CN1114469C - Porous stainless steel membrane for supporting molecular sieve and preparation method thereof - Google Patents
Porous stainless steel membrane for supporting molecular sieve and preparation method thereof Download PDFInfo
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- CN1114469C CN1114469C CN99113992A CN99113992A CN1114469C CN 1114469 C CN1114469 C CN 1114469C CN 99113992 A CN99113992 A CN 99113992A CN 99113992 A CN99113992 A CN 99113992A CN 1114469 C CN1114469 C CN 1114469C
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Abstract
The present invention relates to a porous stainless steel pipe film of loading molecular sieves, and a preparation method thereof. The present invention mainly overcomes the defect that the prior art does not relate to the film formulation of X type molecular sieves on a carrier. The porous material film of molecular sieves adopts a reaction system of which the molar composition of raw materials is aNa2O. bAl2O3. cSiO2. dH2O, wherein 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, the raw materials are crystallized for 3 to 144 hours, and an X type molecular sieve is successfully formed on a porous stainless steel pipe whose pore diameter is from 40 to 10000 angstroms through crystallization growth. The stainless steel pipe film of loading molecular sieves has the characteristics of high mechanical strength, hard damage, temperature resistance and pressure resistance, solves the defect of the prior art, and can be used in industrial production.
Description
The present invention relates to porous stainless steel membrane of load molecular sieve and preparation method thereof.
X type molecular sieve has bigger aperture passage, and higher voidage is applicable to more macromolecular separation and course of reaction.Since stainless steel material have heatproof, withstand voltage, mechanical strength is high, cracky not, machine-shaping is characteristics easily, so it is the industrialized ideal material of membrane process.
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 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 has become the focus and the difficult point of people's researchs.But ceramic material is frangible, the anti-vibration ability, and the machine-shaping inconvenience can make troubles to commercial Application.
U.S. Pat P5464798 adopts at α-Al
2O
3Be coated with γ-Al on the inner surface of porous ceramic pipe
2O
3Gel is modified into the body that supports in 50 dust apertures with it, and the molecular sieve mother liquor that the silica gel of packing in the earthenware, NaOH and TPABr form carries out the crystallization operation, gets final product for general 2～3 times.Synthetic Silicalite-1 zeolite membrane only is 3～14% of a former basement membrane generally at the permeation flux that carries out obviously having reduced after film modified gas, 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-1 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.Adopt this molecular-sieve film catalytic technology and α-Al
2O
3Film is compared, 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.In the test silicon source and aluminium source are disposed through suitable, the mol ratio of last mother liquor consists of 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
CO2/N2Can reach 53～56, CO
2Infiltration rate can reach 1.7 * 10
-7Mole/rice
2. second. handkerchief, and α
CO2/N2And also can reach 42.
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 a pure cyclohexane has separating power.
In sum, the porous ceramics periosteum situation that does not all relate to the situation of X type molecular sieve film forming on carrier in the above-mentioned document and be suitable for the load X type molecular sieve of commercial Application.
One of purpose of the present invention is the shortcoming that does not relate to X type molecular sieve film forming situation on carrier in the conventional art in order to overcome, and a kind of porous stainless steel membrane of novel load molecular sieve is provided.This stainless steel membrane is to form composite membrane at carrier surface growth one deck X type molecular sieve, has the ability of infiltration, separation, and this stainless steel membrane has the mechanical strength height, not cracky, heat resisting and pressure resisting, be suitable for the characteristics of commercial Application.
Two of purpose of the present invention provides the preparation method of the load molecular sieve porous stainless steel membrane that one of a kind of and purpose adapt.
One of purpose of the present invention is to realize by following technical scheme: a kind of porous stainless steel membrane of load molecular sieve, with the aperture is that the porous stainless steel of 40～10000 dusts is a carrier, and crystallization grown silicon al mole ratio is 2～8 X type molecular sieve on carrier.
The preferable range in aperture is 200～5000 dusts in the technique scheme.
Two of purpose of the present invention is to realize by following technical scheme: a kind of preparation method of porous stainless steel membrane of load molecular sieve, with aluminium source, sodium source, silica gel or Ludox and water is raw material, 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 a surface coverage, the aperture is that the porous stainless steel of 40～10000 dusts is dipped in the reaction system, reaction raw materials under 50～120 ℃ of reaction temperature conditions, crystallization 3～144 hours, crystallization growth X type molecular sieve on porous stainless steel.
In the technique scheme, the aluminium source is the aluminium alcoholates of metal aluminum foil, sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or 2～4 carbon atoms, and its 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, with molar ratio computing, the preferable range of a/c was 1.2～9.8, and the preferable range of c/b is 3～5, and the preferable range of d/c is 60～800; The preferable range of reaction temperature is 80～105 ℃, and the preferable range of crystallization time is 24～96 hours.
The present invention adopts porous stainless steel to make carrier, and growth one deck X type molecular sieve thin layer is gone up on the surface within it.The effect of filming explanation: adopt the water base synthetic method of inorganic silicon-aluminum hydrochlorate, the X type of on the surface of porous stainless steel, growing zeolite molecular sieve.But must be through 6～7 times even the even continuous molecular sieve thin layer of more times operation surface formation within it one deck.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.
Zeolite molecular sieve is attached to carrier inner surface film forming, carrier for unit volume can provide bigger infiltrating area, and as the reactor single tube, many stainless steel tube zeolite molecular sieve films can form separation of shell and tube film or reactor by constriction together, can increase the area of unit volume membrane process greatly, have practicality, be suitable for the popularization and the industrialization of membrane process.
Because the fragility of pottery, when being connected, easily split frangiblely with other assemblies in the zeolite membrane that forms on the ceramic body, be unfavorable for the commercial Application of membrane process.And the compound molecule sieve membrane that forms on the porous stainless steel carrier because stainless steel material has mechanical strength height, not cracky, heat resisting and pressure resisting, does not therefore exist dissimilar materials to connect the problem of being brought.
Grow the inorganic substances compound membrane that one deck X type molecular sieve forms on the porous stainless steel pipe internal surface, X type molecular sieve bore diameter is bigger, can be used for the separation of big molecular mixing objects system, has 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.
The three kinds of used crystallization of filming are synthesized liquid S3, S5, S6 prepares according to following method:
Crystallization is synthesized liquid S3: take by weighing 0.746 gram NaOH, 0.3688 gram NaAlO
2, slowly add in the 15.330 gram deionized waters stirred for several minute one-tenth solution A under stirring respectively.Take by weighing the colloidal sol of 1.8018 grams 30% (weight), stir in the adding 12.010 gram deionized waters stirred for several minute one-tenth solution B.Under agitation solution A is slowly added solution B at last, colloidal sol hydrolysis under alkali condition, aging.
Crystallization is synthesized liquid S5: take by weighing 2.560 gram NaOH, 0.258 gram NaAlO
2, stirring and slowly to add respectively down in the 35.910 gram deionized waters, stirred for several minute becomes solution A, takes by weighing the colloidal sol of 1.2644 grams 30% (weight) again, stirs to add in the 20.0422 gram deionized waters, and stirred for several minute becomes solution B.Under agitation solution A is slowly added solution B at last, colloidal sol hydrolysis under alkali condition, aging.
Crystallization is synthesized liquid S6: take by weighing 1.6845 gram NaOH, 0.1158 gram NaAlO
2, slowly add in the 20.420 gram deionized waters stirred for several minute one-tenth solution A under stirring respectively.Take by weighing the colloidal sol of 0.1688 gram 30% (weight), stir in the adding 17.6218 gram deionized waters stirred for several minute one-tenth solution B.Under agitation solution A is slowly added solution B at last, colloidal sol hydrolysis under alkali condition, aging.
Get porous stainless steel, specification is φ 12 * 1.0 * L20 millimeter, and the aperture is 2000 dusts, and an end welds with the atresia stainless steel tube of long 130 millimeters of same diameter mutually with homogeneity porous stainless steel material seal, the other end.Therefore the length of test specimen is 150 millimeters.At room temperature, cleaned sample 1 hour with the NaOH solution of 1 normal concentration under ultrasonic wave, spend deionised water till be neutrality, ambient temperature overnight is dried.Be warming up to 500 ℃, heat treatment 2 hours naturally cools to room temperature.
Get the synthetic liquid S310 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, and 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.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again, repeats above-mentioned steps once.
Get the synthetic liquid S510 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 90 ℃, and 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.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again, repeats above-mentioned steps once.
Get the synthetic liquid S610 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 90 ℃, and hydrothermal crystallizing is 96 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.
Repeat above-mentioned steps once.For the last time, sample temperature programming heat treatment is slowly to be warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, is cooled to room temperature again.
Carrier inner surface sample after the crystallization is carefully cut, insert in the sample cell with complete inner surface, carry out XRD and characterize, amorphous state peak type collection of illustrative plates do not occur, illustrating has one deck X type molecular sieve thin layer to exist really on the carrier surface.
Inner surface sample after the crystallization is carefully cut, carry out SEM with complete inner surface and characterize.Be presented in the photo evenly continuous molecular sieve layer of one deck, about 20 microns of thickness are arranged on the porous substrate body.Also there is crystalline solid to exist in the stainless steel tube porous body, increased compound film strength as the transition zone of composite membrane.
[embodiment 2]
Film required synthetic crystallization liquid compound method with embodiment 1.Used porous stainless steel sample cell specification is with embodiment 1, and just the aperture is 200 dusts.
At room temperature, cleaned sample 1 hour with the HCl solution of 1 normal concentration under ultrasonic wave, spend deionised water till be neutrality, ambient temperature overnight is dried.NaOH solution with 1 normal concentration cleaned sample 1 hour under ultrasonic wave again, spent deionised water till be neutrality, and ambient temperature overnight is dried.Be warming up to 500 ℃, heat treatment 2 hours naturally cools to room temperature.
Get the synthetic liquid S310 milliliter of crystallization of preparation and pour in the porous stainless steel sample cell, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, and 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.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.
Repeat above-mentioned steps seven times.For the last time, sample temperature programming heat treatment is, slowly is warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, is cooled to room temperature again.
Carrier inner surface sample after the crystallization is carefully cut, carry out XRD with complete inner surface and characterize, the XRD figure spectrum shows typical X type crystal formation pattern, amorphous state peak type collection of illustrative plates do not occur.Carrying out SEM with complete inner surface and section characterizes.The photo of SEM, being presented at has evenly continuous molecular sieve layer of one deck, about 30 microns of thickness on the porous substrate body.Also there is crystalline solid to exist in the stainless steel porous body.
[embodiment 3]
Film required synthetic crystallization liquid compound method with embodiment 1.Get porous stainless steel, specification is φ 12 * 1.0 * L20 millimeter, and the aperture is 5000 dusts, and an end welds with the atresia stainless steel tube of long 130 millimeters of same diameter mutually with homogeneity porous stainless steel material seal, the other end.The length of test specimen is 150 millimeters.At room temperature, cleaned sample 1 hour with the NaOH solution of 1 normal concentration under ultrasonic wave, spend deionised water till be neutrality, ambient temperature overnight is dried.Temperature programming to 500 ℃, heat treatment 2 hours naturally cools to room temperature.
Get the synthetic liquid S310 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, and 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.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.Repeat above-mentioned steps three times.
Get the synthetic liquid S610 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, get above-mentioned S65 milliliter again and pour the crystallization synthesis reactor into, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 90 ℃, and hydrothermal crystallizing is 96 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.
Repeat above-mentioned steps once.For the last time, sample temperature programming heat treatment is, slowly is warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, is cooled to room temperature again.
Carrying out SEM with complete inner surface and section characterizes.The photo of SEM shows evenly continuous molecular sieve layer of one deck is arranged, about 15 microns of thickness on the porous substrate body.Also there is crystalline solid to exist in the stainless steel porous body.
The permeation flux of table 1 one-component steam and infiltration ratio, 350 ℃
| (C 4H 9) 3N | (C 4F 9) 3N | The flux ratio | |
| Flux P, 10 -7Mole/rice 2. second. handkerchief | P (C4H9)3N/P(C4F9)3N | ||
| Embodiment 3 | Stainless steel tube | ||
| 410.0 | 237.0 | 1.43 | |
| Stainless steel tube X type molecular screen membrane | |||
| 1.87 | 0.017 | 110 | |
| Embodiment 4 | Stainless steel tube | ||
| 360.0 | 248.0 | 1.45 | |
| Stainless steel tube X type molecular screen membrane | |||
| 8.46 | 0.082 | 103.2 | |
Table 1 has shown (C
4H
9)
3N and (C
4F
9)
3The one-component steam infiltration of N is by the permeation flux of the stainless steel tube molecular screen membrane of above-mentioned preparation.This result and (C
4H
9)
3N and (C
4F
9)
3N traditional absorption behavior on X type molecular sieve is consistent.Because (C
4H
9)
3The kinetic diameter of N is less than the slit aperture of X type zeolite, thereby can adsorb for it; Because (C
4F
9)
3Therefore the kinetic diameter of N can not be adsorbed by it greater than the aperture of X type zeolite.After forming stainless steel tube X type molecular screen membrane, (C
4H
9)
3N can see through, and (C
4F
9)
3N is difficult to see through.
[embodiment 4]
Film required synthetic crystallization liquid compound method with embodiment 1.Used porous stainless steel sample cell specification together
Embodiment 3.
At room temperature, with the HNO of 1 normal concentration
3Solution cleaned sample 1 hour under ultrasonic wave, spend deionised water till be neutrality, and ambient temperature overnight is dried.NaOH solution with 1 normal concentration cleaned sample 1 hour under ultrasonic wave again, spent deionised water till be neutrality, and ambient temperature overnight is dried.Be warming up to 500 ℃, roasting 2 hours naturally cools to room temperature.
Get the synthetic liquid S510 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, and 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.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.
Repeat above-mentioned steps five times.For the last time, sample temperature programming heat treatment is slowly to be warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, is cooled to room temperature again.
Carrier inner surface sample after the crystallization is carefully cut, carry out XRD with complete inner surface and characterize, the XRD figure spectrum shows typical X type crystal formation pattern, amorphous state peak type collection of illustrative plates do not occur.Carrying out SEM with complete inner surface and section characterizes.The photo of SEM shows evenly continuous molecular sieve layer of one deck is arranged, about 25 microns of thickness on the porous substrate body.Also there is crystalline solid to exist in the stainless steel porous body.
[embodiment 5]
Film required synthetic crystallization liquid compound method with embodiment 1.Used porous stainless steel sample cell specification is with embodiment 3.
At room temperature, with the HNO of 1 normal concentration
3Solution cleaned sample 1 hour under ultrasonic wave, spend deionised water till be neutrality, and ambient temperature overnight is dried.NaOH solution with 1 normal concentration cleaned sample 1 hour under ultrasonic wave again, spent deionised water till be neutrality, and ambient temperature overnight is dried.Be warming up to 500 ℃, roasting 2 hours naturally cools to room temperature.
Get the synthetic liquid S310 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, get above-mentioned S35 milliliter and pour in the crystallization synthesis reactor, again stainless steel tube is vertically inserted in the crystallization synthesis reactor envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, and 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.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.
Get the synthetic liquid S610 milliliter of crystallization of above-mentioned preparation and pour in the porous stainless steel sample cell, get above-mentioned S65 milliliter and pour in the crystallization synthesis reactor, again stainless steel tube is vertically inserted in the withstand voltage crystallizing kettle envelope still.Crystallizing kettle is moved in the heated oven that has been preheating to 90 ℃, and hydrothermal crystallizing is 96 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.Under ultrasonic wave, fully wash to carrier with deionized water and to be neutral.Temperature programming heat treatment more slowly is warming up to 0.2 ℃/minute speed and kept under 120 ℃ 4 hours, is cooled to room temperature again.
Repeat above-mentioned steps four times.For the last time, sample temperature programming heat treatment is, slowly is warming up to 450 ℃ of following roastings 4 hours with 0.5 ℃/minute speed, is cooled to room temperature again.
Carrier inner surface sample after the crystallization is carefully cut, carry out XRD with complete inner surface and characterize, the XRD figure spectrum shows typical X type crystal formation pattern, amorphous state peak type collection of illustrative plates do not occur.Carrying out SEM with complete inner surface and section characterizes.The photo of SEM shows evenly continuous molecular sieve layer of one deck is arranged, about 25 microns of thickness on the porous substrate body.
Also listed (C in the table 1
4H
9)
3N and (C
4F
9)
3The steam infiltration of N is by the permeation flux of the molecular screen membrane of above-mentioned preparation.This result and (C
4H
9)
3N and (C
4F
9)
3N traditional absorption behavior on X type molecular sieve is consistent, illustrates that the X type molecular screen membrane that forms on the porous stainless steel carrier is evenly continuous, and the molecular sieve pore passage of zeolite layer is (C
4H
9)
3N and (C
4F
9)
3The main duct that N sees through.
Claims (7)
1, a kind of porous stainless steel membrane of load molecular sieve is that the porous stainless steel of 40～10000 dusts is a carrier with the aperture, and crystallization grown silicon al mole ratio is 2～8 X type molecular sieve on carrier.
2,, it is characterized in that the aperture is 200～5000 dusts according to the porous stainless steel membrane of the described load molecular sieve of claim 1.
3, according to the preparation method of the porous stainless steel membrane of the described load molecular sieve of claim 1, be raw material with aluminium source, sodium source, silica gel or Ludox and water, the feed molar of reaction system is formed and 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 a surface coverage, the aperture is that the porous stainless steel of 40～10000 dusts is dipped in the reaction system, reaction raw materials under 50～120 ℃ of reaction temperature conditions, crystallization 3～144 hours, crystallization growth X type molecular sieve on porous stainless steel.
4, according to the preparation method of the porous stainless steel membrane of the described load molecular sieve of claim 3, 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; The sodium source is that sodium aluminate is or/and NaOH.
5, according to the preparation method of the porous stainless steel membrane of the described load molecular sieve of claim 4, it is characterized in that the aluminium source is a sodium aluminate.
6, according to the preparation method of the porous stainless steel membrane of the described load molecular sieve of claim 3, it is characterized in that with molar ratio computing a/c=1.2～9.8; C/b=3～5; D/c=60～800.
7, according to the preparation method of the porous stainless steel membrane of the described load molecular sieve of claim 3, it is characterized in that reaction temperature is 80～105 ℃, crystallization time is 24～96 hours.
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| 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 |
| CN108117088A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | The method of in-situ synthesis zeolite molecular sieve film |
| CN110548482A (en) * | 2019-09-26 | 2019-12-10 | 中国原子能科学研究院 | preparation method of stainless steel-based molecular sieve membrane material for adsorbing uranium hexafluoride |
| CN111893375B (en) * | 2020-06-16 | 2021-09-28 | 宁波市华涛不锈钢管材有限公司 | Thin-wall stainless steel for three-way pipe fitting and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS504048A (en) * | 1973-05-21 | 1975-01-16 | ||
| JPH04220560A (en) * | 1990-12-19 | 1992-08-11 | Shimadzu Corp | Filling agent of gas chromatography column |
| EP0674939A2 (en) * | 1994-03-31 | 1995-10-04 | Nok Corporation | Gas separation membrane and process for producing the same |
| JPH08257301A (en) * | 1995-03-23 | 1996-10-08 | Mitsui Eng & Shipbuild Co Ltd | Production of y-type zeolite membrane and liquid mixture separation membrane |
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1999
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS504048A (en) * | 1973-05-21 | 1975-01-16 | ||
| JPH04220560A (en) * | 1990-12-19 | 1992-08-11 | Shimadzu Corp | Filling agent of gas chromatography column |
| EP0674939A2 (en) * | 1994-03-31 | 1995-10-04 | Nok Corporation | Gas separation membrane and process for producing the same |
| JPH08257301A (en) * | 1995-03-23 | 1996-10-08 | Mitsui Eng & Shipbuild Co Ltd | Production of y-type zeolite membrane and liquid mixture separation membrane |
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| CN1285234A (en) | 2001-02-28 |
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