CN1193815C - Porous material membrane of molecular sieve and its preparation method - Google Patents
Porous material membrane of molecular sieve and its preparation method Download PDFInfo
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- CN1193815C CN1193815C CNB991139909A CN99113990A CN1193815C CN 1193815 C CN1193815 C CN 1193815C CN B991139909 A CNB991139909 A CN B991139909A CN 99113990 A CN99113990 A CN 99113990A CN 1193815 C CN1193815 C CN 1193815C
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Abstract
The present invention relates to a porous material film of molecular sieves, and a preparation method thereof, which mainly overcomes the defect that the prior techniques don't relate to the film formulation of X type molecular sieves on a carrier. In the present invention, a reaction system of which the mol components of raw materials is aNa2O. bAl2O3. cSiO2. dH2O is adopted. A/c=1.0 to 13.0, c/b=2 to 8 and d/c=50 to 1000. under the reaction temperature condition of 50 to 120 DEG C, a raw material is crystallized for 3 to 144 hours, and an X type molecular sieve is successfully formed on a porous material whose pore diameter is from 40 to 10000 angstroms through crystallization growth. The present invention better solves the problems of the prior art, and can be used in industrial production.
Description
The present invention relates to porous material membrane of molecular sieve and preparation method thereof.
X type molecular sieve, it has bigger aperture passage, and higher voidage is applicable to more macromolecular separation and course of reaction.Modifying by it being carried out physics and chemical method, is the ideal material that obtains different pore size molecular sieve films.
The zeolite molecular sieve of artificial synthetic gained all is granular powder at present, and its size is determined by crystallization operating parameters such as crystallization liquid concentration, crystallization times.Since the molecular sieve bore diameter homogeneous and have the height shape selectivity, in adsorbing separation and heterogeneous catalytic reaction, be widely used.But the two unites separation that molecular sieve is had and response function, utilizing porous material to make carrier synthesizes zeolite molecular sieve on the surface of porous material, thereby form the even zeolite molecular sieve film of one deck, simultaneously this layer zeolite molecular sieve film can have catalytic action can realize separated in synchronization to partial material again, then is scientific worker's a kind of new catalytic material of making great efforts to develop in recent years.
As material of preparing, is to be used in the polymeric membrane as seepage velocity and the selectivity of filler with the raising polymeric membrane molecular sieve the earliest.Because the temperature tolerance of macromolecular material, this respect research is confined to low temperature liquid phase separation process-process of pervaporation always; Gas phase separation process at higher temperature also has research recently, but makes little progress.If molecular sieve directly is created on the ceramic monolith surface, make its adhesion film forming, the separation and the catalysis characteristics that had both kept molecular sieve, improve the separating effect of porous matrix counterdie greatly to material, the realization separating reaction is integrated, advantage-the heatproof, resistance to chemical attack, anti-swelling and the excellent mechanical intensity that have inoranic membrane again, this becomes the focus and the difficult point of people's research.
U.S. Pat P5464798 adopts at α-Al
2O
3Be coated with γ-Al on the porous ceramic surface
2O
3Gel is modified into the body that supports in 50 dust apertures, with the synthetic Silicalite-1 zeolite molecular sieve film of silica gel, NaOH and TPABr.The molecular sieve of packing in earthenware mother liquor carries out the crystallization operating process, gets final product for general 2～3 times.Obviously having reduced the permeation flux of gas after the conducting molecule sieve membrane is modified, only is 3～14% of former basement membrane generally, N
2Low 5 times of saturating amount, n-C
4H
10Low 190 times, low 1000 times of iso-butane.Iso-butane obviously produces absorption on film; Zeolite membrane aligns, the separation of iso-butane mixture can reach 22 (under the room temperatures).
Document WO 95 29751 adopts the original position hydrothermal crystallizing to synthesize the Silicalite-l film on earthenware and porous sintered glass tube, to H
2And i-C
4H
10The ratio of seepage velocity can reach 30, and can be used to study dehydrogenation of isobutane.The reactor outer tube is a stainless steel tube, and the mistress seals with graphite gasket in the pipe, and the film tube cavity is placed industrial Pt-Sn/ γ-Al
2O
3Catalyst.This molecular screen membrane process and α-Al
2O
3Membrane process compares, and its iso-butane productive rate improves 70%.
Document EP 674939 has been introduced at porous α-Al
2O
3The situation of synthetic ZSM-5 molecular screen membrane on the ceramic body forms the two solution of A, B with silicon source and aluminium source through suitably disposing in the test, and the constitutive molar ratio of last mother liquor is SiO
2/ Al
2O
3: 102, Na
2O/SiO
2: 0.23, TPABr/SiO
2: 0.1, H
2O/SiO
2: 200, withstand voltage still is put into heating furnace, keeps 180 ℃, 36 hours film forming of thermally equivalent.This film of making is applied to CO in the air
2Separate α CO
2/ N
2Can reach 53～56, CO
2Infiltration rate can reach 1.7 * 10
-7 moles/meter
2. second. handkerchief, and α CO
2/ N
2And also can reach 42.
Document WO 93 17781 adopts gas phase synthesis method, earlier at α-Al
2O
3The synthetic liquid of molecular sieve on the preload on pipe or the video disc, the xerogel after the film forming is hydrothermal crystallizing under 130～200 ℃ of temperature again, repeatedly repetitive operation film forming.He Cheng ZSM-5 zeolite membrane in this way, to, paraxylene, tri-isopropyl benzene mixed system have the selection osmosis.
Document US P 4699892 utilizes porous carrier to synthesize A type zeolite layer.With the separation property of the mixture characterization of membrane of each 33 moles of % of methane, ethane and propane, the gas mole that penetrates consists of methane 73.5%, ethane 26%, propane 0.5%.
Document JP 08257301 is presented in and has synthesized the y-type zeolite film on the tubulose porous supporting body.The system film consists of H with alumino-silicate colloidal sol mole
2O/SiO
2: 50～120, Na
2O/SiO
2: 0.5～2, SiO
2/ Al
2O
3: 5～15, porous carrier is soaked in hydrothermal crystallizing film forming in the colloidal sol.This film can be made osmotic evaporating and separating membrane, and to pure water, the organic mixed system of alcohol-cyclohexane has separating power.
In sum, the situation that does not all relate to X type molecular sieve film forming on carrier in the above-mentioned document.
To the objective of the invention is the shortcoming that do not relate to X type molecular sieve film forming situation on carrier in the conventional art in order overcoming, a kind of preparation method of novel porous material membrane of molecular sieve to be provided.This material membrane is to form composite membrane at carrier surface growth one deck X type molecular sieve.
The objective of the invention is to realize by following technical scheme: a kind of preparation method of porous material membrane of molecular sieve is a raw material with aluminium source, sodium source, silica gel or Ludox and water, and the feed molar composition of reaction system is counted with oxide: aNa
2ObAl
2O
3CSiO
2DH
2O, a/c=1.0～13.0 wherein, c/b=2～8, d/c=50～1000, with the aperture is that the glass or the stainless steel porous material of 40～10000 dusts is dipped in the reaction system, reaction raw materials crystallization 3～144 hours under 50～120 ℃ of reaction temperature conditions, crystallization growth X type molecular sieve on porous material.
In the technique scheme, the aluminium source is selected from the aluminium alcoholates of metal aluminum foil, sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or 2～4 carbon atoms, and preferred version is a sodium aluminate; The sodium source is that sodium aluminate is or/and NaOH.During the feed molar of reaction system was formed, the a/c preferable range was 1.2～9.8, and the c/b preferable range is 3～5, and the d/c preferable range is 60～800.The reaction temperature preferable range is 80～105 ℃, and the crystallization time preferable range is 24～96 hours.
The present invention adopts porous α-Al
2O
3, γ-Al
2C
3Pottery, stainless steel substrates or glass are made carrier, one deck X type of growing in its surface molecular sieve thin layer.The effect of filming explanation: adopt the water base synthetic method of inorganic silicon-aluminum hydrochlorate, at α-Al
2O
3, γ-Al
2O
3With the X type zeolite of all growing on the stainless steel substrates surface, but generally must could form evenly continuous molecular sieve thin layer of one deck on its surface through 3～4 operations.What is called evenly is meant does not continuously have mechanical crackle, does not have residual non-crystallized baldness surface, and its surface is all evenly covered by molecular sieve.Certainly the molecular sieve that covers not is to be formed by single glomerocryst, but is made up of sieve particle, have granule boundary to exist, so molecular screen membrane is to be formed by the polycrystal adhesion.
The effect of filming is relevant with crystallization liquid concentration with the carrier aperture structure size.The small-bore carrier should be chosen the alumino-silicate crystallization liquid of low concentration and make coating solution, enter the aperture to help molecular sieve forerunner attitude gel, from the aperture to outgrowth with strengthen the intensity of film own.Prolong the molecular sieve generated time, it is even to help surperficial zeolite growth.Macropore carrier then should adopt the alumino-silicate crystallization liquid of higher concentration to make coating solution.Because the bulky grain gel can avoid molecular sieve to influence the permeability of the membrane energy too much in the growth of the depths, aperture of porous carrier.The aperture is too little or too big, even the concentration of adjusting crystallization liquid can not obtain even adhesion and combine than firm molecular sieve thin layer with carrier.
The increment of zeolite crystal changes with the number of times of filming on carrier.After choosing suitable crystallization liquid concentration, obtain molecular sieve crystal increment necessary on carrier, it is necessary filming for several times.
The present invention's inorganic substances compound membrane that one deck X type molecular sieve forms of on the porous carrier surface, having grown.Because X type molecular sieve bore diameter is bigger, can be used for the separation of big molecular mixing objects system, obtained effect preferably.
The invention will be further elaborated below by embodiment.
[embodiment 1]
The used medicine of preparation crystallization liquid is silica gel 30% (weight), sodium aluminate NaAlO
299.9% (weight), NaOH 97% (weight) and deionized water are made into concentration and with molar ratio computing are: Na
2O/SiO
2Be 1.29, SiO
2/ Al
2O
3Be 4.2, H
2O/SiO
2It is 121 reaction system.
Take by weighing 2.1104 gram NaOH, 1.0462 gram NaAlO
2Stir and slowly add respectively down in the 31.7054 gram deionized waters, stirred for several minute one-tenth solution A, take by weighing 5.097 gram 30% (weight) colloidal sols again, stir and add in the 20.08 gram deionized waters, stirred for several minute one-tenth solution B under agitation slowly adds solution B with solution A, colloidal sol hydrolysis under alkali condition, aging at last.
Getting 10 milliliters of the crystallization liquids of above-mentioned preparation inserts in the withstand voltage still of stainless steel of 25 * 40 millimeters tetrafluoro inner bags of liner φ.The porous ceramics piece carrier level in 200 dust apertures is inserted withstand voltage synthesis reactor liquid level top, make the potsherd below just contact (～1 millimeter video disc immerses in the liquid), envelope still with liquid level.The parallel immigration of crystallizing kettle has been preheating in 85 ℃ the heated oven, hydrothermal crystallizing is 40 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Fully wash to carrier with deionized water and to be neutral,, move into again in the high temperature muffle furnace, slowly be warming up to 450 ℃ of following roastings 4 hours, be cooled to room temperature again, to remove the moisture in the zeolite pore with 0.2 ℃/minute speed 90 ℃ of following dried overnight.
Repeat above-mentioned steps four times.The crystallization number of times can be by observing the SEM photo and to the investigation decision of the permeance property of carrier after the film forming.
Fig. 1 is the photo of four synthetic X type molecular sieve film layers that obtain of crystallization operation, and Fig. 1 a is the film surface picture, and Fig. 1 b then is the photo of its section, and Fig. 1 c is the surface picture of its base material porous ceramics.The result is presented at evenly continuous molecular sieve layer of one deck, about 10 microns of thickness on the porous ceramics piece substrate body.
[embodiment 2]
Crystallization liquid is made into concentration: Na
2O/SiO
2Be 1.58, SiO
2/ Al
2O
3Be 3.5, H
2O/SiO
2It is 175 reaction system.Take by weighing 1.5964 gram NaOH, 0.7394 gram NaAlO
2, slowly add in the 30.42 gram deionized waters stirred for several minute one-tenth solution A under the room temperature under stirring respectively.Take by weighing the colloidal sol of 3.6058 grams 30% (weight), stir in the adding 24.40 gram deionized waters, stirred for several minute one-tenth solution B under the room temperature.Under stirring at room, solution A is slowly added in the solution B colloidal sol hydrolysis under alkali condition, aging at last.
Getting 10 milliliters of the crystallization liquids of above-mentioned preparation inserts in the withstand voltage still of stainless steel of 25 * 40 millimeters tetrafluoro inner bags of liner φ.α-Al with 500 dust apertures
2O
3Porous ceramics video disc, level are inserted withstand voltage synthesis reactor liquid level top, make the potsherd below just contact (～1 millimeter video disc immerses in the liquid), envelope still with liquid level.The parallel immigration of crystallizing kettle has been preheating in 90 ℃ the heated oven, hydrothermal crystallizing is 70 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Be neutral with the abundant washing sample of deionized water to carrier,, move into again in the high temperature muffle furnace 90 ℃ of following dried overnight, slowly be warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, be cooled to room temperature again,, repeat aforesaid operations three times to remove the moisture in the zeolite pore.
Sample after the crystallization is carefully cut, insert in the sample cell, carry out XRD and characterize with complete surface.Instrument is a Rigakux optical diffraction analysis instrument.Fig. 2 is an X type crystal formation shape appearance figure.Do not occur amorphous state peak type collection of illustrative plates among the figure, illustrating has one deck X type molecular sieve thin layer to exist really on the carrier surface.Because X type molecular sieve is to be grown on the ceramic monolith, can see α-Al on the collection of illustrative plates
2O
3Characteristic peak.
[embodiment 3]
Crystallization liquid is made into concentration: Na
2O/SiO
2Be 5.26, SiO
2/ Al
2O
3Be 4.5, H
2O/SiO
2It is 500 reaction system.Take by weighing 1.2743 gram NaOH, 0.1304 gram NaAlO
2, slowly add in the 15.7308 gram deionized waters stirred for several minute one-tenth solution A under the room temperature under stirring respectively.Take by weighing the colloidal sol of 0.6502 gram 30% (weight), stir in the adding 12.2347 gram deionized waters, stirred for several minute one-tenth solution B under the room temperature.Under stirring at room, solution A is slowly added in the solution B colloidal sol hydrolysis under alkali condition, aging at last.
Getting 10 milliliters of the crystallization liquids of above-mentioned preparation inserts in the withstand voltage still of stainless steel of 25 * 40 millimeters tetrafluoro inner bags of liner φ.α-Al with 1000 dust apertures
2O
3Porous ceramics video disc level is inserted withstand voltage synthesis reactor liquid level top, makes the potsherd below just contact (～1 millimeter video disc immerses in the liquid), envelope still with liquid level.The parallel immigration of crystallizing kettle has been preheating in 99 ℃ the heated oven, hydrothermal crystallizing is 84 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Fully wash to carrier with deionized water and to be neutral,, move into again in the high temperature muffle furnace 90 ℃ of following dried overnight, slowly be warming up to 500 ℃ of following roastings 5 hours with 0.5 ℃/minute speed, be cooled to room temperature again,, repeat aforesaid operations three times to remove the moisture in the zeolite pore.
The crystalline solid that forms on porous carrier is analyzed qualitative with heat.Fig. 3 carries out differential thermal analysis (DTA) figure to the carrier material after the crystallization.At the 520K place the recessed peak of one heat absorption is arranged among the figure, this is very consistent with X type molecular sieve thermal dehydration differential thermal analysis collection of illustrative plates, illustrates that the crystalline solid that forms on the carrier surface has X type molecular sieve to exist.
[embodiment 4]
Crystallization liquid is made into concentration: Na
2O/SiO
2Be 7.72, SiO
2/ Al
2O
3Be 4.8, H
2O/SiO
2It is 750 reaction system.Take by weighing 1.6837 gram NaOH, 0.1154 gram NaAlO
2, slowly add in the 19.501 gram deionized waters stirred for several minute one-tenth solution A under the room temperature under stirring respectively.Take by weighing the colloidal sol of 0.564 gram 30% (weight), stir in the adding 19.5307 gram deionized waters, stirred for several minute one-tenth solution B under the room temperature.Under stirring at room, solution A is slowly added in the solution B colloidal sol hydrolysis under alkali condition, aging at last.
Getting 10 milliliters of the crystallization liquids of above-mentioned preparation inserts in the withstand voltage still of stainless steel of 25 * 40 millimeters tetrafluoro inner bags of liner φ.γ-Al with 50 dust apertures
2O
3The porous ceramics video disc, level is inserted withstand voltage synthesis reactor liquid level top, makes the potsherd below just contact (～1 millimeter video disc immerses in the liquid) with liquid level, seals still.The parallel immigration of crystallizing kettle has been preheating in 95 ℃ the heated oven, hydrothermal crystallizing is 90 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Fully wash to carrier with deionized water and to be neutral,, move into again in the high temperature muffle furnace 90 ℃ of following dried overnight, slowly be warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, be cooled to room temperature again,, repeat aforesaid operations three times to remove the moisture in the zeolite pore.
Sample after the crystallization is carefully cut, insert in the sample cell with complete surface, carry out XRD and characterize, characterization result has shown typical X type crystal formation pattern, amorphous state peak type collection of illustrative plates do not occur, and illustrating has one deck X type molecular sieve thin layer to exist really on the carrier surface.γ-the Al that the carrier pottery also occurred simultaneously
2O
3Characteristic peak, but the peak type is very little.
Again above-mentioned sample is carried out the SEM electronic microscope photos, the photo of film surface, section is arranged, compare with the porous ceramics photo of base material, being presented at obviously has evenly continuous crystallizing layer of one deck, thick about 5 microns on the porous substrate body.
[embodiment 5]
Crystallization liquid is made into concentration: Na
2O/SiO
2Be 9.02, SiO
2/ Al
2O
3Be 4.5, H
2O/SiO
2It is 750 reaction system.Take by weighing 1.2743 gram NaOH, 0.1304 gram NaAlO
2, slowly add in the 15.7308 gram deionized waters stirred for several minute one-tenth solution A under the room temperature under stirring respectively.Take by weighing the colloidal sol of 0.1902 gram 30% (weight), stir in the adding 12.2347 gram deionized waters, stirred for several minute one-tenth solution B under the room temperature.Under stirring at room, solution A is slowly added in the solution B colloidal sol hydrolysis under alkali condition, aging at last.
Getting 10 milliliters of the crystallization liquids of above-mentioned preparation inserts in the withstand voltage still of stainless steel of 25 * 40 millimeters tetrafluoro inner bags of liner φ.The porous stainless steel video disc level in 5000 dust apertures is inserted withstand voltage synthesis reactor, make sample, the envelope still by the whole submergences of crystallization liquid.The parallel immigration of crystallizing kettle has been preheating in 99 ℃ the heated oven, hydrothermal crystallizing is 90 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Fully wash to carrier with deionized water and to be neutral,, move into again in the high temperature muffle furnace 90 ℃ of following dried overnight, slowly be warming up to 450 ℃ of following roastings 5 hours with 0.5 ℃/minute speed, be cooled to room temperature again,, repeat aforesaid operations three times to remove the moisture in the zeolite pore.
The crystalline solid that forms on porous carrier is analyzed with heat, and the carrier material after the crystallization is carried out differential thermal analysis (DTA).Analysis result shows that the recessed peak of a heat absorption is arranged at the 520K place, and this is very consistent with X type molecular sieve thermal dehydration differential thermal analysis collection of illustrative plates, illustrates that the crystalline solid that forms on the carrier surface has X type molecular sieve to exist.
Above-mentioned sample carries out the SEM electronic microscope photos, and the photo of film surface, section is arranged, and compares with the porous ceramics photo of base material, evenly continuous crystallizing layer of one deck is obviously arranged, thick about 10 microns on porous stainless steel.The crystal grain of also growing is located in inside at stainless steel substrates near the aperture.The crystal adhesion of aperture and carrier outer surface is extended in these crystal growths, becomes the transition zone of anisotropic membrane.This transition zone can increase the mechanical strength of film, can improve the permeability and separation ability of film again.
Claims (5)
1, a kind of preparation method of porous material membrane of molecular sieve is a raw material with aluminium source, sodium source, silica gel or Ludox and water, and the feed molar composition of reaction system is counted with oxide: aNa
2ObAl
2O
3CSiO
2DH
2O, a/c=1.0～13.0 wherein, c/b=2～8, d/c=50～1000, with the aperture is that the glass or the stainless steel porous material of 40～10000 dusts is dipped in the reaction system, reaction raw materials crystallization 3～144 hours under 50～120 ℃ of reaction temperature conditions, crystallization growth X type molecular sieve on porous material.
2,, it is characterized in that the aluminium source is the aluminium alcoholates of metal aluminum foil, sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or 2～4 carbon atoms according to the preparation method of the described porous material membrane of molecular sieve of claim 1; The sodium source is that sodium aluminate is or/and NaOH.
3,, it is characterized in that the aluminium source is a sodium aluminate according to the preparation method of the described porous material membrane of molecular sieve of claim 2.
4,, it is characterized in that a/c=1.2～9.8 according to the preparation method of the described porous material membrane of molecular sieve of claim 1; C/b=3～5; D/c=60～800.
5, according to the preparation method of the described porous material membrane of molecular sieve of claim 1, it is characterized in that reaction temperature is 80～105 ℃, crystallization time is 24～96 hours.
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|---|---|---|---|
| CNB991139909A CN1193815C (en) | 1999-12-02 | 1999-12-02 | Porous material membrane of molecular sieve and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991139909A CN1193815C (en) | 1999-12-02 | 1999-12-02 | Porous material membrane of molecular sieve and its preparation method |
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|---|---|
| CN1303730A CN1303730A (en) | 2001-07-18 |
| CN1193815C true CN1193815C (en) | 2005-03-23 |
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|---|---|---|---|---|
| CN1323944C (en) * | 2005-08-02 | 2007-07-04 | 洛阳市建龙化工有限公司 | Process method of improved 13X molecular screen |
| CN100371078C (en) * | 2006-04-18 | 2008-02-27 | 天津大学 | Method for preparing catalyst with micron-grade zeolite molecular sieve coated on carrier |
| CN100455354C (en) * | 2007-03-27 | 2009-01-28 | 天津大学 | Method for producing zeolite molecular sieve film carrier noble metal catalyst |
| WO2013139121A1 (en) * | 2012-03-21 | 2013-09-26 | 中国科学院大连化学物理研究所 | Preparation of aluminum phosphate molecular sieve membrane supported on porous aluminum oxide carrier |
| CN108187729B (en) * | 2018-01-15 | 2021-03-12 | 中国科学院上海高等研究院 | Composite catalyst film and preparation method and application thereof |
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