stirring, obtaining mol ratio is Na
2o:Al
2o
3: SiO
2: H
2: the synthesis liquid of (50-5000) O=(1-20): 1:(1-200), by in the stainless steel cauldron poured into after synthesis stirred at ambient temperature ageing with polytetrafluoro liner, then the carrier of seeded is vertically put into wherein, reaction terminates rear taking-up carrier, repeatedly cleans and soaks rear drying.
Preferably, the particle size of the mesoporous NaA zeolite crystal of the micron order in described steps A is 2-5 μm, and mesoporous pore size is 4-10nm.
Grinding in described steps A also can adopt ball milling to substitute.
Preferably, the rotating speed of centrifugation in described steps A is 1000rpm, and centrifugation time is 30min.
Preferably, in described step B, carrier is aluminium oxide doughnut or the organic polymer hollow fiber conduit of external diameter <3mm.
Preferably, the proportioning of synthesizing liquid in described step C is Na
2o:Al
2o
3: SiO
2: H
2o=3.4:1:2:155.
The present invention adopts simple 10min to grind mesoporous NaA zeolite crystal, and coordinate centrifugally operated, the 110nm crystal (as shown in Figure 2) of about 10% can be obtained, namely 2wt% grinding mesoporous NaA crystal crystal seed liquid centrifugal after crystal seed liquid concentration be 0.22wt%.The molecular screen membrane of the present invention's synthesis is fine and close continuously, only exposes the tightly packed film forming layer of cubic crystal of wedge angle, does not have visible hole or other defect (as shown in Figure 3).The NaA molecular sieve membrane of the present invention's synthesis is used for infiltration evaporation, and result shows, this film is for the separation factor of the 90wt% ethanol water of 75 DEG C more than 10,000, and the flux of film can reach 8.38kg/m
2h.Therefore the NaA type molecular screen membrane of the inventive method synthesis has good separation selectivity and permeability.
The present invention is adopted to be separated (or long period sedimentation) with low-speed centrifugal by the micron-sized mesoporous NaA crystal of grinding and to obtain a certain amount of nanocrystal like a cork, avoid the complex separations step needed for conventional method synthesis of nano zeolite crystal, and yield is high.This is mainly because micron-sized mesoporous NaA zeolite crystal is made up of nanometer domain.The present invention proves that nanocrystal that mesoporous crystal peels off can the NaA molecular sieve membrane of Induced synthesis densification first, compared to the traditional zeolite crystal of simple stripping nano crystal not having very large advantage.
Accompanying drawing explanation
Fig. 1 is the SEM figure of mesoporous NaA crystal;
Fig. 2 is the SEM figure of the centrifugal rear crystal fragments of mesoporous NaA crystal of grinding;
Fig. 3 is the surperficial SEM figure of aluminium oxide doughnut outer surface synthesis NaA zeolite molecular sieve.
Detailed description of the invention
In order to illustrate that the present invention makes the method for crystal seed synthesis NaA zeolite molecular sieve by the nanocrystal of the mesoporous NaA zeolite stripping of micron order better, and compared to the advantage of traditional zeolite crystal, enumerate the synthetic example of some molecular screen membranes below, but the invention is not restricted to cited example.
The preparation of mesoporous crystal
Synthesising mesoporous crystal cause mesoporous dose for dimethyl hexadecyl base [3-(trimethoxy is silica-based) propyl group] ammonium chloride (i.e. TPHAC), synthesis formula of liquid is 100SiO
2: 333Na
2o:67Al
2o
3: 20000H
2o:5TPHAC.Synthesis step is as follows: by the 54wt%TPHAC solution of 5 × 0.172g, the nine water sodium metasilicate (SiO of 5.69g
2=21.1%) and the NaOH of 2.36g (>=96%) be dissolved in 38.75g deionized water, and 2.58g sodium aluminate (Al/NaOH=0.79) to be dissolved in 30.00g deionized water.After two kinds of solubilize are complete, by its disposable mixing, and acutely rock 5 minutes, then synthesis liquid is transferred in band teflon-lined stainless steel cauldron, rotate in an oven with the rotating speed of 30rpm, at 373K crystallization 4h, then with deionized water by product filtration washing repeatedly, the baking oven being placed in 373K is dry, then at 823K roasting 3h to remove template.Fig. 1 is the SEM figure of mesoporous NaA crystal.Fig. 2 is the SEM figure of the centrifugal rear crystal fragments of mesoporous NaA crystal of grinding.
The preparation of synthesis liquid
The molar ratio of synthesis liquid is 3.4Na
2o:Al
2o
3: 2SiO
2: 155H
2o.First nine water sodium metasilicate are added in deionized water, and be placed in 323K stirred in water bath dissolving 15min.Then taking sodium aluminate adds in deionized water, and stirring at room temperature is to dissolving completely.Then sodium aluminate solution is dropwise added in the sodium silicate solution in stirring, after being added dropwise to complete, by the gel of emulsus synthesis liquid with certain mixing speed room temperature ageing 0.5h.
Embodiment 1
A. the preparation of crystal seed liquid
Get the mesoporous NaA zeolite crystal of micron order and grind 10min in agate mortar, then taken out by product, be mixed with the aqueous solution of 2wt%, and use as crystal seed liquid after the centrifugal 30min of 1000rpm removes bulky grain, its mass fraction is 0.22%.
B. the preparation of crystal seed layer
Crystal seed layer adopts dip-coating-abrasive tumbling legal system standby.First carrier is dipped vertically into 10s in crystal seed suspension, after proposition, carrier is put into baking oven, more dried carrier is taken out, carrier is rotated, carry out abrasive tumbling from the bottom to top on one side, obtain seeding carrier.
C. the preparation of rete
Synthesis liquid is poured in the stainless steel cauldron of band polytetrafluoro liner, then the doughnut carrier of seeded is vertically put into wherein, ensure that the liquid level of synthesis liquid is higher than carrier.Sealed reactor also puts into baking oven 373K crystallization 3h, and reaction terminates rear running water shower reactor to room temperature, then takes out film pipe, after repeatedly cleaning by deionized water and soaking, dry in 333K baking oven, obtain NaA zeolite molecular sieve, operate for infiltration evaporation.Fig. 3 is the surperficial SEM figure of aluminium oxide doughnut outer surface synthesis NaA zeolite molecular sieve.
Embodiment 2
With embodiment 1, steps A intermediary hole crystal adopts ball milling to pulverize, and crystal seed liquid mass fraction is 0.1%; 30s in crystal seed suspension is immersed in step B.
Embodiment 3
With embodiment 1, the crystal seed liquid mass fraction in steps A is 5%; Immerse 30s in crystal seed suspension in step B, carrier is Polyethersulfone Hollow Fiber Plasma pipe.
Comparative example 1
A. the preparation of crystal seed liquid
Get traditional NaA crystal (Luoyang is built dragon and bought) and grind 10min in agate mortar, then product is taken out, be mixed with the aqueous solution of 2wt%, and use as crystal seed liquid after the centrifugal 30min of 1000rpm removes bulky grain, its mass fraction <0.05%.
B. the preparation of crystal seed layer
Crystal seed layer adopts dip-coating-abrasive tumbling legal system standby.First carrier is dipped vertically into 10s in crystal seed suspension, after proposition, carrier is put into baking oven, more dried carrier is taken out, carrier is rotated, carry out abrasive tumbling from the bottom to top on one side, obtain seeding carrier.
C. the preparation of rete
Synthesis liquid is poured in the stainless steel cauldron of band polytetrafluoro liner, then the doughnut carrier of seeded is vertically put into wherein, ensure that the liquid level of synthesis liquid is higher than carrier.Sealed reactor also puts into baking oven 373K crystallization 3h, and reaction terminates rear running water shower reactor to room temperature, then takes out film pipe, after repeatedly cleaning by deionized water and soaking, dry in 333K baking oven, obtain NaA zeolite molecular sieve, operate for infiltration evaporation.
Following table is the result that embodiment 1-4 and comparative example 1 synthesize the experiment of NaA zeolite molecular sieve seepage slope.Material liquid is 90wt.% ethanol water, and experimental temperature is 75 DEG C.
| Embodiment | Carrier porosity (%) | Total flux (kg/m 2h) | Separation factor |
| 1 | 52 | 8.38 | >10,000 |
| 2 | 50 | 8.05 | >10,000 |
| 3 | 51 | 8.19 | >10,000 |
| Comparative example 1 | 53 | - | - |
"-" expression film quality is too poor and cannot carry out infiltration evaporation operation.
Claims (6)
1. adopt a method for mesoporous zeolite Opacity in lens NaA molecular sieve membrane, it is characterized in that its step is as follows:
A. the preparation of crystal seed liquid
Crystal seed aqueous dispersions is mixed with by after mesoporous for micron order NaA zeolite crystal grinding, its mass fraction is 0.1%-5%, then this dispersion liquid is carried out centrifugation removing micron-sized crystals, the rotating speed of centrifugation is 500-5000rpm, centrifugation time is 5-60 min, crystal seed aqueous dispersions after removing micron-sized crystals, is called crystal seed liquid;
B. the preparation of crystal seed layer
Crystal seed layer adopts dip-coating-abrasive tumbling legal system standby, first carrier is dipped vertically into 5-30s in crystal seed liquid, after proposition, carrier is put into baking oven, then taken out by dried carrier, is rotated by carrier, carries out abrasive tumbling from the bottom to top on one side, obtains seeding carrier;
C. the preparation of rete
Adopt hydrothermal synthesis method to prepare rete, pour in the stainless steel cauldron with polytetrafluoro liner, then vertically put into the synthesis liquid configured wherein by the carrier of seeded, reaction terminates rear taking-up film pipe, repeatedly cleans and soaks rear drying.
2. in accordance with the method for claim 1, it is characterized in that the particle size of the mesoporous NaA zeolite crystal of micron order in described steps A is 2-5 μm, mesoporous pore size is 4-10 nm.
3. in accordance with the method for claim 1, it is characterized in that the grinding in described steps A also can adopt ball milling to substitute.
4. in accordance with the method for claim 1, it is characterized in that the rotating speed of centrifugation in described steps A is 1000 rpm, centrifugation time is 30 min.
5. in accordance with the method for claim 1, it is characterized in that in described step B, carrier is aluminium oxide doughnut or the organic polymer hollow fiber conduit of external diameter <3 mm.
6. the proportioning that in accordance with the method for claim 1, it is characterized in that synthesizing in described step C liquid is Na
2o:Al
2o
3: SiO
2: H
2o=3.4:1:2:155.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107174954A (en) * | 2017-05-27 | 2017-09-19 | 大连理工大学 | A kind of method that snead process quickly prepares ultra-thin NaA zeolite membranes |
| CN109970075A (en) * | 2019-03-26 | 2019-07-05 | 上海工程技术大学 | A kind of method of low temperature synthesis A type molecular sieve film |
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| CN101381087A (en) * | 2008-10-15 | 2009-03-11 | 南京工业大学 | Method for synthesizing NaA zeolite membrane |
| CN102583430A (en) * | 2012-03-01 | 2012-07-18 | 浙江大学 | Method for synthesizing NaA-type molecular sieve membrane on inner wall of support body |
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2015
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107174954A (en) * | 2017-05-27 | 2017-09-19 | 大连理工大学 | A kind of method that snead process quickly prepares ultra-thin NaA zeolite membranes |
| CN109970075A (en) * | 2019-03-26 | 2019-07-05 | 上海工程技术大学 | A kind of method of low temperature synthesis A type molecular sieve film |
| CN109970075B (en) * | 2019-03-26 | 2023-03-31 | 上海工程技术大学 | Method for synthesizing A-type molecular sieve membrane at low temperature |
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