CN101716470A - Method for preparing fluorine-containing mordenite zeolite membrane - Google Patents
Method for preparing fluorine-containing mordenite zeolite membrane Download PDFInfo
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Abstract
The invention provides a method for preparing high-performance fluorine-containing mordenite zeolite membrane. The method is characterized in that crystallization is performed for 5 to 30 hours at a synthesis temperature between 130 and 190 DEG C by a secondary growth method so as to form a layer of dense defect-free fluorine-containing mordenite zeolite membrane on the outer surface of a porous tubular supporting body; the molar ratios of synthesis materials are as follow: the molar ratio of SiO2 to Al2O3 is 10 to 60; the molar ratio of H2O to SiO2 is 15 to 60; the molar ratio of Na2O to SiO2 is 0.15 to 0.5; and the molar ratio of F- to SiO2 is 0.01 to 2. NaF, KF, AlF3, (NH4) SiF6 and NH4F and the like can be used as a fluoride source. The preparation method avoids adding expensive organic template agents, and the fluoride source added greatly improves the permeability and acid resistance of the membrane. For example, when the method is applied to permeation experiment on water/ethanol (10/90 percent by weight) system at 75 DEG C, the average water permeation flux J is 1.2 to 2.5 kg/m2 h; the separation factor (alpha) is more than 1,000; and the synthesized membrane still maintains good stability in acid solution with a pH of less than 1. The method has the advantages of simple novel process, good repeatability and suitability for industrial production.
Description
Technical field
The invention provides a kind of preparation method of fluorine-containing mordenite molecular sieve membrane and the application in ethanol water mixture thereof, belong to inorganic material permeability and separation field.
Background technology
In recent decades, because environmental protection and requirements of saving energy, make infiltration evaporation process (being called for short PV) be used for the research focus that is separated into this field of ORGANIC SOLVENT MIXTURES, especially since the eighties, PV is in the successful industrialization of aqueous organopolysiloxane separation process, provides some important theory foundations for the PV of ORGANIC SOLVENT MIXTURES separates.It is as a new membrane separation technique, has single-stage separating degree height, pollution-free, energy-conservation, advantage such as equipment is simple, is specially adapted to that the way of distillation is difficult separates or the separation of indissociable nearly boiling point, constant boiling point mixture and isomer; To minor amount of water in organic solvent and the mixed solvent remove and waste water in separating of a small amount of organic pollution have advantage significantly technical and economically; Can also product constantly be removed (as removing of esterification water) with biology and chemical reaction coupling, improve reaction conversion ratio.So the infiltration evaporation technology is in petrochemical industry, biodiesel, medicine, food, industrial circles such as environmental protection have wide application prospect and market.
Zeolite molecular sieve film is as the important inorganic separating film of a class, have higher heat endurance, chemical inertness and mechanical strength, it prepares normally on porous supporting body surface or near the surface forms compacted zone one continuous, that be made up of a large amount of zeolite crystals.Because the pore size of zeolite molecular sieve is close with many important gas molecular sizes, so zeolite molecular sieve film can utilize molecular size to come divided gas flow and liquid mixture, has very high separation selectivity; On the other hand, according to the difference of Si/Al ratio in the zeolitic frameworks, its surface presents hydrophobic or hydrophily, therefore by selecting absorption, zeolite molecular sieve film separation of organic substances/aqueous mixtures also has very high selectivity, and the research of zeolite molecular sieve film is in recent years used and received increasing concern.
Modenite has the oval duct that is parallel to each other, and the aperture is 0.695nm * 0.581nm, and structure cell consists of Na
8[(AlO
2)
8(SiO
2)
40] 24H
2O.Owing to have higher heat endurance and superior acid resistance, it has become important industrial catalyst and adsorbent.The big and possess hydrophilic property in modenite aperture, the inoranic membrane made from modenite separate application promise in clinical practice are arranged in that petrochemical industry and field of fine chemical are more macromolecular, and also are applicable to the separation of organic matter/water and the membrane reactor in the esterification.
The preparation method of mordenite membrane mainly contains in-situ synthesis, vaporization transfer method and diauxic growth method.In-situ synthesis is one of method of extensive use in the synthetic field of molecular screen membrane, this method synthesis step is simple, and to the requirement harshness of synthesis condition, synthetic liquid concentration is big, the microstructure of wayward molecular screen membrane, and the film forming procedure of this method depends on the performance of carrier surface to a great extent.So, in the mother liquor of preparation, adding organic lamina membranacea agent usually, to be filmed carrying out afterwards calcined under the high temperature, can influence the integrality and the absorption property of film like this.Piera etc. (J.Memb.Sci., 1998, vol149:p99) by under the situation that adds the agent of tetraethyl ammonium hydroxide template, be worth mordenite membrane to have a certain amount of ZSM-5 and Chabazite stray crystal to exist at the porous alumina carrier outer surface.Zhang Yanfeng etc. (J.Memb.Sci., 2002, vol 210p361-368) adopt tetraethylammonium bromide as the template agent, at α-Al
2O
3On the tubular carrier the synthetic mordenite membrane of original position 70 ℃ of branches dried up/mixed system of ethanol (15mol%) in, flux and separation factor are respectively 1.32kg/m
2.h with 5200.Lin etc. (J.Chem Commun, 2000, reported do not added under the condition of template agent p957-958) that the synthetic mordenite membrane of original position is applied to 348K and divides in dried up/isopropyl alcohol system on porous alumina carrier, flux and separation factor are respectively 0.2kg/m
2.h with (M.Micropor.Mesopor.Mater. such as 192.Matsufuji, 1999, vol 32:p159) on alumina ceramic tube, made mordenite membrane with vapour phase transfer method (the template agent is triethylamine and ethylenediamine), but with the molecular screen membrane that this method makes is unsound, can observe a large amount of defectives and exist.
The synthetic mechanism of diauxic growth method belongs to the synthetic category of hydro-thermal substantially, the solution concentration of its growth needs is more much lower than nucleation, the probability of so further nucleation is very little, nearly all grain growth all occurs on the existing crystal seed, by the composition and the concentration of control diauxic growth solution, control synthesis temperature and time, can realize to a certain extent the growth rate and the orientation of crystal grain are controlled, crystallization time is short, and is simple to operate, easily realizes industrial production.The mordenite membrane that M.Matsukat etc. (US0012505) disclose the preparation of utilization diauxic growth method has certain orientation.Laura Casado etc. (J.Memb.Sci., 2003, vol216:p135-147) by the diauxic growth method, the molar constituent of synthetic liquid is than being 0.76NaOH: 0.05Al2O3: 1SiO
2: 40H
2O has prepared mordenite membrane and has been applied in the infiltration evaporation experiment of mixed system of water/ethanol (8wt.%) on earthenware, water flux and ethanol flux be respectively 0.023kg/m
2.h and 0.043kg/m
2.h.G.Li etc. (J.Sep Purif Tech, 2003, vol 32:p199-206) have reported that the mole proportioning is 0.28OH: 0.0042Al2O3: 1SiO2: 12.2H
2The synthetic liquid of O is formed, and to have prepared total flux on porous alumina carrier be 0.6kg/m to crystallization 2h under the 180K
2.h the mordenite membrane of (10/90wt.%water-isopropanol system).Subsequently, G.Li etc. (J.Sep Purif Tech, 2007, vol 56:p378-382) report once more and synthetic mordenite membrane is carried out the hydrochloric acid post processing promptly are immersed in 1mol dm
-3Hydrochloric acid solution in, treatment temperature is 373K, time 2h can be with the total flux of film from 0.07kg/m
2.h be promoted to 0.1kg/m
2.h, thus reach the purpose of the performance of improving film.
Sum up the preparation technology and the performance characterization of the mordenite molecular sieve membrane of above patent and bibliographical information, the synthetic liquid of the preparation film that researchers investigate all is by the aluminium source, the silicon source, alkali source and deionized water are formed, and the preparation of the mordenite molecular sieve membrane of interpolation villiaumite does not also have bibliographical information.
(Microporous and Mesoporous Materials such as Louis, 2004, vol 74:p171-178) reported synthetic a kind of high-crystallinity, the H-[F of high special list area] the ZSM-5 molecular sieve, can improve the crystal size and the surface acidity of molecular sieve by the content that changes fluorine in the colloidal sol.The present invention has improved permeability of the membrane energy and acid resistance greatly by adding the fluorine-containing mordenite membrane that the fluorine source successfully prepares.Synthetic fluorine-containing mordenite molecular sieve membrane has important practice significance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-throughout fluorine-containing mordenite molecular sieve membrane and the application in water/ethanol system thereof.The composition of raw materials that the present invention prepares mordenite molecular sieve membrane, synthesis temperature, generated time is optimized, and is intended to eliminate the defective of crystal growth, causes the crystal continuous growth, and the molecular screen membrane surface is evenly complete, reduces intracrystalline pore, improves the permeability of the membrane energy.Utilize the diauxic growth method, be applied to realize that its flux and separation factor reach 1.4kg/m respectively in the infiltration evaporation experiment of water/ethanol system at the prepared film of porous supporting body outer surface
2.h with more than 1000, thereby be applied to industrialization faster.
The preparation method of MOR type molecular screen membrane of the present invention is as follows:
(1) crystal seed preparation: with silicon powder, sodium metaaluminate, NaOH, amine fluoride and deionized water is raw material, preparation raw material liquid SiO
2-Al
2O
3-NaOH-NH
4F-H
2The O system, each component mol ratio is:
SiO
2/Al
2O
3＝15～40，
H
2O/SiO
2＝10～30，
Na
2O/SiO
2＝0.1～0.3，
NH
4F/SiO
2＝0.1～0.5
Best colloidal sol ratio range is:
SiO
2/Al
2O
3＝15～30，
H
2O/SiO
2＝10～25，
Na
2O/SiO
2＝0.1～0.2，
NH
4F/SiO
2＝0.2～0.5。
The material liquid for preparing is put into band teflon-lined stainless steel cauldron through aged at room temperature 6～24h, and reaction temperature is 160～200 ℃, and hydro-thermal is synthesized 12～36h; Take out after reaction is finished with centrifuge and clean to neutral 100 ℃ of dryings.
(2) supporter coating crystal seed: the tubulose porous ceramic support is smooth with sand papering, use and supporter is put into beaker and pour deionized water in ultrasonic cleaning machine cleaning 3 times, each 3 minutes, it is dry that supporter is put into convection oven.Homemade crystal seed is made into seed-solution, and by the outer surface uniform load one deck crystal seed of czochralski method at the tubulose porous supporting body, seed layer thickness is 0.1～3 μ m, dries.
(3) mordenite molecular sieve membrane preparation: in certain density alkali lye, until the stable milk shape colloidal sol that forms, the mol ratio that forms colloidal sol is with aluminium source, silicon source and fluorine source solution successively:
SiO
2/Al
2O
3＝10～60，
H
2O/SiO
2＝15～60，
Na
2O/SiO
2＝0.15～0.5，
F
-/SiO
2＝0.01～2
Best colloidal sol ratio range is:
SiO
2/Al
2O
3＝10～50，
H
2O/SiO
2＝15～50，
Na
2O/SiO
2＝0.15～0.4，
F
-/SiO
2＝0.1～1
The solution for preparing is put into stainless steel cauldron, and inserts the porous tubular type supporter of precoating crystal seed, and crystallization 5～30h under 130～190 ℃ the synthesis temperature takes out after reaction is finished with the washed with de-ionized water of heat, dry in baking oven.
The present invention adopts the crystal seed method hydro-thermal to synthesize fluorine-containing mordenite molecular sieve membrane, and the crystal seed of employing is fluorine-containing modenite crystal, it is characterized in that adding NH
4The original position hydro-thermal is synthesized in the F colloidal sol, avoids using expensive organic template.
The present invention need add fluorine source, aluminium source etc. when the preparation film synthesizes colloidal sol, the fluorine source can be selected NaF, KF, AlF for use
3, (NH
4) SiF
6And NH
4F, NaF are preferred, and the aluminium source can be selected Al (OH) for use
3, NaAlO
2, Al (i-OC
3H
7)
3And Al
2(SO
4)
3, Al (OH)
3For preferably.
It is 140～180 ℃ that the present invention adopts hydrothermal temperature, and hydro-thermal is synthesized 6～24h.
The porous tubular type support body material that the present invention adopts is porous mullite, stainless steel and aluminium oxide, and porous stainless steel is preferred.Described perforated tubular supporter, average pore size are about 0.1～10 μ m, and porosity is about 30～60%, and external diameter of pipe is 8～20mm, thickness of pipe wall 1～3mm.
Adopt the synthesis condition of optimizing in the simple preparation method of the mordenite molecular sieve membrane of high flux provided by the invention and high selectivity, by the diauxic growth technology, on the mullite tubular support, prepared continuously and be evenly distributed, the fluorine-containing mordenite membrane of defective such as free of pinholes, crack goes for the infiltration evaporation separation process fully, realizes the separation of organic mixture.
The airtight synthetic method of the present invention, synthesizer is simple, and quick, the mordenite molecular sieve membrane that synthesizes has the good penetration performance.It is characterized in that being used for the ethanol/water system, 75 ℃, during feed side concentration of alcohol 90wt%, average water permeation flux J=1.0～1.5kg/m
2H, separation (α) is more than 1000.Except that the ethanol/water system, the film that the present invention synthesizes can also be applied to other alcohol (as methyl alcohol, isopropyl alcohol and normal propyl alcohol etc.), organic acid/water (CH3COOH/H
2O) and the dehydration of organic mixture such as higher fatty acids fat/water.Have broad application prospects at aspects such as infiltration evaporation, membrane reactors.
Description of drawings:
Fig. 1 is the XRD figure of synthetic mordenite molecular sieve crystal
Fig. 2 is the installation drawing of the infiltration evaporation performance of fluorine-containing mordenite molecular sieve membrane
Fig. 3 is X-ray diffraction (XRD) comparison diagram of porous mullite supporter, mordenite molecular sieve crystal and synthetic mordenite molecular sieve membrane
Fig. 4 is the surperficial Electronic Speculum figure at the mordenite molecular sieve membrane of porous mullite supporter outer surface formation
Fig. 5 is the mordenite molecular sieve membrane section Electronic Speculum figure that forms at porous mullite supporter outer surface
In order to further describe the present invention, provided several concrete case study on implementation below, but patent right is not limited to these examples.
The specific embodiment
The preparation of embodiment 1 mordenite molecular sieve
With silicon powder, sodium metaaluminate, NaOH, ammonium fluoride and deionized water is raw material, preparation raw material liquid SiO
2-Al
2O
3-NaOH-NH
4F-H
2The O system, each component mol ratio is:
SiO
2/Al
2O
3＝20，H
2O/SiO
2＝15，
Na
2O/SiO
2＝0.15，NH
4F/SiO
2＝0.4
The material liquid for preparing is put into band teflon-lined stainless steel cauldron through aged at room temperature 12h, and this stainless steel cauldron is put into 180 ℃ of baking oven Synthetic 2 4h.Crystal after synthetic is washed till neutral back in 105 ℃ of dry 12h with deionized water.Synthetic powder carries out XRD and characterizes, and as shown in Figure 1, meets with MOR type molecular sieve standard diagram, is the pure silk geolyte.
The preparation of embodiment 2 fluorine-containing mordenite molecular sieve membranes
The supporter that this experiment is adopted is that (mullite consists of 67wt.%Al to the tubulose mullite that produces of system company of Japanese Nikkato Co., Ltd.
2O
3And 33wt.%SiO
2) as the carrier of synthesizing flokite film, this carrier internal diameter and external diameter are respectively 9mm and 12mm, length is 100mm, porosity is about 43%, average pore size is about 1 μ m, and carrier is after 1000 purpose sand paperings are smooth, with drying after the preliminary treatment such as deionized water ultrasonic cleaning, at supporter outer surface coating skim mordenite molecular sieve powder, the load density of crystal seed is at 0.5-2mg/cm
2, the supporter of coating crystal seed descends dry 1 hour with standby at 30 ℃.
With aluminium hydroxide is the aluminium source, and Ludox is the silicon source, and sodium fluoride is that fluorine source and NaOH are alkali source, mixes with a certain amount of deionized water, stirs into stable milk shape colloidal sol.The mole proportioning of colloidal sol is:
SiO
2/Al
2O
3＝15，H
2O/SiO
2＝35，
Na
2O/SiO
2＝0.25，NaF/SiO
2＝0.25
Colloidal sol is changed in the stainless steel cauldron, simultaneously precoating is made by oneself the supporter of modenite crystal seed and vertically put into reactor, guarantee that the mixture liquid level is higher than supporter.The baking oven of airtight stainless steel cauldron being put into preheating adds thermal response, synthesizes 16 hours under 170 ℃ of constant temperature.Synthetic film boils 2h with 100 ℃ of deionized waters, and the alkali lye that adsorbs in the amorphous substance of flush away film surface and inwall and the supporter is then at 60 ℃ of dry 12h.
Synthetic mordenite molecular sieve membrane is applied to the infiltration evaporation experiment and characterizes, and the film of preparation is through the infiltration evaporation performance of infiltration evaporation device characterization film shown in Figure 2.Water bath with thermostatic control 10 and heater 7 are heated to predetermined temperature with feed liquid 8, and employing magnetic stirring apparatus 11 stirs the feeding liquid concentration and temperature is even.Film pipe 9 one ends are airtight, and the other end connects by the triple valve 5 of emulsion tube with vacuum line.It is below the 100Pa that vavuum pump 6 is kept the system vacuum degree, buffering cold-trap 4 ' be used to protect vavuum pump, and liquid enters in the pump when preventing accident.Infiltration steam enters cold-trap 4 (switching every 1h by triple valve 2,3 and 5) under negative pressure promotes, and collects by the rapid condensation of liquid nitrogen.Electronic pressure transmitter 1 links to each other with detection system vacuum with vacuum line.
The infiltration evaporation result of experiment sees Table M-1 and the M-2 in 1.The infiltration evaporation performance of film is represented by permeation flux J and two parameters of separation α.Infiltration sees through quality/(unit interval * membrane area) of thing by the material gross mass of the film of unit are in the permeation flux J representation unit time in the J=unit interval, and unit is kg/m
2.h; Separation α is used for the height of evaluated for film separative 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 penetrant (organic matter) and two kinds of components of B (water), X
AWith X
BBe illustrated respectively in the mass percent concentration of A and two kinds of components of B in the material liquid.Component A, the content of B adopts the GC-14C gas chromatographic detection.Effective XRD of film and SEM instrument that supporter before synthetic, modenite crystal are reached after synthesizing characterize, and XRD is day island proper Tianjin (SHIMADZU) XRD-6100 of company, and SEM is the JSM-6350 of company of NEC (JEOL).Molecular screen membrane through X-ray diffraction turn out to be mordenite molecular sieve membrane (as shown in Figure 3) and from the electron scanning micrograph as can be seen the porous mullite carrier the fine and close and continuous molecular screen membrane (as Fig. 4 and Fig. 5) of one deck is arranged, the molecular sieve crystal shape is typical MOR crystal shape.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system on the table 1 mullite carrier
The preparation of embodiment 3 fluorine-containing mordenite molecular sieve membranes
Synthetic liquid raw material that adopts and operation only will foreshorten to 12h as embodiment 2 time.Synthetic molecular screen membrane is used for the infiltration evaporation experiment and characterizes, and the infiltration evaporation result of experiment sees Table M-3 and the M-4 in 2.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system on the table 2 mullite carrier
The preparation of embodiment 4 fluorine-containing mordenite molecular sieve membranes
Synthetic liquid raw material that adopts and operation are as embodiment 2, and just the proportioning of the synthetic liquid that forms is:
SiO
2/Al
2O
3＝15，H
2O/SiO
2＝35，
Na
2O/SiO
2＝0.25，NaF/SiO
2＝0.5
Other preparation process is identical with embodiment 1.Synthetic molecular screen membrane is applied to the infiltration evaporation experiment and characterizes, and the infiltration evaporation result of experiment sees Table M-5 and the M-6 in 3.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system on the table 3 mullite carrier
The preparation of embodiment 5 fluorine-containing mordenite molecular sieve membranes
Synthetic liquid raw material that adopts and operation be as embodiment 1, and only with synthesis temperature falling-rising to 160 ℃, crystallization time transfers to 18h.
Synthetic molecular screen membrane is applied to the infiltration evaporation experiment and characterizes, and the infiltration evaporation result of experiment sees Table M-7 and the M-8 in 4.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system on the table 4 mullite carrier
The preparation of embodiment 6 fluorine-containing mordenite molecular sieve membranes
Synthetic liquid raw material that adopts and operation only change the fluorine source NaF are adjusted into NH as embodiment 5
4F, other preparation process is identical with embodiment 5.
Synthetic molecular screen membrane is used for the infiltration evaporation experiment and characterizes, and the infiltration evaporation result of experiment sees Table M-9 and the M-10 in 5.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system on the table 5 mullite carrier
The preparation of embodiment 7 fluorine-containing mordenite molecular sieve membranes
The supporter of film is synthesized in the stainless steel tube conduct of adopting U.S. Mott company to produce, the preliminary treatment of supporter such as embodiment 5, synthetic liquid raw material that adopts and operating procedure are as embodiment 5, synthetic molecular screen membrane is used for the infiltration evaporation experiment and characterizes, and the infiltration evaporation result of experiment sees Table M-11 and the M-12 in 6.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system on table 6 stainless steel carrier
The employing mullite is a supporter, synthesizing flokite molecular screen membrane in for the colloidal sol that adds the fluorine source, and the proportioning of colloidal sol is:
SiO
2/Al
2O
3＝15，H
2O/SiO
2＝35，Na
2O/SiO
2＝0.25。
Other preparation process is identical with embodiment 5.
Synthetic molecular screen membrane is used for the infiltration evaporation experiment and characterizes, and the infiltration evaporation result of experiment sees Table M-13 and the M-14 in 7.
The infiltration evaporation performance (75 ℃) of mordenite molecular sieve membrane in water/ethanol system on the table 7 mullite carrier
Be applied to water/isopropyl alcohol system respectively with repeating fluorine-containing mordenite molecular sieve membrane synthetic under embodiment 5 conditions, different temperatures in the water/ethanol system of variable concentrations, is investigated the selectivity of this film.Its result is as shown in table 8.
The synthetic fluorine-containing mordenite molecular sieve membrane of table 8 is applied to the infiltration evaporation performance under the different infiltration conditions
Repeat the condition of embodiment 5, synthetic fluorine-containing mordenite molecular sieve membrane carries out the acid resistance test.Synthetic molecular screen membrane is handled 24h through 75 ℃ in acetate/ethanol/water (50/40/10wt.%) solution, is applied to the infiltration evaporation experiment.The result is as shown in table 9.Synthetic fluorine-containing mordenite molecular sieve membrane is before and after acid treatment, and the infiltration evaporation performance does not have significant change, shows that synthetic film has good stable.Not fluorine-containing mordenite membrane (M-14) is after acid treatment, and the infiltration evaporation performance shows obvious decline, and this derives from the acid corrosion of crystal and molecular acid and is absorbed in the molecular sieve crystal duct due to the acting in conjunction.Compare with not fluorine-containing mordenite membrane, fluorine-containing mordenite membrane has more excellent permeation vaporization performance under acid condition, show that it has better stability at acid condition, the infiltrating and vaporizing membrane separation process at acid condition preferably.
The infiltration evaporation performance (75 ℃) of fluorine-containing mordenite molecular sieve membrane in water/ethanol system after table 9 is handled
Claims (6)
1. the preparation method of a fluorine-containing mordenite molecular sieve membrane, it is characterized in that adopting mordenite molecular sieve is crystal seed, at the fluorine-containing mordenite molecular sieve membrane of the synthetic one deck densification of perforated tubular supporter outer surface hydro-thermal, it prepares as follows:
(1) crystal seed preparation: with silicon powder, sodium metaaluminate, NaOH, amine fluoride and deionized water is raw material, preparation raw material liquid SiO
2-Al
2O
3-NaOH-NH
4F-H
2The O system, each component mol ratio is:
SiO
2/Al
2O
3＝15～40，H
2O/SiO
2＝10～30，
Na
2O/SiO
2＝0.1～0.3，NH
4F/SiO
2＝0.1～0.5
The material liquid for preparing is put into band teflon-lined stainless steel cauldron through aged at room temperature 6～24h, and reaction temperature is 160～200 ℃, and hydro-thermal is synthesized 12～36h; Take out after reaction is finished with centrifuge and clean to neutral 100 ℃ of dryings;
(2) supporter coating crystal seed: the tubulose porous ceramic support is smooth with sand papering, use and supporter is put into beaker and pour deionized water in ultrasonic cleaning machine cleaning 3 times, each 3 minutes, it is dry that supporter is put into convection oven.Homemade crystal seed is made into seed-solution, and by the outer surface uniform load one deck crystal seed of czochralski method at the tubulose porous supporting body, seed layer thickness is 0.1～3 μ m, dries;
(3) mordenite molecular sieve membrane preparation: aluminium source, silicon source and fluorine source are dissolved in the alkali lye successively, and until the stable milk shape colloidal sol that forms, the mol ratio that forms colloidal sol is:
SiO
2/Al
2O
3＝10～60，H
2O/SiO
2＝15～60，
Na
2O/SiO
2＝0.15～0.5，F-/SiO
2＝0.01～2
The solution for preparing is put into stainless steel cauldron, and inserts the porous tubular type supporter of precoating crystal seed, and crystallization 5～30h under 130～190 ℃ the synthesis temperature takes out after reaction is finished with the washed with de-ionized water of heat, dry in baking oven.
2. according to the described a kind of fluorine-containing mordenite molecular sieve membrane preparation method of claim 1, it is characterized in that: add the fluorine source in synthetic colloidal sol, be mixed with milk shape stable sol, each component mol ratio is:
SiO
2/Al
2O
3＝10～50，H
2O/SiO
2＝15～50，
Na
2O/SiO
2＝0.15～0.4，F
-/SiO
2＝0.1～1
3. according to the described a kind of fluorine-containing mordenite molecular sieve membrane preparation method of claim 1, it is characterized in that: add fluorine source, aluminium source etc. in colloidal sol, the fluorine source can be selected NaF, KF, AlF for use
3, (NH
4) SiF
6And NH
4F, NaF are preferred, and the aluminium source can be selected Al (OH) for use
3, NaAlO
2, Al (i-OC
3H
7)
3And Al
2(SO
4)
3, Al (OH)
3For preferably.
4. according to the described a kind of fluorine-containing mordenite molecular sieve membrane preparation method of claim 1, it is characterized in that: reaction temperature is 140～180 ℃, and hydro-thermal is synthesized 6～24h.
5. according to the preparation method of the described fluorine-containing mordenite molecular sieve membrane of claim 1, it is characterized in that porous tubular type support body material is porous mullite, stainless steel and aluminium oxide, porous stainless steel is preferred.Described perforated tubular supporter, average pore size are about 0.1～10 μ m, and porosity is about 30～60%, and external diameter of pipe is 8～20mm, thickness of pipe wall 1～3mm.
6. according to the described a kind of fluorine-containing mordenite molecular sieve membrane preparation method of claim 1, it is characterized in that crystal seed is adding NH
4The original position hydro-thermal is synthesized in the colloidal sol of F, and the proportioning of colloidal sol is: SiO
2/ Al
2O
3=15～30, H
2O/SiO
2=10～25, Na
2O/SiO
2=0.1～0.2, NH
4F/SiO
2=0.2～0.5.
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|---|---|---|---|
| CN 200910186437 CN101716470B (en) | 2009-11-05 | 2009-11-05 | Method for preparing fluorine-containing mordenite zeolite membrane |
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