CN1382519A - Process for preparing zeolite film with self-supporting multi-stage artery structure - Google Patents
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- CN1382519A CN1382519A CN 02111871 CN02111871A CN1382519A CN 1382519 A CN1382519 A CN 1382519A CN 02111871 CN02111871 CN 02111871 CN 02111871 A CN02111871 A CN 02111871A CN 1382519 A CN1382519 A CN 1382519A
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Abstract
A process for preparing the zeolite film with self-supporting multi-stage artery structure includes statically or dynamically attaching the nano zeolite colloid onto cellulose filter membrane, calcining to remove the cellulose template and obtained the self-supporting zeolite membrane with spongy artery structure, and gas-solid phase hydrothermal treating. Its advantages are high mass transfer performance, high activity and high utilization rate.
Description
Technical field
The present invention is a kind of method for preparing zeolite film with self-supporting multi-stage artery structure with static assembling, gas-solid phase and diauxic growth treatment technology.
Background technology
Zeolite possesses the micropore, ion-exchange performance, molecular screening performance and good heat and the hydrothermal stability that enrich homogeneous as a kind of porous inorganic material, is widely used in catalysis and the adsorptive separation technology.General direct synthetic zeolite is comparatively loose crystal powder, in actual applications, generally need to add various adhesives (as clay or silicate etc.) moulding, but its result often makes the effective surface area of material obviously reduce, and has introduced diffusion-restricted.A kind of better increase zeolite effective surface area, the method that reduces diffusional resistance is that molecular sieve is deposited on the pseudostructure, preparation zeolite net membrane structure not only can reduce diffusion influence, also can guarantee low pressure drop and high zeolite utilization rate.
Recently, (R.A.Caruso such as Caruso, Jan H.Schattka, Adv.Mater., 2000,12,1921.) to adopt the carboxylic acid cellulose filter membrane cheaply be easy to get be that template successfully synthesizes the metal oxide film with three-dimensional micro network structure, this method at first is poured into the method for metal alkoxide by pre-soaking or filtration in the filter membrane template, and by hydrolytic polymerization, organic formwork agent is removed in roasting then.But this method can not be applied directly to the synthetic field of zeolitic material.This area research personnel are seeking the preparation method of easy, the respond well zeolite membrane of a kind of method always.
Summary of the invention
The objective of the invention is to study a kind of simple and easy to control, economic and method of synthetic zeolite film with self-supporting multi-stage artery structure apace.
The objective of the invention is to study the method for the zeolite film with self-supporting multi-stage artery structure that a kind of synthetic effective surface area is big, diffusion-restricted reduces.
The objective of the invention is to study a kind of synthetic intensity height, duct method that be evenly distributed, widely used multi-stage artery structure zeolite membrane.
The method for preparing zeolite film with self-supporting multi-stage artery structure involved in the present invention is as follows:
1. synthetic zeolite crystallite colloid being dispersed in and forming required 0.05～20% (wt%) concentration and pH value in the aqueous solution is 1～14 zeolite colloidal solution;
2. preliminary treatment is carried out on the cellulose filter membrane surface, method is to be that 0.1～5% polycation electrolyte solution soaked 20 minutes～24 hours with cellulose filter membrane in concentration, cleans 1～6 time with distilled water then, makes the cellulose filter membrane surface lotus that becomes positively charged; Also available polyanion electrolyte solution soaks and makes the cellulose filter membrane surface be with negative electrical charge during processing;
3. the cellulose filter membrane that the surface is charged is static state or 5 minutes～12 hours time of dynamic soaking in the zeolite glue of desired concn, dynamically as hyperacoustic ultrasonic radiation etc., after absorption is finished filter membrane is pressed from both sides out airing (Texturized in order to prevent that filter membrane from taking place in the airing process, as it can be clipped between two slides) from the zeolite glue in the airing process.Alternately adsorb polyelectrolyte and nano zeolite colloid then to desired thickness; General 100～500nm thickness.
4. with the nano zeolite/cellulose composite membrane roasting that obtains, promptly obtain zeolite film with self-supporting multi-stage artery structure;
Wherein in 1 the zeolite grain size of said zeolite glue in nanometer between the micrometer range, concentration is (wt%) between 0.05-20%, the pH value is between 1-14.
Polycation electrolyte and polyanion electrolyte can be respectively PDDA (PDDA) and poly-p-sulfonic acid base styrene (PSS) or the like in 2, can positively charged after the cellulose filter membrane modification, and also can be electronegative.
3 mesolite colloids can be used surperficial positively charged, also can realize by regulator solution pH value with electronegative zeolite, and the zeolite lotus positive electricity in the general acid solution, the zeolite bear electricity in the alkaline solution, the zeolite solution of not handling is alkaline bear.Per deposition process time in step is 10 minutes to 24 hours, dries can at room temperature dry or heat and dry, and the airing temperature is 5～200 ℃.
Sintering temperature is 200-1000 ℃ in 4.
Above-mentioned nano zeolite/the cellulose composite membrane that makes dried be placed in nitrogen or other inert gas, as argon gas, helium etc., the intensification roasting, again in aerating oxygen or the air atmosphere 200-1000 ℃ of roasting, or directly aerating oxygen or air total roasting time 1-50 hour, obtain zeolite film with self-supporting multi-stage artery structure at same roasting temperature.
Used cellulose is considered film such as carboxylic acid cellulose filter membrane, unmodified cellulose filter membrane etc.
In order to improve zeolite membrane intensity of the present invention, make it be applicable to various environment, the zeolite membrane after the roasting under 100～240 ℃ and under the power of boosting certainly of this temperature, is handled zeolite membrane under the vapor action of organic amine and water.1 hour to 20 days processing time, handle the back same as above in air or oxygen atmosphere roasting get final product.Handle one or more (as 2～3 kinds) mixtures in used organic amine such as primary amine, secondary amine, tertiary amine or the diamines, as ammonia, ethylenediamine, triethylamine or their mixture.
If will make nano zeolite/carboxylic acid cellulose composite zeolite film carries out after-treatment once more in siliceous nutrient source, can reach the purpose that improves zeolite membrane equally.60～160 ℃ of hydrothermal growth treatment temperatures, 0.5～5 day processing time.Use NH after the processing
4OH solution washing several, the distilled water washing is dried; Roasting in air or oxygen atmosphere at last.Siliceous nutrient source such as the ethyl orthosilicate hydrolysate in TPAOH solution, sodium silicate solution etc.
Zeolite grain size of the present invention is in 1～200 nanometer range, and the zeolite membrane surface area that this scope makes is big, diffusion-restricted is little, better effects if.
The present invention's implementation condition preferably is:
The concentration of zeolite colloidal particle is 0.1-10%.
The pH value of zeolite colloidal solution is at 2-12.
Used polyelectrolyte is polycation electrolyte or polyanion electrolyte, as PDDA (PDDA), and poly-p-sulfonic acid base styrene (PSS).
Absorption deposition afterproduct dries at 40-180 ℃.
Cellulose filter membrane can be the fiber of various celluloses and modification thereof as matrix, but optimum with the carboxylic acid cellulose filter membrane, and price is not high, and is respond well.
The aperture of carboxylic acid cellulose microporosity filter membrane can be at 0.1 μ m between the 2 μ m
Among the present invention if with further handling under the vapor action of ammonia or organic amine and water, used organic amine primary amine, secondary amine, tertiary amine is as follows:
C
nH
2n+1NH
2, n=0～5, as: n-propylamine, n-butylamine;
C
nH
2n+1C
mH
2m+1NH, n, m=0～5, as: diethylamine, tripropyl amine (TPA);
C
nH
2n+1C
mH
2m+1C
iH
2i+1N, n, m, i=0～5, as: triethylamine.
The organic amine that gas-solid is handled mutually is a n-butylamine, n-propylamine, ethylenediamine, a kind of or their mixture, for example 1-4 kind organic amine mixture in the triethylamine.
120～200 ℃ of the temperature that gas-solid is handled mutually.
6 hours～10 days time that gas-solid is handled mutually.
Hydrothermal growth liquid is siliceous akaline liquid, as the hydrolysate of ethyl orthosilicate in TPAOH solution, sodium silicate solution etc.
The hydrothermal growth treatment temperature is 80～140 ℃.
The hydrothermal growth processing time is 0.5-3 days.
The inventive method can prepare various structural zeolite films, as has MFI, BEA, A, the isostructural zeolite film with self-supporting multi-stage artery structure of FAU.
The zeolite membrane that the inventive method obtains has evenly abundant macroporous structure, therefore is expected in catalysis fields such as adsorbing separation performance important application.
By preparing the product of the present invention that various types of zeolite molecular sieves obtain, has remarkable advantages aspect catalyst, adsorbent, release agent and the large biological molecule separation membrane.Can be applicable to the cleanser of waste water, waste gas.
As the adsorbing separation film of large biological molecule, the zeolite membrane that the inventive method obtains has broad application prospects.
The zeolite film with self-supporting multi-stage artery structure that method provided by the present invention obtains, has the time cycle weak point that produces finished product, the zeolite membrane even compact, has abundant multistage pore canal, the promptly three-dimensional sponge shape macropore (aperture is about 1 μ m) that connects, three-dimensional zeolite microtubule (the zeolite micropore road on aperture about 200～300nm) and the microtubule wall that connects.The film-strength that obtains after process gas-solid phase and hydrothermal growth are handled is fine, can satisfy the needs of practical application.The inventive method technology is simple, preparation efficiency is high, good product quality.
Description of drawings
Following example will be described further method provided by the invention.Part photo in the example is listed in the Figure of description.
Fig. 1 is the SEM photo of carboxylic acid cellulose filter membrane.
Fig. 2 is a product B
1The SEM photo.
Fig. 3 is a product B
2The SEM photo.
Fig. 4 is a product B
3SEM photo (insertion portion is the SEM photo of low multiple among the figure).
Fig. 5 is a products C
1SEM photo (insertion portion is the SEM photo of low multiple among the figure).
Fig. 6 is product D
1The SEM photo.
Fig. 7 is product D
8The SEM photo.
Fig. 8 is the XRD figure spectrum of part nano zeolite/carboxylic acid cellulose composite membrane product; A is the XRD figure spectrum of carboxylic acid cellulose filter membrane, and b is a product A
3XRD figure spectrum, c is a product A
10XRD figure spectrum, d is a product A
12XRD figure spectrum, e is a product A
16XRD figure spectrum.
The specific embodiment
Following example is not to be limitation of the present invention, these those skilled in the art can by example with other not the mode of super authority replace, thereby reach purpose of the present invention.
Example 1
Tetraethoxy-silicane, TPAOH and distilled water are mixed according to 25: 9: 480 mole proportioning, vigorous stirring is 1 day under the room temperature, in the 373K oil bath backflow 18-36 hour, obtain nanometer silicalite-1 (MFI skeleton structure) zeolite glue, again with the colloid centrifugation repeatedly that obtains, again be dispersed in the distilled water after the washing, obtain pH and be about 9.5, mass percent is 4% silicalite-1 zeolite glue (the zeolite particle diameter is 80nm).Be that 0.3% polycation electrolyte PDDA carries out preliminary treatment to carboxylic acid cellulose filter membrane (the filter membrane aperture is 0.45 μ m) surface with concentration earlier before the deposition zeolite, adsorption time is about 1h, fully soaks, washs with deionized water after the absorption.It is in 1% the nano zeolite glue (regulating about pH to 9.5) that the cellulose filter membrane of modification is immersed in concentration, static absorption 1 hour.After absorption is finished filter membrane is pressed from both sides out room temperature airing (Texturized in order to prevent that filter membrane from taking place in the airing process, as in the airing process, to need it is clipped between two slides) from the zeolite glue.Can obtain nano zeolite/carboxylic acid cellulose composite membrane.
Example 2-4
Experimentize with the method identical, but the mass percent concentration of zeolite colloidal solution is carried out modulation, use 0.1%, 0.5%, 20% silicalite-1 zeolite glue respectively with example 1; Obtain nano zeolite/carboxylic acid cellulose composite membrane, be designated as A respectively
2, A
3, A
4
Example 5-8
Experimentizing with the method identical with example 3, but the pH value of zeolite colloidal solution is carried out modulation, is respectively 1,4,7 and 12 silicalite-1 zeolite glue with the pH value; Obtain nano zeolite/carboxylic acid cellulose composite membrane, be designated as A respectively
5, A
6, A
7, A
8
Example 9-12
Experimentize with the method identical with example 3, but the thickness to the deposition zeolite membrane is regulated and control, by changing the zeolite membrane that the cycle-index of alternately adsorbing polycation electrolyte and nano zeolite colloid obtains different-thickness, through 2,3,4,5 times sorption cycle has obtained nano zeolite/carboxylic acid cellulose composite membrane, is designated as A respectively
9, A
10, A
11, A
12
Example 13
Experimentize with the method identical, but select for use 0.5% polyanion electrolyte PSS that preliminary treatment is carried out on carboxylic acid cellulose filter membrane surface in the experimentation, obtained nano zeolite/carboxylic acid cellulose composite membrane, be designated as A with example 3
13
Example 14-15
Experimentizing with the method identical with example 13, but the pH value of zeolite colloidal solution is carried out modulation, is respectively 1 and 4 silicalite-1 zeolite glue with the pH value; Obtain nano zeolite/carboxylic acid cellulose composite membrane, be designated as A respectively
14, A
15
Example 16
Experimentize with the method identical with example 3, (50kHz 120W) dynamically adsorbs under the effect, and adsorption time is 5 minutes, has obtained nano zeolite/carboxylic acid cellulose composite membrane, is designated as A in ultrasonic radiation but use instead in the experimentation
16
Example 17-20
Experimentize with the method identical, but adsorption time is respectively 1,10 with example 16,15,30 minutes, obtained nano zeolite/carboxylic acid cellulose composite membrane, be designated as A respectively
17, A
18, A
19, A
20
Example 21-23
Experimentizing with the method identical with example 16, but use the zeolite of different-grain diameter to be building block, is 60nm with particle diameter respectively, the silicalite-1 zeolite glue of 150nm and 300nm; Obtain nano zeolite/carboxylic acid cellulose composite membrane, be designated as A respectively
21, A
22, A
23
Example 24-29
Experimentize with the method identical, but change the type of employed nano zeolite with example 16, by ZSM-5, TS-1, Beta, A, type nano zeolites such as X and Y are building block, have obtained nano zeolite/carboxylic acid cellulose composite membrane, are designated as A respectively
24, A
25, A
26, A
27, A
28, A
29
Example 30
Experimentize with the method identical, but the carboxylic acid cellulose microporosity filter membrane of using aperture 0.1 μ m instead is a template, has obtained nano zeolite/carboxylic acid cellulose composite membrane, is designated as A with example 16
30
Example 31
With example 3 resulting sample A
3Remove organic matter at the tubular type kiln roasting and obtain pure zeolite membrane, during roasting at first under nitrogen protection with 2K min
-1Programming rate be heated to 873K and keep 4h, under air atmosphere, continue roasting 8h then.The zeolite film with self-supporting multi-stage artery structure that obtains is designated as B
1
Example 32-33
Experimentize with the method identical, but the roasting sample changes A into example 31
16, A
23, the zeolite film with self-supporting multi-stage artery structure that obtains is designated as B respectively
2, B
3
Example 34
With 0.2 gram sample B
1Place reactor porous plate top.Inject 2 gram ethylenediamines with syringe to reactor bottom, the mixture of triethylamine and distilled water (mol ratio is 2: 9: 6) was 180 ℃ of following crystallization 5 days, and product takes out the back and washs with distilled water; After 393K dries 12h directly in air atmosphere in 823K roasting 8h, promptly obtain multi-stage artery structure zeolite membrane material C
1
Example 35-38
Experimentize with the method identical with example 34, but change gas-solid phase treatment temperature, respectively at 140 ℃, 160 ℃, 180 ℃ and 200 ℃ of processing obtain the multi-stage artery structure zeolite membrane material of self-supporting, are designated as C respectively
2, C
3, C
4, C
5
Example 39-41
Experimentize with the method identical with example 34, but change crystallization time, through 1 day, 3 days and 10 days crystallization obtained the multi-stage artery structure zeolite membrane material of self-supporting, are designated as C respectively
6, C
7, C
8
Example 42-44
Experimentize with the method identical with example 34, but change the mole proportioning of used organic amine, change the mixture ethylenediamine, the mol ratio of triethylamine and distilled water is 1: 0: 3,1: 0: 6, and 6: 0: 1,1: 9: 6,0: 9: 6, obtain the multi-stage artery structure zeolite membrane material of self-supporting, be designated as C respectively
9, C
10, C
11, C
12, C
13
Example 45-47
Experimentize with the method identical with example 34, but change the kind of used organic amine, the triethylamine in the mixture is replaced with ammonia, butylamine or n-propylamine obtain the multi-stage artery structure zeolite membrane material of self-supporting, are designated as C respectively
14, C
15, C
16
Example 48
With 0.1 gram sample A
16Putting into the 10g proportioning is 3 TPAOH: 25 SiO
2: 1,500 H
2O: in the clarification growth-promoting media of 100 EtOH, behind 373K hydrothermal treatment consists certain hour, take out, use 0.2M NH
4OH solution washing three times is used the distilled water washed twice again; After 393K dries 12h directly in the 873K air atmosphere roasting 6h remove organic matter, promptly obtain multi-stage artery structure zeolite membrane material D
1
Example 47-48
Experimentize with the method identical, but the quality of growth-promoting media is respectively the multi-stage artery structure zeolite membrane material that 5,20 grams have obtained self-supporting, is designated as D respectively with example 48
2And D
3
Example 49-51
Experimentize with the method identical with example 48, but change the hydrothermal treatment consists temperature, at 80 ℃, 120 ℃ and 140 ℃ of crystallization have obtained the multi-stage artery structure zeolite membrane material of self-supporting, are designated as D respectively
4, D
5, D
6
Example 52-54
Experimentize with the method identical with example 48, but change crystallization time, through 1 day, 3 days and 10 days crystallization obtained the multi-stage artery structure zeolite membrane material of self-supporting, are designated as D respectively
7, D
8, D
9
Example 55
The stereoscan photograph of the said goods (SEM) all absorbs on Philips XL30 D6716 instrument, Fig. 1-the 7th, and the electromicroscopic photograph of sample segment, the electromicroscopic photograph of all the other samples is similarly.With XRD (on RigakuD/Max-IIA type X-ray diffractometer, carry out, see Fig. 8) nano zeolite/carboxylic acid cellulose composite membrane is characterized.As can be seen from Figure 8, except the steamed bun peak that unformed carboxylic acid cellulose filter membrane causes, the characteristic peak of MFI structural zeolite has appearred all in the XRD spectrum through the carboxylic acid cellulose membrane after the nano zeolite assembling.And, show that increasing the absorption number of times can improve the load capacity of zeolite on cellulose along with the increase zeolite diffraction maximum of frequency of depositing strengthens gradually.From the XRD spectrum as can be seen, the zeolite diffraction maximum of the nano zeolite that the dynamic absorption of carrying out under the ultrasonic wave radiation makes/carboxylic acid cellulose composite membrane significantly strengthens (Fig. 8 e), even also stronger than the sample that obtains through 5 static absorption assemblings.SEM photo from Fig. 5 as can be seen, through gas-solid handle mutually the back zeolite membrane structure become more clear, fine and close.From tangent plane as can be seen this film have tangible three grades of pore passage structures, the promptly three-dimensional sponge shape macropore (aperture is about 1 μ m) that connects, three-dimensional zeolite microtubule (the zeolite micropore road on aperture about 200～300nm) and the microtubule wall that connects.Because the raising of film-strength makes that its contraction is less, orifice throat ratio is abundanter, and the density of sample is very low after the roasting, only 0.1gcm
-3About, about membrane volume of about 95% is surrounded by the space.Handle the porous zeolite film-strength that obtains mutually and obviously improve through gas-solid, (50kHz 120W) can keep about 10min and can not destroy in ultrasound bath.Diauxic growth is handled can make complete self-supporting zeolite membrane in Centimeter Level.The zeolite membrane thickness that obtains after the roasting improves greatly, can reach about 110 μ m, and is more close with employed cellulose filter membrane template thickness, and the zeolite microtubule is obviously thickening (Fig. 6) also.Prolong the hydrothermal growth processing time, the spherical nano zeolite particle that constitutes the microchannel hole wall grows up to the crystal of the rectangular-shaped staggered growth of sub-micron gradually.And the thickness of zeolite microchannel hole wall increases gradually, and the aperture of microchannel progressively reduces, and until disappearance, stays the porous zeolite film (Fig. 7) by the zeolite bar construction that is cross-linked.Because the further growth of nano zeolite in nutrient source, the density of zeolite membrane also increases to 0.25gcm after the roasting
-3About, about membrane volume of about 85% is surrounded by the space.Because intercrystalline alternating growth makes that the connection between the particle is tightr.Resulting porous zeolite film-strength is also higher, can keep in ultrasound bath more than the 15min and does not have breakage.
Because such membrane material has the pore structure on the many levels, and the duct distribution is more even, might make the most of the advantage in the separation of high-speed Gas Phase Adsorption, liquid phase adsorption separation; In addition, by making affine separating and filtering film after the modification with property, especially after the method for organo-functional group molecule by grafting is implanted to zeolite microtubule surface, may play certain effect aspect the affine diffusion barrier of the immobilized and large biological molecule of enzyme.
Claims (20)
1. method for preparing zeolite film with self-supporting multi-stage artery structure, it is characterized in that the glue of zeolite and polyelectrolyte solution as the absorption deposit fluid, cellulose filter membrane is as matrix, utilize the electrostatic attraction between nano zeolite and the polyelectrolyte, nano zeolite is deposited on the cellulose filter membrane, the gelatin concentration that nano zeolite is dispersed in the water is 0.05-20% (wt%), pH is 1～14, polyelectrolyte solution concentration is 0.1-5%, make cellulose filter membrane in polyelectrolyte solution and alternately absorption deposition of nano zeolite glue, dry at 5～200 ℃ then, in inert atmosphere or air or oxygen atmosphere, can obtain the multi-stage artery structure zeolite membrane of self-supporting at last respectively in 200～1000 ℃ of roastings.
2. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that under the steam effect of the organic amine of the power of boosting certainly under 100～240 ℃ of temperature and the treatment temperature and water the zeolite membrane after the above-mentioned roasting being handled 1 hour to 20 days.
3. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1, it is characterized in that the nano zeolite/cellulose composite membrane hydrothermal growth treatment temperature in siliceous nutrient source before the roasting is 60～160 ℃, the processing time is 0.5-5 days.
4. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that the zeolite grain size is the 1-200 nanometer.
5. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that the gelatin concentration that zeolite grain disperses is 0.1～10%.
6. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that the pH value of zeolite glue is 2～12.
7. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that polyelectrolyte solution can be polycation electrolyte solution or polyanion electrolyte solution.
8. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that adsorbing the product that obtains after the deposition and dries at 40～180 ℃.
9. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1 is characterized in that used cellulose filter membrane is the carboxylic acid cellulose filter membrane.
10. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 1, the aperture that it is characterized in that the carboxylic acid cellulose microporosity filter membrane at 0.1 μ m between the 2 μ m.
11. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 2 is characterized in that organic amine is a primary amine, secondary amine, and tertiary amine or diamines:
C
nH
2n+1NH
2，n＝0～5；
C
nH
2n+1C
mH
2m+1NH，n，m＝0～5；
C
nH
2n+1C
mH
2m+1C
iH
2i+1N，n，m，i＝0～5；
NH
2C
nH
2nNH
2，n＝0～5。
12. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 2, it is characterized in that under organic amine and water vapor acting gas-solid mutually treatment temperature be 120～200 ℃.
13. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 2 is characterized in that 6 hours～10 days time that gas-solid is handled mutually.
14. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 11, it is characterized in that gas-solid handle mutually in organic amine be ammonia, n-butylamine, n-propylamine, ethylenediamine, the mixture of one or more in the triethylamine.
15. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 3 is characterized in that growth-promoting media is siliceous akaline liquid.
16. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 3 is characterized in that the hydrothermal growth treatment temperature is 80～140 ℃
17. a kind of method for preparing zeolite film with self-supporting multi-stage artery structure according to claim 3 is characterized in that the hydrothermal growth processing time is 0.5-3 days.
18., it is characterized in that the porous zeolite film that this method makes is used for catalyst or adsorbent or release agent according to the described a kind of method for preparing zeolite film with self-supporting multi-stage artery structure of claim.
19., it is characterized in that the porous zeolite film that this method makes is used for waste water and waste gas purification agent according to the described a kind of method for preparing zeolite film with self-supporting multi-stage artery structure of claim.
20., it is characterized in that the porous zeolite film that makes is used for the adsorbing separation film of large biological molecule according to a kind of method for preparing zeolite film with self-supporting multi-stage artery structure described in the claim.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103903664A (en) * | 2014-04-17 | 2014-07-02 | 武汉大学 | Irradiation resistance nano-porous membrane |
| US10427108B2 (en) | 2015-03-31 | 2019-10-01 | Ngk Insulators, Ltd. | Zeolite film structure |
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2002
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103903664A (en) * | 2014-04-17 | 2014-07-02 | 武汉大学 | Irradiation resistance nano-porous membrane |
| CN103903664B (en) * | 2014-04-17 | 2016-06-29 | 武汉大学 | A kind of Flouride-resistani acid phesphatase nano-porous films |
| US10427108B2 (en) | 2015-03-31 | 2019-10-01 | Ngk Insulators, Ltd. | Zeolite film structure |
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| Publication number | Publication date |
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