CN1112231C - Preparation of x-type molecular sieve film - Google Patents
Preparation of x-type molecular sieve film Download PDFInfo
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- CN1112231C CN1112231C CN 00111719 CN00111719A CN1112231C CN 1112231 C CN1112231 C CN 1112231C CN 00111719 CN00111719 CN 00111719 CN 00111719 A CN00111719 A CN 00111719A CN 1112231 C CN1112231 C CN 1112231C
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- molecular sieve
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Abstract
The present invention relates to a method for preparing an X type molecular sieve film, which mainly overcomes the deficiencies that the previous techniques don't relate to the film forming of X type molecular sieves on carriers and film forming processes are complicated and has long time. In the present invention, a reaction system of which the mol components of raw materials is aNa2O. bAl2O3. cSiO2. dH2O is adopted. In the reaction system, a/c=1.0 to 12.9; c/b=2 to 6; d/c=200 to 1000. in a synthetic process, a silicon source, an aluminium source and a sodium source are respectively put at both sides of a porous material pipe, and are crystallized for 36 to 168 hours under the condition that the reaction temperature is from 50 to 120 DEG C. X type molecular sieves are successfully formed on the inner surface of a porous material pipe of which the pore diameters are from 40 to 10000 angstroms through crystallization growth. Furthermore, the present invention has the characteristics of simple process of film forming operation, strong adhesive force of molecular sieves and high yield of molecular sieves, better overcomes the previous deficiencies, and can be used for industrial production.
Description
The present invention relates to prepare the method for X type molecular screen membrane.
X type molecular sieve has bigger aperture passage, and higher voidage is applicable to more macromolecular separation and course of reaction, and 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,
Can reach 53～56, CO
2Infiltration rate can reach 1.7 * 10
-7Mole/rice
2. second. handkerchief, and
And 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 alcohol-cyclohexane has separating power.
In sum, the porous material membrane 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.The inventor finds by test in addition, load X type molecular sieve on porous material, and the X type molecular sieve of formation and the adhesive force of carrier are relatively poor, and the required material quantity of crystallization is big, and promptly He Cheng X type molecular sieve yield is low.
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 method of the X of preparation type molecular screen membrane to be provided.This preparation method has X type molecular screen membrane and the carrier strong adhesion that makes, the high characteristics of X type molecular sieve yield that obtain simultaneously.
The objective of the invention is to realize by following technical scheme: a kind of method of the X of preparation type molecular screen membrane 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=1.0～12.9, c/b=2～6, d/c=200～1000, in building-up process, earlier silica gel or Ludox and water wiring solution-forming being placed the aperture is in the glass tube or stainless steel tube porous material pipe of 40～10000 dusts, sodium source and aluminium source and water wiring solution-forming are placed outside the porous material pipe, under 50～120 ℃ of reaction temperature conditions, crystallization 36～168 hours is at porous material pipe internal surface crystallization growth X type molecular sieve, wherein before crystallization, preload amorphous aluminosilicate or X type molecular sieve in the porous material pipe, its preload amount is 0.01～0.5% of porous material pipe weight by weight percentage.
The aluminium source is the aluminium alcoholates of metal aluminum foil, sodium aluminate, aluminum sulfate, boehmite, alumino-silicate or 2～4 carbon atoms in the technique scheme, and its preferred version is a sodium aluminate; The sodium source is that sodium aluminate is or/and NaOH.With molar ratio computing, the preferable range of a/c is 1.2～9.8 in the reaction system, and the preferable range of c/b is 3～5, and the preferable range of d/c is 250～800; During crystallization, the preferable range of reaction temperature is 80～105 ℃, and the preferable range of crystallization time is 72～120 hours.
Adopt the new method of the preparation X type molecular screen membrane of the present invention's description, at even, the continuous X type molecular sieve thin layer of porous material Guan Shangneng growth one deck.Can be used for the separation of bigger molecular mixing objects system, the molecule sieve aperture is modified reached adjustment aperture, especially can be widely used at separation field with the method for modifying of physics or chemistry.
X type molecular sieve zeolites is mainly in carrier inner surface film forming, characterize by SEM, in the close hole of carrier inner surface, the crystal growth of X type molecular sieve zeolites is arranged, the crystal layer of growth in this layer hole, go deep into 150～200 microns of hole Nei Keda,, improved the adhesive ability of the whole load X of X type molecular sieve type molecular sieve zeolites layer with the X type molecular sieve zeolites layer adhesion mutually on the carrier surface.Carrier for unit volume can provide bigger infiltrating area, and as the reactor single tube, many zeolite membrane can form separation of shell and tube film or reactor by constriction together, can increase the area of unit volume membrane process, have practicality, help the popularization and the industrialization of membrane process.
When the method that the reaction system raw material is mixed is synthesized X type molecular sieve zeolites film earlier, owing to adopt gelatinous initial liquid, outside growth centre crystallization that partial gel provides with carrier was favourable to film forming, most of gel formed Powdered X type molecular sieve with the homogeneous phase crystallization in the solution main body.After the crystallization operation each time, the X type molecular sieve that cleans carrier surface forms layer, the result who cleans from ultrasonic wave as can be seen, most formations layer is the sedimentary deposit of X type molecular sieve powder, be easy to remove, the X type molecular sieve amount of crystallization and the crosslinked growth of carrier each time seldom.Through seven, eight times operation, could form certain thickness X type molecular sieve top layer.Adopt method of the present invention at porous material pipe internal surface synthesis of molecular sieve top layer, after synthesizing each time, sample cleans, and washing is 30 minutes under ultrasonic wave, and the carrier surface growth-gen is washed seldom.After the operation of four to five crystallization, top layer is characterized with SEM, its thickness reaches～and 20 microns, under light microscope, can observe one deck crystal layer and exist, with the spoon scraping, be difficult to scrape, the mechanical strength of composite membrane obviously improves.
The main composition of the initial liquid of the present invention splits the method for operating of porous material pipe both sides, avoided occurring in the crystallization effect unhelpful of crystallization liquid main body to film forming, therefore adopt the initial liquid of fully dilution to form, can obviously reduce the input amount of medicine, improve the yield of X type molecular sieve, obtained effect preferably.
The invention will be further elaborated below by embodiment.[embodiment 1]
It is as follows that the used crystallization of filming is synthesized liquid making method: take by weighing 0.560 gram (30% weight) Ludox, add successively under stirring in the 18.680 gram deionized waters, stirred for several minute one-tenth solution A takes by weighing 1.9622 gram NaOH again, 0.1146 gram NaAlO
2, stirring slowly adds in the 18.6823 gram deionized waters, stirred for several minute one-tenth solution B.
Used α-Al
2O
310 * 1.5 * 20 millimeters of porous ceramic pipe Φ, aperture 200 nanometers.At room temperature, use 1N HNO
3Solution cleaned sample 1 hour under ultrasonic wave, spend deionised water till be neutrality, and ambient temperature overnight is dried.Again at room temperature, cleaned sample 1 hour with 1N NaOH solution 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.
Molecular sieve crystal seed liquid X1 is by following prescription and condition is synthetic and processing: with molar ratio computing: SiO
2/ Al
2O
3=4.0, Na
2O/SiO
2=1.29, H
2O/SiO
2=60.5,95 ℃ of crystallization temperatures, crystallization time 9 hours; Spend deionised water, be neutral to sample.Dried 3 hours down at 120 ℃, be cooled to room temperature; Take by weighing 0.2562 gram X type molecular sieve powder, join in the 49.7584 gram deionized waters, keep stirring, be suspension to molecular sieve pulp.
The X type molecular sieve crystal seed liquid X1 that gets above-mentioned preparation pours in the porous sample cell for 10 milliliters, in pressurization N2 access tube, maintains under the 345KPa and is extracted until liquid in pipe.Use the washed with de-ionized water sample.Repeat aforesaid operations once.Ambient temperature overnight is dried.Temperature programming to 180 ℃ kept 2 hours, naturally cooled to room temperature.
Get the solution A of above-mentioned preparation and pour in the antipriming pipe for 5 milliliters, get solution B again and pour in the stainless steel crystallizing kettle for 5 milliliters, samples vertical is inserted synthesis reactor, the envelope still, room temperature left standstill 48 hours.Crystallizing kettle is moved in the heated oven that has been preheating to 80 ℃, and hydrothermal crystallizing is 120 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.With deionized water washing sample 30 minutes under ultrasonic wave, further wash again to carrier and be neutral.Be warming up to and kept under 120 ℃ 4 hours, be cooled to room temperature again.Repeat above-mentioned film-forming process four times.After the last crystallization operation, be warming up to 450 ℃ of following roastings 4 hours, be cooled to room temperature again.
Carrier inner surface after the crystallization is carried out XRD, SEM to be characterized.It is X type molecular sieve crystal formation collection of illustrative plates that XRD shows; SEM shows that inner surface has a top layer, and section SEM shows thick about 10～15 microns, also has molecular sieve to grow up in the carrier duct under the top layer, forms transition zone, deeply reaches 100 microns.
Form the initial liquid of mixed preparing gel crystallization with same sial, just above-mentioned porous ceramic pipe is put in aluminium source, sodium source, silicon source simultaneously, by the synthetic X type molecular screen membrane of above-mentioned condition, through the crystallization operation of five repetitions, the thickness of the molecular sieve layer that obtains is about 15～20 microns.Because the surface attachment layer is very thin, its tack with carrier surface detects and is difficult for, and tests and checks with the method for experience.Firmly scrape on molecular sieve layer with spoon, use synthetic method of the present invention, the molecular sieve layer of load combines firmly with carrier on the carrier, be difficult to scrape, and when firmly scraping with aforementioned method in the past, load layer is cracked easily, has many molecular sieve powder to produce.Show the method for the present invention of using, surface molecular sieve layer adheres to well with carrier, can form firm top layer on carrier.[embodiment 2]
It is as follows that the used crystallization of filming is synthesized liquid making method: take by weighing 1.2823 gram (30% weight) Ludox, add successively under stirring in the 14.010 gram deionized waters, stirred for several minute one-tenth solution A takes by weighing 0.5313 gram NaOH again, 0.2624 gram NaAlO
2Stir and slowly add in the 13.983 gram deionized waters stirred for several minute one-tenth solution B.
Used α-Al
2O
310 * 1.5 * 20 millimeters of porous ceramic pipe Φ, aperture 4500 nanometers.At room temperature, use 1NHNO
3Solution cleaned sample 1 hour under ultrasonic wave, spend deionised water till be neutrality, and ambient temperature overnight is dried.Again at room temperature, cleaned sample 1 hour with 1N NaOH solution 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 solution A of above-mentioned preparation and pour in the above-mentioned antipriming pipe for 5 milliliters, get solution B again and pour in the stainless steel crystallizing kettle for 5 milliliters, samples vertical is inserted synthesis reactor, the envelope still, room temperature left standstill 48 hours.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, and hydrothermal crystallizing is 72 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.With deionized water washing sample 30 minutes under ultrasonic wave, further wash again to carrier and be neutral.Be warming up to and kept under 120 ℃ 4 hours, be cooled to room temperature again.Repeat above-mentioned film-forming process four times.After the last crystallization operation, be warming up to 450 ℃ of following roastings 4 hours, be cooled to room temperature again.
Forming the initial liquid of mixed preparing gel crystallization with same sial is that above-mentioned porous ceramic pipe is put in aluminium source, sodium source, silicon source simultaneously, by the synthetic X type molecular screen membrane of above-mentioned condition, crystallization operation through six repetitions, the load capacity of record molecular sieve each time and the thickness by the molecular sieve carried layer of electron microscopic observation, table one have provided by above-mentioned two kinds of methods the growth situation of change of carrier weightening finish and film thickness when synthetic.
The comparison of the initial formula of liquid synthesizing molecular sieve film of table one gel state and limpid shape
| The crystallization number of times | The initial liquid of gel state | The initial liquid of limpid shape (the present invention) |
| The carrier gain in weight, % thickness, micron | The carrier gain in weight, % thickness, micron | |
| 1 3 5 7 | 0.27 3 1.38 8 2.06 15 2.73 20 | 0.74 5 1.52 13 2.49 18 |
In the inventive method, load on difficult drop-off in the ultrasonic wave processing of crystallization product after crystallization on the carrier, help the quick growth of molecular sieve layer, thereby quickening film forming speed, realize the molecular sieve cover layer of same thickness and the load capacity of molecular sieve, use method of the present invention, can save drug dosage and can reach 30%～40%.[embodiment 3]
It is as follows that the used crystallization of filming is synthesized liquid making method: take by weighing 0.560 gram (30% weight) Ludox, add successively under stirring in the 18.680 gram deionized waters, stirred for several minute one-tenth solution A takes by weighing 0.1146 gram NaAlO again
2, 1.9622 gram NaOH stir and slowly to add down in the 18.6823 gram deionized waters, stirred for several minute becomes solution B.
Used α-Al
2O
310 * 1.5 * 20 millimeters of porous ceramic pipe Φ, aperture 50 nanometers.At room temperature, cleaned sample 1 hour with 1N HCl solution under ultrasonic wave, spend deionised water till be neutrality, ambient temperature overnight is dried.Again at room temperature, cleaned sample 1 hour with 1N NaOH solution 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 solution A of above-mentioned preparation and pour in the antipriming pipe for 5 milliliters, get solution B again and pour in the stainless steel crystallizing kettle for 5 milliliters, samples vertical is inserted synthesis reactor, the envelope still, room temperature left standstill 48 hours.Crystallizing kettle is moved in the heated oven that has been preheating to 95 ℃, 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.With deionized water washing sample 30 minutes under ultrasonic wave, further wash again to carrier and be neutral.Be warming up to and kept under 120 ℃ 4 hours, be cooled to room temperature again.Repeat above-mentioned film-forming process three times.After the last crystallization operation, be warming up to 450 ℃ of following roastings 4 hours, be cooled to room temperature again.
Carrier inner surface after the crystallization is carried out XRD, SEM characterize, it is X type crystal formation collection of illustrative plates that XRD shows.SEM shows on the inner surface a top layer, and thick about 5～10 microns, also there is molecular sieve to grow up in the carrier duct under the top layer, there is transition zone.The one pack system steam that is used under the normal pressure, 300 ℃ is tested the gas flow of its infiltration by film, collects also cooling, calculates (C
4H
9)
3The permeation flux of N is 1.18 * 10
-7Mole/rice
2. second. handkerchief, and (C
4F
9)
3The permeation flux of N is 2.46 * 10
-9Mole/rice
2. second. handkerchief, select rate to reach 48.Synthermal (C down
4H
9)
3N and (C
4F
9)
3N is 2.84 by the saturating rate of the choosing of earthenware.[embodiment 4]
It is as follows that the used crystallization of filming is synthesized liquid making method: take by weighing 0.5640 gram (30% weight) Ludox, add successively under stirring in the 18.820 gram deionized waters, stirred for several minute one-tenth solution A takes by weighing 0.1154 gram NaAlO again
2, 1.6837 gram NaOH,, stir and slowly to add in the 18.819 gram deionized waters, stirred for several minute becomes solution B.
Used α-Al
2O
310 * 1.5 * 20 millimeters of porous ceramic pipe Φ, aperture 100 nanometers.At room temperature, use 1N HNO
3Solution cleaned sample 1 hour under ultrasonic wave, spend deionised water till be neutrality, and ambient temperature overnight is dried.Again at room temperature, cleaned sample 1 hour with 1N NaOH solution 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.
Molecular sieve crystal seed liquid X1 is by following prescription and condition is synthetic and processing: SiO
2/ Al
2O
3=4.0, Na
2O/SiO
2=1.29, H
2O/SiO
2=60.5,95 ℃ of crystallization temperatures, crystallization time 9 hours; Spend deionised water, be neutral to sample.Dried 3 hours down at 120 ℃, be cooled to room temperature; Take by weighing 0.2562 gram X type molecular sieve powder, join in the 49.7584 gram deionized waters, keep stirring, be suspension to molecular sieve pulp.
Get the X type molecular sieve crystal seed liquid X110 milliliter of above-mentioned preparation and pour in the porous sample cell, in pressurization N2 access tube, maintain under the 345KPa and extracted until liquid in pipe.Use the washed with de-ionized water sample.Repeat aforesaid operations once.Ambient temperature overnight is dried.Be warming up to 180 ℃, kept 2 hours, naturally cool to room temperature.
Get the solution A of above-mentioned preparation and pour in the antipriming pipe for 5 milliliters, get solution B again and pour in the stainless steel crystallizing kettle for 5 milliliters, samples vertical is inserted synthesis reactor, the envelope still, room temperature left standstill 48 hours.Crystallizing kettle is moved in the heated oven that has been preheating to 105 ℃, and hydrothermal crystallizing is 120 hours under self-generating pressure, does not have and stirs.Behind the end of synthesis,, uncap with running water chilling crystallizing kettle.With deionized water washing sample 30 minutes under ultrasonic wave, further wash again to carrier and be neutral.Be warming up to and kept under 120 ℃ 4 hours, be cooled to room temperature again.Repeat above-mentioned film-forming process four times.After the last crystallization operation, be warming up to 450 ℃ of following roastings 4 hours, be cooled to room temperature again.
Inner surface with carrier carries out XRD, SEM sign, and the XRD figure spectrum shows X type molecular sieve crystal formation pattern.The photo of SEM shows on the inner surface has one deck X type molecular sieve layer, about 8～14 microns of surperficial thickness.The one pack system steam that is used under the normal pressure, 300 ℃ is tested the gas flow of its infiltration by film, collects also cooling, calculates (C
4H
9)
3The permeation flux of N is 9.42 * 10
-7Mole/rice
2. second. handkerchief, and (C
4F
9)
3The permeation flux of N is 2.38 * 10
-8Mole/rice
2. second. handkerchief, select rate to reach 39.Synthermal (C down
4H
9)
3N and (C
4F
9)
3N is 2.33 by the saturating rate of the choosing of earthenware.This result and (C
4H
9)
3N and (C
4F
9)
3The traditional absorption behavior of N on X type molecular sieve is consistent, illustrates that the X type molecular screen membrane that forms on porous carrier does not have big defective, and the X type molecular sieve pore passage of zeolite layer is (C
4H
9)
3N and (C
4F
9)
3The main duct that N sees through.
Claims (5)
1, a kind of method for preparing X type molecular screen membrane 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=1.0～12.9, c/b=2～6, d/c=200～1000, it is characterized in that earlier it is in the glass tube or stainless steel tube porous material pipe of 40～10000 dusts that silica gel or Ludox and water wiring solution-forming are placed the aperture, sodium source and aluminium source and water wiring solution-forming are placed outside the porous material pipe, under 50～120 ℃ of reaction temperature conditions, crystallization 36～168 hours, at porous material pipe internal surface crystallization growth X type molecular sieve, wherein before crystallization, preload amorphous aluminosilicate or X type molecular sieve in the porous material pipe, its preload amount is 0.01～0.5% of porous material pipe weight by weight percentage.
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 described method for preparing X type molecular screen membrane 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 described method for preparing X type molecular screen membrane of claim 2.
4, according to the described method for preparing X type molecular screen membrane of claim 1, it is characterized in that with molar ratio computing a/c be 1.2～9.8, c/b is 3～5, d/c is 250～800.
5, according to the described method for preparing X type molecular screen membrane of claim 1, it is characterized in that reaction temperature is 80～105 ℃, crystallization time is 72～120 hours.
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|---|---|---|---|
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|---|---|---|---|
| CN 00111719 CN1112231C (en) | 2000-02-24 | 2000-02-24 | Preparation of x-type molecular sieve film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344352C (en) * | 2005-06-03 | 2007-10-24 | 大连理工大学 | Process for separating mixture of benzene and nitrogen gas by X-type fluorite film |
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|---|---|---|---|---|
| JP6611295B1 (en) * | 2019-05-09 | 2019-11-27 | 株式会社三井Ｅ＆Ｓマシナリー | Method for producing zeolite membrane |
| CN115417424B (en) * | 2022-09-06 | 2023-07-25 | 华东师范大学 | Swelling type silicon-aluminum ECNU-28 molecular sieve precursor and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344352C (en) * | 2005-06-03 | 2007-10-24 | 大连理工大学 | Process for separating mixture of benzene and nitrogen gas by X-type fluorite film |
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