CN101837989B - Preparation method of fluorine-containing T-type zeolite membrane - Google Patents
Preparation method of fluorine-containing T-type zeolite membrane Download PDFInfo
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Abstract
The invention provides a preparation method of a fluorine-containing T-type zeolite membrane, which is characterized in that a T-type zeolite membrane is used as an induced crystal seed, and is evenly coated on a porous tubular supporting body, and fluoride (MF) is directly added into a synthetic liquid; a layer of continuous dense fluorine-containing T-type zeolite membrane is formed in sol, and the sole comprises the following components by molar ratio: SiO2/Al2O3 = 10-60, H2O/SiO2 = 10-70, (Na2O + K2O) / SiO2 = 0.2-0.6, Na/K = 0.2-0.8, and MF/SiO2 = 0.05-1.5, and the crystal of the membrane layer has full c-axis oriented growth. Compared with the non-fluorine-containing T-type zeolite membrane, the fluorine-containing T-type zeolite membrane prepared by the invention has higher acid resistance and better application prospects in the fields of pervaporation liquid separation, gas separation, membrane reactors and the like. The method has simple preparation process and operation step, low synthesis cost, and good repeatability, and is suitable for industrial scale production.
Description
Technical field
The invention belongs to the inorganic material film technical field, relate to the preparation and the application of fluorine-contained T-shaped zeolite molecular sieve film.
Background technology
Zeolite molecular sieve film is a kind of novel inorganic separating film, compares advantages such as having chemicalstability and thermostability with polymeric membrane.Owing to having ion characteristic, the molecular sieve crystal internal surface has the coulomb field effect; The coulomb field effect changes along with the variation of silica alumina ratio in the framework of molecular sieve; Thereby change the hydrophilic and hydrophobic of molecular sieve; The very big possess hydrophilic property of electrostatic field that the molecular sieve crystal of low silica-alumina ratio is inner, the molecular screen membrane that is made up of it can extract water through infiltration evaporation from the organism of high density.The molecule that varies in size in addition also can obtain selecting type through infiltration evaporation to be separated.
Infiltration evaporation is the important means that the separation and azeotropic azeotropic mixture is gone up in industry.Use this technology and deviate from the important component part that water in organism or the mixed solvent has become application of membrane separation technology.This method compare with traditional method have power consumption less, advantage such as environmental protection.The infiltration evaporation of molecular screen membrane thereby extremely people's attention, it is with the fastest developing speed to become the film field, also is one of the most promising technology.
Prepare film forming molecular screen material Silicalite, ZSM-5, A type zeolite, T type zeolite and mordenite etc. are arranged.The silica alumina ratio of T type zeolite molecular sieve is 3～4, and wetting ability is inferior to NaA type molecular sieve.It is the unordered symbiote of offretite (OFF) and erionite (ERI).T type zeolite molecular sieve active adsorption aperture has only about 0.36nm.(Journal ofMembrane Science 236 (2004) 17-27) such as Ying Cui are SiO in the colloidal sol proportioning
2: Al
2O
3: Na
2O: K
2O: H
2O=1: 0.05: 0.26: 0.09: 14,130 ℃ of following hydro-thermals synthetic 30 hours, synthesized the T type zeolite molecular sieve thin layer that thickness is about 20 μ m in a tubular support surface.In patent JP 2005305371, announced that the employing crystal seed method synthesizes T type zeolite molecular sieve film, be to have synthesized T type zeolite molecular sieve film on the porous supporting body of 0.14 μ m in the aperture.With proportioning is SiO
2/ Al
2O
3=50, OH-/SiO
2=0.77, Na
+/ (Na
++ K
+)=0.77, H
2O/ (Na
++ K
+The colloidal sol aged at room temperature of)=20 48 hours places colloidal sol with the porous supporting body that scribbles crystal seed, reacts 72 hours down with normal pressure at 100 ℃, synthesizes erionite: the T type zeolite molecular sieve film of offretite=7: 3.(catalysis journal, 2008,7 (29): such as Zhou Han 592～594) with proportioning SiO
2: Al
2O
3: Na
2O: K
2O: H
2O=20: 1: 5.2: 1.8: 280, utilize the microwave-assisted hydro-thermal synthetic, at porous α-Al
2O
3Supporting body surface has prepared the T type zeolite molecular sieve film of high performance a&b orientation.
More than the type T molecular sieve film of these patents and bibliographical information all in non-fluorine-containing system, prepare synthetic T type zeolite molecular sieve film report not so far at home and abroad in fluorine-containing system.
In fluorine-containing molecular sieve field; (Desalination such as Tavolaro; 147 (2002) 333) utilize Sodium Fluoride to substitute the alkali in the synthetic liquid; On the tubulose alumina support, successfully prepare the VS-1 molecular screen membrane, but in the synthetic colloidal sol content of silicon source and template higher (synthetic liquid molar constituent is than being 0.5VOSO
4-10NaF-1.25TPABr-10SiO
2-330H
2O), and need 170 ℃ of crystallization 6 days, preparation process is complicated, loaded down with trivial details.Gualtieri etc. (Microp.Mesop.Mater., 111 (2008) 604) utilize in the hydrofluoric acid and tetrapropylammonium hydroxide (synthetic liquid molar constituent 3TPAOH: 25SiO
2: 975H
2O: 100EtOH: 3HF), under the neutrallty condition on sintered glass and aluminum oxide sheet supporter successful preparation the TPA-MFI molecular screen membrane, but need be at thicker (H
2O/SiO
2=39) 100 ℃ of crystallization could form one deck TPA-MFI molecular screen membrane in supporting body surface in 120 hours in the synthetic colloidal sol, and crystal seed layer comes off so that can not form fine and close molecular sieve layer easily in hydro-thermal synthetic process.
In existing existing bibliographical information; Investigators just obtain active higher molecular screen membrane with the aftertreatment that molecular sieve or molecular screen membrane carry out fluorine; But when taking off framework aluminum, tend to produce to some extent lattice imperfection and non-skeleton fragment, thereby cause molecular sieve to can not get at aspects such as structure and performances improving.In fluorine-containing system, in the preparation MFI molecular screen membrane, do not detect fluorine element in the synthetic MFI molecular screen membrane crystalline framework and get into skeleton.
This patent adopts the fluorine-contained T-shaped zeolite molecular sieve crystal seed for inducing, and in colloidal sol, directly adds the fluorine source, and single stage method has been synthesized the fluorine-contained T-shaped zeolite molecular sieve film.Through in crystal, introducing fluorine element, improved the crystalline acid resistance, expanded the fluorine-contained T-shaped zeolite molecular sieve film in the infiltration evaporation of acid system and the application in the film reaction process.
Summary of the invention
The invention provides that single stage method prepares the method for fluorine-contained T-shaped zeolite molecular sieve film and in the organic mixture applications in separation, this method is simple to operation, repeatability is high, the prices of raw and semifnished materials are cheap, film properties is high.For inducing crystal seed, precoating is adopted the synthetic diauxic growth method of hydro-thermal to supporting body surface with fluorine-contained T-shaped zeolite molecular sieve, under 90～180 ℃ temperature, reacts to obtain densification and successive fluorine-contained T-shaped zeolite molecular sieve film in supporting body surface in 12～120 hours.
The present invention at first induces down in the nano T-type zeolite; Directly synthetic fluorine-contained T-shaped zeolite molecular sieve in fluorine-containing colloidal sol; This crystal has higher activity in inducing formation fluorine-contained T-shaped zeolite molecular sieve membrane process; Fluorine-containing T type prepare zeolite step is following: select for use white lake or sodium metaaluminate or aluminium foil or aluminium powder as the aluminium source, the aluminium source is added in the alkali lye of Pottasium Hydroxide, the heating for dissolving clarification;
(2) again silica flour or silicon sol silicon source and fluorine source are slowly dropped in the alkali lye formed SiO under stirring state
2-K
2O-Al
2O
3-MF-H
2The O system, the colloidal sol proportioning is expressed as with each material mol ratio:
SiO
2/Al
2O
3＝10～50，
H
2O/SiO
2＝18～50，
K
2O/SiO
2＝0.2～0.5，
MF/SiO
2＝0.05～1.5，
Colloidal sol adds 0.1～2wt% nano molecular sieve crystal seed after 50～60 ℃ stirring was worn out 20～30 hours down;
(3) the colloidal sol reaction kettle of packing into, hydro-thermal is synthetic 0.5～5 day under 90～130 ℃ of synthesis temperatures, after centrifugal, cleaning and drying, obtains fluorine-contained T-shaped zeolite molecular sieve.
The preparation method of fluorine-contained T-shaped zeolite molecular sieve film of the present invention is as follows:
(1) seeded supporter: tubulose porous mullite or stainless steel or alumina support are immersed in supporter in the methanol solution of the dimethyldiethoxysilane that contains 5～80wt% through polishing, ultrasonic cleaning and drying then, flood 10～30 minutes; Make the supporting body surface lotus that becomes positively charged; In 5～15wt% fluorine-contained T-shaped zeolite molecular sieve seed-solution, dripping NaOH solution adjusting pH value is 9～10, makes seed surface electronegative, and positively charged supporter is placed electronegative seed-solution; Automatically be adsorbed on crystal seed on the outside surface of supporter equably through charge effect; Repeat 1～3 time, seed layer thickness is 0.5～3 μ m, dries;
(2) preparation synthesis material liquid: with silicon sol or amorphous silica powder or water glass is the silicon source; White lake or sodium metaaluminate or aluminium foil or aluminium powder are the aluminium source; Aluminium source, villiaumite, silicon source are added in the mixed alkali liquor of sodium hydroxide and Pottasium Hydroxide, continue to stir aging 12～48 hours to forming stable SiO
2-Na
2O-K
2O-Al
2O
3-MF-H
2The O system, each component mol ratio is:
SiO
2/Al
2O
3＝10～60，
H
2O/SiO
2＝10～70，
(Na
2O+K
2O)/SiO
2＝0.2～0.6，
Na/K＝0.2～0.8，
MF/SiO
2＝0.05～1.5；
The optimal components ratio scope is:
SiO
2/Al
2O
3＝20～50，
H
2O/SiO
2＝10～40，
(Na
2O+K
2O)/SiO
2＝0.2～0.5，
Na/K＝0.2～0.6，
MF/SiO
2＝0.1～1；
(3) the synthetic fluorine-contained T-shaped zeolite molecular sieve film of secondary hydro-thermal: the liquid stock of step (2) preparation is put into stainless steel cauldron, insert the porous tubular type supporter of handling through step (1), under 90～180 ℃ temperature, synthesized 12～120 hours.After reacting completely, after cleaning, drying, obtain the fluorine-contained T-shaped zeolite molecular sieve film, rete crystal F/Si mol ratio is 0.00001～0.2, is oriented growth.
The silicon source that preparation fluorine-contained T-shaped zeolite molecular sieve film adopts among the present invention is silicon sol or amorphous silica powder or water glass, and the aluminium source of employing is white lake or sodium metaaluminate or aluminium foil or aluminium powder etc.The alkali that adopts is the mixed base of sodium hydroxide and Pottasium Hydroxide, and sodium-chlor or Repone K also can be used as Na and K source.The employing villiaumite is Sodium Fluoride (NaF) or Neutral ammonium fluoride (NH
4F) or Potassium monofluoride (KF), preferred fluorinated ammonium.
It is Porous Stainless Steel, mullite and α-Al that the present invention adopts the tubulose porous supporting body
2O
3, preferred porous mullite.Adopting the mean pore size of porous tubular type supporter is 0.1～10 μ m, and porosity is 30%～60%, and O.D.T. is 8～15mm, and thickness of pipe is 0.5～3mm.
The hydro-thermal synthesis temperature is 90～180 ℃ when synthesizing the fluorine-contained T-shaped zeolite molecular sieve film among the present invention, and optimum value is 100～160 ℃; Generated time is 12～120 hours, and optimum value is 24～96 hours.
T type zeolite molecular sieve strong (001) and (002) crystal face characteristic peak appear in synthetic fluorine-contained T-shaped zeolite molecular sieve film rete crystal among the present invention under X-ray diffraction; And the peak of other crystal face does not occur; Prepared rete crystal is complete c axle oriented growth, and rete crystal F/Si mol ratio is 0.0001～0.1.
Synthetic fluorine-contained T-shaped zeolite molecular sieve film of the present invention has better infiltration evaporation performance and acid resistance.Under the hydrothermal condition of optimizing, synthetic T type zeolite molecular sieve film is at 75 ℃ in the fluorine-containing system of this patent, and flux and separation factor in water/Virahol (10/90wt%) solution separating system are respectively 3.42kgm
-2H
-1With 10000.And application number is the preparation method shown in the 200810106837.9 patent workings example 1, synthetic T type zeolite molecular sieve film in not fluorine-containing system.The flux and the separation factor that are applied in the same system are respectively 3.20kgm
-2H
-1With 4000.Comparative result shows that fluorine-containing type T molecular sieve film shows more excellent permeation vaporization separation performance.
Above-mentioned fluorine-contained T-shaped zeolite molecular sieve film and non-fluorine-contained T-shaped zeolite molecular sieve film use the acetic acid soln (pH ≈ 2) of 50 wt% and 0.1M hydrochloric acid soln (pH ≈ 1) to carry out the s.t. of static immersing formula respectively.Adopting the acetic acid soln treatment temperature is 75 ℃, and the treatment time is 7 days, and adopting the treatment temp of hydrochloric acid soln is 28 ℃, and the treatment time is 7 days.Film before and after the s.t. is measured the infiltration evaporation performance in 75 ℃, water/ethanol (10/90wt%) solution.Fluorine-contained T-shaped zeolite molecular sieve film and non-fluorine-contained T-shaped zeolite molecular sieve film still have very high infiltration evaporation performance after acetic acid soln is handled, show that two kinds of films have temperature property preferably at this acidity condition.And having bigger difference after two kinds of film processing in the 0.1M hydrochloric acid soln, not fluorine-containing film does not have separation performance, and the fluorine-contained T-shaped zeolite molecular sieve film has separation selectivity preferably.This shows, the fluorine-contained T-shaped zeolite molecular sieve film has than fluorine-contained T-shaped zeolite molecular sieve film not and has better acid acceptance.
The compound method of the fluorine-contained T-shaped zeolite molecular sieve film that provides among the present invention, its preparation process is simple and easy to repetition, is prone to amplify; The prices of raw and semifnished materials are cheap; Adopt the diauxic growth method to shorten film formation time greatly, the synthetic symphysis is continuous and be evenly distributed defectives such as free of pinholes, crack; Excellent performance reduces the loaded down with trivial details subsequent processes of the fluorine-containing molecular screen membrane of other kind of similar preparation.The fluorine-contained T-shaped zeolite molecular sieve film is compared with non-fluorine-containing T molecular sieve has stronger acid resistance, can be applicable to organic mixture separation, gas delivery, has more wide application prospect.
Description of drawings
Fig. 1 is x XRD X (XRD) figure of synthetic fluorine-contained T-shaped zeolite molecular sieve film.
Fig. 2 is synthetic fluorine-contained T-shaped zeolite molecular sieve film surface scan electron microscope (SEM) figure.
Fig. 3 is synthetic fluorine-contained T-shaped zeolite molecular sieve film section SEM figure.
Fig. 4 is an infiltration evaporation device synoptic diagram.
Embodiment
In order to further describe the present invention, provided several practical implementation cases below, but patent right is not limited to these examples.
Embodiment 1: the preparation of fluorine-contained T-shaped zeolite molecular sieve crystal seed
Select for use white lake as the aluminium source, silicon sol is the silicon source, and Neutral ammonium fluoride is the fluorine source, under agitation, aluminium source, silicon source and fluorine source is added in the alkali lye of Pottasium Hydroxide, and silicon sol adds rate-controlling at 5～10ml/min, formed SiO
2-K
2O-Al
2O
3-MF-H
2The O system, the colloidal sol proportioning is expressed as with each material mol ratio: SiO
2/ Al
2O
3=20, H
2O/SiO
2=20, K
2O/SiO
2=0.35, MF/SiO
2=0.1, colloidal sol adds 0.5wt% nano molecular sieve crystal seed after 60 ℃ stirring was worn out 24 hours down; The colloidal sol reaction kettle of packing into, hydro-thermal is synthetic 3 days under 100 ℃ of synthesis temperatures, after centrifugal, cleaning and drying, obtains fluorine-contained T-shaped zeolite molecular sieve.
The synthetic molecular sieve characterizes through the x XRD X, and the molecular sieve of preparation locates to occur T type zeolite molecular sieve characteristic diffraction peak diffraction angle 2 θ=7.7 °, 11.6 °, 20.5 ° and 23.53 °, and crystal is pure T type zeolite molecular sieve crystal.Adopt
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, promptly F gets in the crystalline framework fully, combines x XRD X sign, plasma emission spectrum and the analysis of F electrode characterization result, the elementary composition of synthetic fluorine-contained T-shaped zeolite molecular sieve is: K
3.6[Si
14.5Al
3.5O
36F
0.1]
3.6-
Embodiment 2: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
With silicon sol, Pottasium Hydroxide, sodium hydroxide, white lake, Neutral ammonium fluoride and deionized water uniform mixing, the mol ratio that forms colloidal sol is: SiO
2/ Al
2O
3=25, H
2O/SiO
2=30, (Na
2O+K
2O)/SiO
2=0.35, Na/K=0.6, MF/SiO
2=0.1.Colloidal sol stirred aging 24 hours.Japan Nikkato Co., Ltd. system porous mullite pipe is as film synthetic supporter, and mullite consists of 67wt%Al
2O
3And 33wt%SiO
2Supporter is immersed in supporter in the methanol solution of the dimethyldiethoxysilane that contains 10wt% after 800 order sand paperings and ultrasonic cleaning, floods 30 minutes; Make the supporting body surface lotus that becomes positively charged; In 8wt% fluorine-contained T-shaped zeolite molecular sieve crystal seed (like embodiment 1 preparation) solution, dripping NaOH solution adjusting pH value is 9～10, makes seed surface electronegative, and positively charged supporter is placed electronegative seed-solution; Automatically be adsorbed on crystal seed on the outside surface of supporter equably through charge effect; Repeat 1 time, seed layer thickness is 0.5～3 μ m, dries.The supporter that scribbles crystal seed is inserted in the reaction kettle that colloidal sol is housed, under 150 ℃ temperature, synthesized 40 hours.After reacting completely, after cleaning, drying, obtain the fluorine-contained T-shaped zeolite molecular sieve film.
Synthetic film characterizes through XRD, and as shown in Figure 1, T type zeolite molecular sieve strong (001) and (002) crystal face characteristic peak appear in X-ray diffraction figure, and the peak of other crystal face does not occur, and shows that prepared rete crystal is complete c axle oriented growth.Further confirmed T type zeolite molecular sieve film orientation through SEM sign (as shown in Figures 2 and 3), bar-shaped T type zeolite molecular sieve crystal is grown in the porous supporting body outside surface vertically, and crystal layer thickness is 15 μ m.Composite crystals adopts
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, promptly F gets in the crystalline framework fully, plasma emission spectrum is 0.0085 with F electrode characterization result demonstration crystal with f and f/Si mol ratio.
The synthetic film is through the infiltration evaporation performance of infiltration evaporation device characterization film shown in Figure 4.Water Tank with Temp.-controlled 4 is heated to predetermined temperature with the liquid stock in the raw material flow container 5, and adopts magnetic stirrer feeding liquid concentration and temperature even.Molecular screen membrane pipe 8 one ends are airtight, and the other end connects through the T-valve 6 of emulsion tube with vacuum line.It is below the 100Pa that vacuum pump 2 is kept the system vacuum degree, and the buffering cold-trap is used to protect vacuum pump, and liquid gets in the pump when preventing accident.Infiltration steam gets into cold-trap 3 (switching at regular intervals through T-valve 6) under negative pressure promotes, and through the rapid condensation and collection of liquid nitrogen.The electronic pressure transmitter 7 detection system vacuum tightnesss that vacuumometer 1 links to each other through vacuum line.
The infiltration evaporation performance of film is by permeation flux Q and two parametric representations of separation factor α.Infiltration sees through quality/(unit time * membrane area) of thing through the material total mass of the film of unit surface in the permeation flux Q representation unit time in the Q=unit time, and unit is kgm
-2H
-1Separation factor α is used for the height of evaluated for film separation efficiency, α=(Y
A/ Y
B)/(X
A/ X
B), Y wherein
AWith Y
BBe illustrated respectively in the mass concentration of A in the permeate (water) and two kinds of components of B (organism), X
AWith X
BBe illustrated respectively in the mass percent concentration of A and two kinds of components of B in the liquid stock.
It is as shown in table 1 to close film forming infiltration evaporation performance.
Embodiment 3: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
Building-up process such as embodiment 2 are said, and different is with NH in the colloidal sol proportioning
4F/SiO
2Increase to 0.3, generated time increased to 50 hours, took out after reaction finishes, and used the washed with de-ionized water mould material, to wash film surface and the amorphous substance of inwall and the alkali lye of absorption, dried.Composite crystals adopts
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, promptly F gets in the crystalline framework fully, plasma emission spectrum is 0.013 with F electrode characterization result demonstration crystal with f and f/Si mol ratio.It is as shown in table 1 to close film forming infiltration evaporation performance.
Embodiment 4: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
Building-up process such as embodiment 2 are said, and different is with NH in the colloidal sol proportioning
4F/SiO
2Increase to 0.5, generated time increased to 60 hours, took out after reaction finishes, and used the washed with de-ionized water mould material, to wash film surface and the amorphous substance of inwall and the alkali lye of absorption, dried.Composite crystals adopts
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, promptly F gets in the crystalline framework fully, plasma emission spectrum is 0.020 with F electrode characterization result demonstration crystal with f and f/Si mol ratio.It is as shown in table 1 to close film forming infiltration evaporation performance.
Embodiment 5: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
Building-up process such as embodiment 2 are said, and different is to change Neutral ammonium fluoride into Sodium Fluoride, add a certain amount of Repone K simultaneously to keep sodium potassium than constant; After finishing, reaction takes out; Use the washed with de-ionized water mould material,, dry to wash film surface and the amorphous substance of inwall and the alkali lye of absorption.It is as shown in table 1 to close film forming infiltration evaporation performance.
Embodiment 6: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
Building-up process such as embodiment 2 are said, and different is, and the colloidal sol proportioning is adjusted to synthesis temperature is 170 ℃, and generated time foreshortens to 30 hours; After finishing, reaction takes out; Use the washed with de-ionized water mould material,, dry to wash film surface and the amorphous substance of inwall and the alkali lye of absorption.It is as shown in table 1 to close film forming infiltration evaporation performance.
Embodiment 7: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
Building-up process such as embodiment 2 are said, and different is the tubulose stainless steel supporter that adopts U.S. Mott company to produce.Take out after should finishing, use the washed with de-ionized water mould material,, dry to wash film surface and the amorphous substance of inwall and the alkali lye of absorption.It is as shown in table 1 to close film forming infiltration evaporation performance.
Embodiment 8: the fluorine-contained T-shaped zeolite molecular sieve membrane prepare
Building-up process such as embodiment 2 are said, and different is, and to adopt the Na/K mol ratio of colloidal sol be 0.4.Take out after should finishing, use the washed with de-ionized water mould material,, dry to wash film surface and the amorphous substance of inwall and the alkali lye of absorption.It is as shown in table 1 to close film forming infiltration evaporation performance.
Comparing embodiment 1: the preparation of floride-free T type zeolite molecular sieve film
Like application number is the preparation method shown in the 200810106837.9 patent workings example 1, synthetic T type zeolite molecular sieve film.Concrete steps are: the aluminium source is added in an amount of sodium hydroxide and the white lake alkali lye, and dissolving under heating and agitation condition waits to dissolve complete back, back with required water dilution.Under stirring state, add the silicon source, form uniform and stable colloidal sol, the proportioning of colloidal sol is calculated in molar ratio as: 1SiO
2: 0.01Al
2O
3: 0.25Na
2O: 0.08Na
2O: 55H
2O.Nanometer crystal seed and water are blended together steady suspension, and at mullite supporter coating nanometer type T molecular sieve crystal seed, seed density is 0.5～2mg/cm
2, the supporter of precoating crystal seed in 70 ℃ of baking ovens dry 3 hours subsequent use.The supporter that applies crystal seed reacted 15 hours in 150 ℃ of baking ovens, and after reaction finished, the layering of reactant solid-liquid was taken out film and cleaned repeatedly to pH value neutrality with deionized water, dries naturally.Close film forming performance and list in table 2.
Embodiment 2 fluorine-contained T-shaped zeolite molecular sieve films are at 75 ℃, and flux and separation factor in water/Virahol (10/90wt%) solution separating system are 3.42kgm
-2H
-1With 10000.And flux and separation factor that comparing embodiment 1 synthetic film is applied in the same system are 3.20kgm
-2H
-1With 4000.Comparative result shows that fluorine-containing type T molecular sieve film shows more excellent permeation vaporization separation performance.
Embodiment 9: the acid resistance test
At embodiment 2 and comparing embodiment 1 synthesis condition synthesizing molecular sieve film repeatedly, use the acetic acid soln (pH ≈ 2) of 50wt% and 0.1M hydrochloric acid soln (pH ≈ 1) to carry out the s.t. of static immersing formula respectively.Adopting the acetic acid soln treatment temperature is 75 ℃, and the treatment time is 7 days, and adopting the treatment temp of hydrochloric acid soln is 28 ℃, and the treatment time is 7 days.Film before and after the s.t. is listed in table 2 at 75 ℃, the infiltration evaporation of water/ethanol (10/90wt%) solution.Data analysis from table can know that fluorine-contained T-shaped zeolite molecular sieve film (embodiment 2) still has very high infiltration evaporation performance with fluorine-contained T-shaped zeolite molecular sieve film not after the acetic acid soln processing, show that two kinds of films have temperature property preferably at this acidity condition.And having bigger difference after two kinds of film processing in the 0.1M hydrochloric acid soln, not fluorine-containing film does not have separation performance, and the fluorine-contained T-shaped zeolite molecular sieve film has separation selectivity preferably.This shows, the fluorine-contained T-shaped zeolite molecular sieve film has than fluorine-contained T-shaped zeolite molecular sieve film not and has better acid acceptance.
Table 1 embodiment 2～8 synthetic fluorine-containing T type zeolite membrane synthesis condition and penetrating qualities
Annotate: osmotic system is: 75 ℃, and water/Virahol (10/90wt%) solution
Handle the infiltration evaporation performance of caudacoria under table 2 different acidic conditions
Annotate: osmotic system is: 75 ℃, and water/Virahol (10/90wt%) solution.
Claims (6)
1. the preparation method of a fluorine-contained T-shaped zeolite molecular sieve film is characterized in that inducing with the fluorine-contained T-shaped zeolite molecular sieve crystal seed, and its preparation process is following:
(1) fluorine-containing T type zeolite seed crystal preparation: aluminium source, silicon source and fluorine source slowly are added in the alkali lye, and fluorine source MF is Neutral ammonium fluoride or Sodium Fluoride or Potassium monofluoride, formed SiO
2-K
2O-Al
2O
3-MF-H
2The O system, the colloidal sol proportioning is expressed as with each material mol ratio: SiO
2/ Al
2O
3=10～50, H
2O/SiO
2=18～50, K
2O/SiO
2=0.2～0.5, MF/SiO
2=0.05～1.5, add 0.1～2wt% nano molecular sieve crystal seed, hydro-thermal is synthetic 0.5～5 day under 90～130 ℃ of synthesis temperatures, prepares fluorine-containing T type zeolite seed crystal preparation;
(2) seeded supporter: tubulose porous mullite or stainless steel or alumina support are through polishing, ultrasonic cleaning and drying; Then supporter is immersed in the methanol solution of the dimethyldiethoxysilane that contains 5～80wt%, makes the supporting body surface lotus that becomes positively charged, in step (1) the crystal seed aqueous solution of 5～15wt%, dripping NaOH solution, to regulate the pH value be 9～10; Make seed surface electronegative; Positively charged supporter is placed electronegative seed-solution, crystal seed is adsorbed on the supporter outside surface automatically equably, repeat 1～3 time through charge effect; Seed layer thickness is 0.5～3 μ m, dries;
(3) the synthetic fluorine-contained T-shaped zeolite molecular sieve film of secondary hydro-thermal: aluminium source, villiaumite, silicon source are added in the mixed alkali liquor of sodium hydroxide and Pottasium Hydroxide, continue to stir aging 12～48 hours to forming stable SiO
2-Na
2O-K
2O-Al
2O
3-MF-H
2The O system, each component mol ratio is: SiO
2/ Al
2O
3=10～60, H
2O/SiO
2=10～70, (Na
2O+K
2O)/SiO
2=0.2～0.6, Na/K=0.2～0.8, MF/SiO
2=0.05～1.5, tubulose porous mullite that step (2) is handled or stainless steel or alumina support are inserted in the colloidal sol, under 90～180 ℃ temperature synthetic 12～120 hours, after reacting completely, after cleaning, drying, obtain the fluorine-contained T-shaped zeolite molecular sieve film.
2. the preparation method of fluorine-contained T-shaped zeolite molecular sieve film according to claim 1 is characterized in that H in the synthetic sol system of step (3)
2O/SiO
2=10～40.
3. the preparation method of fluorine-contained T-shaped zeolite molecular sieve film according to claim 1 is characterized in that (Na in the synthetic sol system
2O+K
2O)/SiO
2=0.2～0.5, Na/K=0.2～0.6.
4. the preparation method of fluorine-contained T-shaped zeolite molecular sieve film according to claim 1 is characterized in that villiaumite is Neutral ammonium fluoride or Sodium Fluoride or Potassium monofluoride, and its addition is MF/SiO
2=0.1～1.
5. the preparation method of fluorine-contained T-shaped zeolite molecular sieve film according to claim 1 is characterized in that hydro-thermal that step 3 adopts synthesizes the diauxic growth method, and hydro-thermal synthetic temperature is 100～170 ℃, and the hydro-thermal generated time is 20～96 hours.
6. the preparation method of fluorine-contained T-shaped zeolite molecular sieve film according to claim 1; It is characterized in that T type zeolite molecular sieve strong (001) and (002) crystal face characteristic peak appear in the rete crystal under X-ray diffraction; And the peak of other crystal face does not occur; Prepared rete crystal is complete c axle oriented growth, and rete crystal F/Si mol ratio is 0.0001～0.2.
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