CN1500730A - Method for synthesizing porous material mordenite membrane - Google Patents
Method for synthesizing porous material mordenite membrane Download PDFInfo
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- CN1500730A CN1500730A CNA02145230XA CN02145230A CN1500730A CN 1500730 A CN1500730 A CN 1500730A CN A02145230X A CNA02145230X A CN A02145230XA CN 02145230 A CN02145230 A CN 02145230A CN 1500730 A CN1500730 A CN 1500730A
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Abstract
The present invention relates to the synthesis process of porous flokite film material and solves the problems in the preparation process, including high preparation cost of flokite film, and loose structure of flokite film with great amount of pores, cracks and other faults. The technological scheme of the present invention is that flokite film is synthesized directly on porous material by using relatively dilute crystallization mother liquid and no template agent. The present invention may be used in industrial process of preparing porous flokite film.
Description
Technical field
The present invention relates to the preparation method of porous material mordenite membrane, particularly form the method for composite inorganic film about preparation loaded mordenite on porous material.
Background technology
Mordenite has the oval duct that is parallel to each other, and its aperture is 6.95 * 5.81 , and structure cell consists of Na
8[(AlO
2)
8(SiO
2) 40] 24H
2O.Owing to have high thermostability and superior acid resistance, it has become important commercial catalysts and sorbent material.Mordenite is made film, and it all has application prospect in fields such as gas delivery, film catalysis.
The zeolite molecular sieve of synthetic gained all is granular powder at present, and its size is determined by crystallization operating parameterss such as crystallization liquid concentration, crystallization times.Since the molecular sieve bore diameter homogeneous and have the height shape selectivity, in fractionation by adsorption and heterogeneous catalytic reaction, be widely used.But the two unites separation that molecular sieve is had and response function, utilize porous material do carrier with zeolite synthesis 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 katalysis 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 weighting agent 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 sepn process-process of pervaporation always; Gas phase separation process at comparatively high temps 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 mineral membrane again, this has become the focus and the difficult point of people's researchs.
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 process 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.
WO93 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.Synthetic ZSM-5 zeolite membrane in this way, to, paraxylene, tri-isopropyl benzene mixed system have the selection osmosis.
Document US P4699892 utilizes porous support 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 silico-aluminate colloidal sol mole
2O/SiO
2: 50～120, Na
2O/SiO
2: 0.5～2, SiO
2/ Al
2O
3: 5～15, porous support 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-hexanaphthene has separating power.
People such as Masahiko (JP93-259166) are coated in gel on the porous support, after the drying, are exposed to again in the steam of organic amine and water, and the vapour phase crystallization, and use it for gas delivery.Human vapour phase processes (VPT) such as Nishiyama have made mordenite membrane on the aluminum oxide video disc, but obviously are unsound with the molecular screen membrane that this method makes, and can observe the existence of a large amount of defectives.People such as Piera adopt hydrothermal synthesis method to make mordenite membrane on alumina tube, but have a large amount of ZSM-5 and Chabazite stray crystal to exist, and use expensive tetraethyl ammonium hydroxide to do template.
In sum, shorter mention mordenite molecular sieve film forming situation on the inorganic porous material carrier in the above-mentioned document, and in a spot of report, owing to use template, molecular sieve is after roasting more than 500 ℃, the synthetic mordenite membrane is not fine and close, has the problem of a large amount of defectives such as sharp neck hole, crackle.And the tetraethyl ammonium hydroxide template of using in the building-up process costs an arm and a leg, and makes synthetic cost very high.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist the synthetic mordenite membrane not fine and close in the document, has a large amount of defectives such as sharp neck hole, crackle, and synthetic defect of high cost, and a kind of synthetic method of new porous material mordenite membrane is provided.It is low that this method has a synthetic cost, and the synthetic mordenite membrane on porous material, cover complete, crosslinked good, and low characteristics of synthetic cost.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of synthetic method of porous material mordenite membrane is a raw material with aluminium source, sodium source, silicon source and water, and the feed molar composition of reaction system is counted with oxide compound: aNa
2ObAl
2O
3CSiO
2DH
2O, the span of a is 10～14, the span of b is 1～2, the span of c is 10～80, and the span of d is 2000～2750, is that the porous material of 40～10000 dusts is dipped in the reaction system with the aperture, raw material is 140～200 ℃ in temperature of reaction, crystallization time is under 36～168 hours conditions, grows silica alumina ratio and be 10～80 mordenite membrane on porous material, and wherein porous material cleaned under ultrasonic wave with bronsted lowry acids and bases bronsted lowry solution respectively before use.
The preferred version in aluminium source is selected from the aluminium alcoholates of sodium aluminate, Tai-Ace S 150, pseudo-boehmite, silico-aluminate or 2～4 carbon atoms in the technique scheme, and more preferably scheme is for being selected from sodium aluminate; Sodium source preferred version for being selected from sodium aluminate or/and sodium hydroxide; Silicon source preferred version is for being selected from silica gel, silicate, silicon sol or positive tetraethyl orthosilicate, and preferred version is for being selected from silicon sol.The porous material preferred version is selected from pottery, glass or stainless steel.The value preferable range of a is 11～13, and the value preferable range of c is 15～50, and the value preferable range of d is 2000～2500.The temperature of reaction preferable range is 160～180 ℃, and the crystallization time preferable range is 72～120 hours, and the silica alumina ratio preferable range of mordenite membrane is 15～50.
Adopting the novel method of the preparation mordenite membrane of the present invention's description, is raw material with silicon source, aluminium source, sodium source and water, and without template, growing on porous material, one deck is even, the successive mordenite membrane.The covering of synthetic mordenite membrane is complete, crosslinked well, adhesion strength is high.Adopt rarer crystallization mother liquor and do not use template, can reduce synthetic cost widely, help its industrial application.Mordenite membrane has wide application prospect in gas delivery, membrane reactor field, has obtained better technical effect.
Description of drawings
Fig. 1 a and Fig. 1 b be respectively in the preparation process of the present invention after collected powdery product in crystallizing kettle bottom and the crystallization XRD figure spectrum of film on the ceramic video disc.
Fig. 2 a and Fig. 2 b are respectively powdered products at the bottom of the still in the preparation process of the present invention
27Al and
29The Si nuclear magnetic resonance spectrum.
Fig. 3 a and Fig. 3 b are respectively the section and the surface scan electron micrographs of mordenite membrane.
Fig. 4 is the surface scan electron micrograph of mordenite membrane.
Adopt mother liquor to consist of 11.4Na2O∶1.5Al
2O
3∶40SiO
2∶2500H
2The crystallization mother liquor of O 170 ℃ of lower crystallization 3 days, characterizes the powder at the bottom of prepared film pipe and the still. Fig. 1 a and Fig. 1 b are respectively the XRD collection of illustrative plates of film on the ceramic video disc after the collected powdery product in crystallizing kettle bottom and the crystallization, and the build environment of these powder is basically identical with the product that is attached to earthenware, thereby they should have similar composition. Compare with the modenite XRD collection of illustrative plates of standard, as seen they have consistent diffraction maximum. On the XRD of ceramic video disc collection of illustrative plates, only have the diffraction maximum of modenite, and do not have the diffraction maximum of alumina support, this explanation is only through a Hydrothermal Synthesis, carrier surface just can form one deck continuous, cover completely modenite rete. Fig. 2 a and Fig. 2 b are powdered products at the bottom of the still27Al and29The Si nuclear magnetic resoance spectrum. By27As seen the Al nuclear magnetic resoance spectrum has sharp-pointed unimodal at the 54ppm place, this is the characteristic resonances peak of four-coordination aluminium atom. By29The Si nuclear magnetic resoance spectrum as seen-100 (acromions) ,-106 and-there are three formants at the 112ppm place, this corresponds respectively to Si (2Al), Si (1Al) and Si (0Al). This shows that synthetic result is mordenite membrane.
Fig. 3 is the α-Al after a crystallization2O
3The electron scanning micrograph of basement membrane inner surface. Can find out from electron micrograph, membrane surface have cover complete, crosslinked good, crystal size evenly, more smooth molecular screen membrane forms, the molecular sieve crystal size is about 20～30 microns. Can find out from the section electron micrograph of Fig. 3, synthesize molecular screen membrane and basement membrane strong bonded in membrane surface, the junction does not have the hole to exist, and the line of demarcation of molecular sieve rete and basement membrane is very clear, and thickness is about 30～40 microns.
In molecular screen membrane synthetic, usually to add organic amine as template, this accounts for a sizable part in synthetic cost, also bring larger pressure to wastewater treatment; Crystallization mother liquor also often adopts denseer proportioning (forming similar with the mother liquor of preparation molecular sieve), has both caused a large amount of wastes of raw material, again because the deposition of the molecular sieve crystal that forms in the mother liquor, so that the adhesive strength of molecular screen membrane is lower. Adopt the method for this patent, can avoid the use of organic amine, and use the fully crystallization mother liquor of dilution, can greatly reduce synthetic cost, the adhesive strength of the mordenite membrane that makes is also very high. Can avoid removing the high-temperature calcination process of template without the template synthetic method, thereby the as much as possible generation of reduce injection defect is conducive to improve its infiltration, separating property. In addition, do not use organic amine to do template, can reduce the discharging of noxious material yet, be conducive to environmental protection.
Result of study shows, improving one's methods of the preparation modenite that the employing this patent is described, need not add template, even, the continuous mordenite membrane of one deck of on porous ceramic pipe, growing, than patent (Chinese patent application number 011321970,011321989), preparation cost is cheap, operate easier, and the film forming post-processing step reduces, and need not high-temperature heat treatment, is expected industrialization and reaches the purpose of falling energy synergy.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
The compound method of crystallization mother liquor is as follows: the mole of crystallization mother liquor consists of: 11.4Na
2O: 1.5Al
2O
3: 40SiO
2: 2500H
2O.Get 20.26 milliliters of sodium hydroxide solutions (1.7913M), mix, stirred 5 minutes with 51.98 ml deionized water; Take by weighing 0.620 gram sodium aluminate, add above-mentioned solution, stirred 30 minutes; Get 7.96 milliliters of silicon sol, under violent stirring, dropwise add, stirred 2 hours, obtain crystallization mother liquor.
Used α-Al
2O
312 millimeters * 250 millimeters * 2 millimeters of porous ceramic pipe φ, internal surface top layer aperture is about 150 nanometers.Be cut to the segment of about 1 cm long.At room temperature, cleaned 1 hour under ultrasonic wave with 5% hydrochloric acid and 5% sodium hydroxide solution successively, to neutral, placed the 383K baking oven dry 24 hours with deionized water wash, it is standby to put into the moisture eliminator cooling.
Get 60 milliliters of the crystallization mother liquors of above-mentioned configuration, pour in the stainless steel crystallizing kettle.Get above-mentioned standby alumina ceramic tube, with its vertical fixing in crystallizing kettle.Crystallizing kettle is put into to be preheating to the baking oven of 443K, and hydrothermal crystallizing is 72 hours under self-generating pressure, does not have and stirs.Crystallization is cooled off crystallizing kettle with tap water after finishing, and drives still, and is extremely neutral with the washed with de-ionized water support tube.This support tube is placed the wave beam central authorities of ultrasonic washing instrument, and ultrasonic cleaning 30 minutes is taken out, and places the 383K baking oven dry 24 hours.
Carrier internal surface after the crystallization is carried out XRD, SEM to be characterized.It is the collection of illustrative plates of mordenite crystal formation that XRD shows, and does not have the (see figure 1) that exists of stray crystal.It is complete, crosslinked good that the SEM photo shows that zeolite membrane covers, and the thickness of film is about 30 microns (see figure 3)s.
[embodiment 2]
The compound method of crystallization mother liquor is as follows: the mole of crystallization mother liquor consists of: 11.4Na
2O: 2.0Al
2O
3: 60SiO
2: 2600H
2O.Get 16.62 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 52.58 ml deionized water; Take by weighing 0.748 gram and add above-mentioned solution, stirred 4 hours; Get 7.98 milliliters of silicon sol, under violent stirring, dropwise add, stirred 2 hours, obtain crystallization mother liquor.
Used α-Al
2O
312 millimeters * 250 millimeters * 2 millimeters of porous ceramic pipe φ, internal surface top layer aperture is 150 nanometers.Be cut to the segment of about 1 cm long.At room temperature, cleaned 1 hour under ultrasonic wave with 5% hydrochloric acid and 5% sodium hydroxide solution successively, to neutral, placed the 383K baking oven dry 24 hours with deionized water wash, it is standby to put into the moisture eliminator cooling.
Get 60 milliliters of the crystallization mother liquors of above-mentioned preparation, pour in the stainless steel crystallizing kettle.Get above-mentioned standby alumina ceramic tube, with its vertical fixing in crystallizing kettle.Crystallizing kettle is put into the baking oven that is preheating to 443K, and hydrothermal crystallizing is 72 hours under autogenous pressure, does not have and stirs.Crystallization is cooled off crystallizing kettle with tap water after finishing, and drives still, and is extremely neutral with the washed with de-ionized water support tube.This support tube is placed the wave beam central authorities of ultrasonic washing instrument, and ultrasonic cleaning 30 minutes is taken out, and places the 383K baking oven dry.
Carrier internal surface after the crystallization is carried out XRD, SEM to be characterized.It is the collection of illustrative plates of mordenite crystal formation that XRD shows, and does not have the existence of stray crystal.The SEM photo shows that zeolite membrane covers complete, crosslinked good (Fig. 4).
[embodiment 3]
The compound method of crystallization mother liquor is as follows: the mole of crystallization mother liquor consists of: 11.4Na
2O: 1.5Al
2O
3: 40SiO
2: 2500H
2O: 1.5TEABr.Get 20.26 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 52.89 ml deionized water; Take by weighing 0.620 the gram sodium aluminate and 0.55 the gram tetraethylammonium bromide add above-mentioned solution, stirred 30 minutes; Get 7.96 milliliters of silicon sol, under violent stirring, dropwise add, stirred 2 hours, obtain crystallization mother liquor.
Used α-Al
2O
312 millimeters * 250 millimeters * 2 millimeters of porous ceramic pipe φ, internal surface top layer aperture is 150 nanometers.Be cut to the segment of about 1 cm long.At room temperature, cleaned 1 hour under ultrasonic wave with 5% hydrochloric acid and 5% sodium hydroxide solution successively, to neutral, placed the 383K baking oven dry 24 hours with deionized water wash, it is standby to put into the moisture eliminator cooling.
Get 60 milliliters of the crystallization mother liquors of above-mentioned preparation, pour in the stainless steel crystallizing kettle.Get above-mentioned standby alumina ceramic tube, with its vertical fixing in crystallizing kettle.Crystallizing kettle is put into the baking oven that is preheating to 443K, and hydrothermal crystallizing is 72 hours under autogenous pressure, does not have and stirs.Crystallization is cooled off crystallizing kettle with tap water after finishing, and drives still, and is extremely neutral with the washed with de-ionized water support tube.This support tube is placed the wave beam central authorities of ultrasonic washing instrument, and ultrasonic cleaning 30 minutes is taken out, and places the 383K baking oven dry.Repeat above crystallization steps 4 times.
Through check, the mordenite membrane after the crystallization is airtight before roasting, and this explanation institute synthetic mordenite membrane is flawless before roasting.Above-mentioned vitrified pipe is heated to 350 ℃, constant temperature 4 hours with 1 ℃/minute temperature rise rate; Be heated to 500 ℃, constant temperature 8 hours with 0.2 ℃/minute temperature rise rate again; Cool to room temperature with 1.0 ℃/minute speed again.
Shown that by table 1 tetraethylammonium bromide does the rate of permeation that template is come the single-component gas of synthesizing flokite film, its H
2/ N
2The desired separated ratio is 3.82.
The rate of permeation of table 1 single-component gas (298K)
| Gas permeability (10 -7mol·m -2·s -1·Pa -1) | Separation selectivity | |||
| Gas | ????N 2 | ?????Ar | ????H 2 | ????H 2/N 2 |
| Rate of permeation | ????1.81 | ?????1.79 | ????6.92 | ????3.82 |
[embodiment 4]
The compound method of crystallization mother liquor is as follows: the mole of crystallization mother liquor consists of: 11.4Na
2O: 1.5Al
2O
3: 30SiO
2: 2500H
2O.Get 20.26 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 51.98 ml deionized water; Take by weighing 0.620 gram sodium aluminate and add above-mentioned solution, stirred 30 minutes; Get 7.96 milliliters of silicon sol, under violent stirring, dropwise add, stirred 2 hours, obtain crystallization mother liquor.
Used α-Al
2O
312 millimeters * 250 millimeters * 2 millimeters of porous ceramic pipe φ, internal surface top layer aperture is 150 nanometers.Be cut to the segment of about 2 cm long.At room temperature, cleaned 1 hour under ultrasonic wave with 5% hydrochloric acid and 5% sodium hydroxide solution successively, to neutral, placed the 383K baking oven dry 24 hours with deionized water wash, it is standby to put into the moisture eliminator cooling.
Get 60 milliliters of the crystallization mother liquors of above-mentioned preparation, pour in the stainless steel crystallizing kettle.Get above-mentioned standby alumina ceramic tube, with its vertical fixing in crystallizing kettle.Crystallizing kettle is put into the baking oven that is preheating to 443K, and hydrothermal crystallizing is 72 hours under autogenous pressure, does not have and stirs.Crystallization is cooled off crystallizing kettle with tap water after finishing, and drives still, and is extremely neutral with the washed with de-ionized water support tube.This support tube is placed the wave beam central authorities of ultrasonic washing instrument, and ultrasonic cleaning 30 minutes is taken out, and places the 383K baking oven dry.Repeat above crystallization steps 4 times.
Above-mentioned vitrified pipe is heated to 110 ℃ with 1 ℃/minute temperature rise rate, and constant temperature 24 hours is cooled to room temperature with 1 ℃/minute speed again.
Table 2 has shown the permeability data of the single-component gas of the film that does not carry out high-temperature heat treatment, shows that film is to H
2/ N
2Separation selectivity can reach 6.04, suitable with embodiment 3 results.
The rate of permeation of table 2 single-component gas (298K)
| Gas permeability (10 -7mol·m -2·s -1·Pa -1) | Separation selectivity | |||
| ????N 2 | ????Ar | ????H 2 | ????H 2/N 2 | |
| The film pipe | ????1.01 | ????1.00 | ????6.13 | ????6.04 |
[embodiment 5]
The compound method of crystallization mother liquor is as follows: the mole of crystallization mother liquor consists of: 11.4Na
2O: 1.5Al
2O
3: 40SiO
2: 2500H
2O.Take by weighing 20.26 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 51.98 ml deionized water; Take by weighing 0.620 gram sodium aluminate and add above-mentioned solution, stirred 30 minutes; Get 7.96 milliliters of silicon sol, under violent stirring, dropwise add, stirred 2 hours, obtain crystallization mother liquor.
Used α-Al
2O
312 millimeters * 250 millimeters * 2 millimeters of porous ceramic pipe φ, internal surface top layer aperture is 150 nanometers.Be cut to the segment of about 2 cm long.At room temperature, cleaned 1 hour under ultrasonic wave with 5% hydrochloric acid and 5% sodium hydroxide solution successively, to neutral, placed the 383K baking oven dry 24 hours with deionized water wash, it is standby to put into the moisture eliminator cooling.
Get 50 milliliters of the crystallization mother liquors of above-mentioned preparation, pour in the stainless steel crystallizing kettle.Get above-mentioned standby alumina ceramic tube, with its vertical fixing in crystallizing kettle.Crystallizing kettle is put into the baking oven that is preheating to 443K, and hydrothermal crystallizing is 72 hours under autogenous pressure, does not have and stirs.Crystallization is cooled off crystallizing kettle with tap water after finishing, and drives still, and is extremely neutral with the washed with de-ionized water support tube.This support tube is placed the wave beam central authorities of ultrasonic washing instrument, and ultrasonic cleaning 30 minutes is taken out, and places the 383K baking oven dry.Repeat above crystallization steps 4 times.
Above-mentioned vitrified pipe is heated to 350 ℃, constant temperature 4 hours with 1 ℃/minute temperature rise rate; Be heated to 500 ℃, constant temperature 8 hours with 0.2 ℃/minute temperature rise rate again; Cool to room temperature with 1.0 ℃/minute speed again.
Table 3 has shown the permeability data of the single-component gas of the film that carries out high-temperature heat treatment, shows that film is to H
2/ N
2Separation selectivity compare with embodiment 4 slightly and to descend, but still suitable with embodiment 3 results.
The rate of permeation of table 3 single-component gas (298K)
| Gas permeability (10 -7mol·m -2·s -1·Pa -1) | Separation selectivity | |||
| ????N 2 | ????Ar | ????H 2 | ????H 2/N 2 | |
| The film pipe | ????1.52 | ????1.47 | ????7.24 | ????4.76 |
Claims (8)
1, a kind of synthetic method of porous material mordenite membrane is a raw material with aluminium source, sodium source, silicon source and water, and the feed molar composition of reaction system is counted with oxide compound: aNa
2ObAl
2O
3CSiO
2DH
2O, the span of a is 10～14, the span of b is 1～2, the span of c is 10～80, and the span of d is 2000～2750, is that the porous material of 40～10000 dusts is dipped in the reaction system with the aperture, raw material is 140～200 ℃ in temperature of reaction, crystallization time is under 36～168 hours conditions, grows silica alumina ratio and be 10～80 mordenite membrane on porous material, and wherein porous material cleaned under ultrasonic wave with bronsted lowry acids and bases bronsted lowry solution respectively before use.
2,, it is characterized in that the aluminium source is selected from the aluminium alcoholates of sodium aluminate, Tai-Ace S 150, pseudo-boehmite, silico-aluminate or 2～4 carbon atoms according to the synthetic method of the described porous material mordenite membrane of claim 1; The sodium source is selected from sodium aluminate or/and sodium hydroxide, and the silicon source is selected from silica gel, silicate, silicon sol or positive tetraethyl orthosilicate.
3, according to the synthetic method of the described porous material mordenite membrane of claim 2, it is characterized in that the aluminium source is selected from sodium aluminate, the silicon source is selected from silicon sol.
4,, it is characterized in that porous material is selected from pottery, glass or stainless steel according to the synthetic method of the described porous material mordenite membrane of claim 1.
5, according to the synthetic method of the described molecular sieve film of porous material of claim 1, the span that it is characterized in that a is 11～13, and the span of c is 15～50, and the span of d is 2000～2500.
6,, it is characterized in that temperature of reaction is 160～180 ℃ according to the synthetic method of the described porous material mordenite membrane of claim 1.
7,, it is characterized in that crystallization time is 72～120 hours according to the synthetic method of the described porous material mordenite membrane of claim 1.
8, according to the synthetic method of the described porous material mordenite membrane of claim 1, the silica alumina ratio that it is characterized in that mordenite membrane is 15～50.
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|---|---|---|---|
| CNA02145230XA CN1500730A (en) | 2002-11-13 | 2002-11-13 | Method for synthesizing porous material mordenite membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA02145230XA CN1500730A (en) | 2002-11-13 | 2002-11-13 | Method for synthesizing porous material mordenite membrane |
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ID=34232325
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514024B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | Beta zeolite /Magadiite/mordenite coexisting material and method for synthesizing same |
| CN105366689A (en) * | 2015-11-14 | 2016-03-02 | 大连理工大学 | Microwave-assisted method for synthesizing MOR zeolite molecular sieve membrane for dilute solution |
-
2002
- 2002-11-13 CN CNA02145230XA patent/CN1500730A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514024B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | Beta zeolite /Magadiite/mordenite coexisting material and method for synthesizing same |
| CN105366689A (en) * | 2015-11-14 | 2016-03-02 | 大连理工大学 | Microwave-assisted method for synthesizing MOR zeolite molecular sieve membrane for dilute solution |
| CN105366689B (en) * | 2015-11-14 | 2018-11-13 | 大连理工大学 | A kind of method of weak solution Microwave-assisted synthesis MOR zeolite molecular sieve films |
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