CN1418814A - Porous material mordenite membrane - Google Patents
Porous material mordenite membrane Download PDFInfo
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- CN1418814A CN1418814A CN 01132197 CN01132197A CN1418814A CN 1418814 A CN1418814 A CN 1418814A CN 01132197 CN01132197 CN 01132197 CN 01132197 A CN01132197 A CN 01132197A CN 1418814 A CN1418814 A CN 1418814A
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- membrane
- mordenite
- porous material
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Abstract
The present invention uses ammonium tetraethyl bromide as temptate agent, and utilizes the thiner crystallizatino mother liquor to in-situ grow mordenite membrane on the porous material whose pore size is 40-10000 dngstrom, and can make the thickness of mordenite membrane be up to 10-50 micrometers. Said invention can be used in industrial production.
Description
Technical field
The present invention relates to the porous material mordenite membrane, particularly the composite inorganic film that forms about 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, oneself is widely used in fractionation by adsorption and heterogeneous catalytic reaction.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 one 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 one 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,
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.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, the synthetic mordenite membrane exists stray crystal or molecular screen membrane not fine and close, has the problem of a large amount of defectives.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist the synthetic mordenite membrane to exist stray crystal or molecular screen membrane not fine and close in the document, has the problem of a large amount of defectives, and a kind of new porous material mordenite membrane is provided.It is complete, crosslinked good that this mordenite membrane has covering, and do not have the characteristics of stray crystal.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of porous material mordenite membrane, comprise that the aperture is the porous material of 40～10000 dusts, silica alumina ratio is arranged is 10～80 mordenite membrane in growth on porous material surface, the thickness of mordenite membrane is 10～50 microns, and the mordenite grain size is 20～30 microns.
The porous material preferred version is for being selected from pottery, glass or stainless steel in the technique scheme, and the silica alumina ratio preferable range of mordenite is 15～50, and the thickness preferable range of mordenite membrane is 30～40 microns.
The preparation method of porous material mordenite membrane of the present invention is that the tetraethylammonium bromide with cheapness is a template, adopts rarer crystallization mother liquor, and by the crystallization operation, growth in situ forms mordenite membrane on porous material carrier.Wherein porous material carrier is selected from pottery, glass or stainless steel, and the aperture of porous material carrier is 40～10000 dusts.System film crystallization liquid mole consists of: ANa
2O: 1.0Al
2O
3: BSiO
2: CH
2O: DTEABr, wherein, A is 10.0～14.0, best 11.0～13.0; B is 10.0～80, best 15.0～50.0; C is 1500.0～2750.0, best 2000.0～2500.0; D is 1.0～5.0, best 1.0～3.0.140～200 ℃ of crystallization temperatures, best 160～180 ℃; Crystallization time is 36～168 hours, best 72～120 hours.
The porous material mordenite membrane that makes among the present invention evenly, continuously, thickness reaches 10～50 microns, carrier internal surface after the crystallization is carried out XRD, SEM to be characterized, XRD characterizes and shows that the synthetic porous material membrane is the mordenite crystal formation, and there is not the existence of stray crystal, it is complete, crosslinked good that the SEM photo shows that zeolite membrane covers, and obtained better technical effect.
Description of drawings
Fig. 1 a and Fig. 1 b be respectively in the building-up process of the present invention after collected powdery product in crystallizing kettle bottom and the crystallization XRD figure spectrum of film on the porous material.
Fig. 2 a and Fig. 2 b are respectively powdered products at the bottom of the still in the building-up process of the present invention
27Al and
29The Si nuclear magnetic resonance spectrum.
Fig. 3 is mordenite membrane (a): section and (b): the surface scan electron micrograph.
Fig. 4, Fig. 5 and Fig. 6 are the surface scan electron micrograph of mordenite membrane.
Can find out that from Fig. 1 a and Fig. 1 b because the growing environment of the collected powdery product in crystallizing kettle bottom and the film of growing at porous material is basically identical, so they have similar composition. Compare with the modenite XRD collection of illustrative plates of standard, they have consistent diffraction maximum. On the XRD of porous material 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 test has obtained 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, have in membrane surface cover complete, crosslinked good, homogeneous grain size, more smooth molecular screen membrane forms, the zeolite 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.
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: 1.5TEABr.Take by weighing 10.13 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 25.89 ml deionized water; Take by weighing 0.310 gram sodium aluminate, 0.275 gram tetraethylammonium bromide, add above-mentioned solution successively, stirred 30 minutes; Get 3.98 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 40 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 (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: 1.5Al
2O
3: 40SiO
2: 2500H
2O: 1.5TEABr.Get 10.11 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 24.90 ml deionized water; Take by weighing 0.160 gram PURAL200,0.275 gram tetraethylammonium bromide, add above-mentioned solution successively, stirred 4 hours; Get 3.99 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 350 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 40 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.It is complete, crosslinked good that the SEM photo shows that zeolite membrane covers, and sees 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: 1.0Al
2O
3: 40SiO
2: 2500H
2O: 1.5TEABr.Take by weighing 10.11 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 24.91 ml deionized water; Take by weighing 0.540 gram aluminum isopropylate, 0.275 gram tetraethylammonium bromide, add above-mentioned solution successively, stirred 4 hours; Get 3.99 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 250 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 40 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.It is complete, crosslinked good that the SEM photo shows that zeolite membrane covers, and sees Fig. 5.[embodiment 4]
The compound method of crystallization mother liquor is as follows: the mole of crystallization mother liquor consists of: 11.4Na
2O: 0.75Al
2O
3: 30SiO
2: 2500H
2O: 1.5TEABr.Take by weighing 9.21 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 25.54 ml deionized water; Take by weighing 0.138 gram sodium aluminate, 0.244 gram tetraethylammonium bromide, add above-mentioned solution successively, stirred 30 minutes; Get 5.25 milliliters of tetraethoxys, under violent stirring, dropwise add, stirred 4 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 500 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 40 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.It is complete, crosslinked good that the SEM photo shows that zeolite membrane covers, and sees Fig. 6.[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: 1.5TEABr.Take by weighing 10.13 milliliters of sodium hydroxide solutions (1.7913 mol), mix, stirred 5 minutes with 25.89 ml deionized water; Take by weighing 0.310 gram sodium aluminate, 0.275 gram tetraethylammonium bromide, add above-mentioned solution successively, stirred 30 minutes; Get 3.98 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 800 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.
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 temperature rise rate again.
The rate of permeation of table 1 single-component gas (298K)
| Gas permeability (10 -7Mole rice -2Second -1Handkerchief -1) | Separation selectivity | |||
| Gas | ????N 2 | ????Ar | ????H 2 | ??H 2/N 2 |
| Rate of permeation | ????1.81 | ????1.79 | ????6.92 | ??3.82 |
By table 1 as seen, the H of mordenite membrane
2/ N
2The desired separated ratio is 3.82, and greater than exerting gloomy selectivity (3.74), this illustrates that this mordenite membrane has the molecule sieve performance.
Claims (4)
1, a kind of porous material mordenite membrane, comprise that the aperture is the porous material of 40～10000 dusts, silica alumina ratio is arranged is 10～80 mordenite membrane in growth on porous material surface, and the thickness of mordenite membrane is 10～50 microns, and the mordenite grain size is 20～30 microns.
2,, it is characterized in that porous material is pottery, glass or stainless steel according to the described porous material mordenite membrane of claim 1.
3, according to the described porous material mordenite membrane of claim 1, the silica alumina ratio that it is characterized in that mordenite is 15～50.
4, according to the described porous material mordenite membrane of claim 1, the thickness that it is characterized in that mordenite membrane is 30～40 microns.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01132197 CN1418814A (en) | 2001-11-14 | 2001-11-14 | Porous material mordenite membrane |
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|---|---|---|---|
| CN 01132197 CN1418814A (en) | 2001-11-14 | 2001-11-14 | Porous material mordenite membrane |
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|---|---|
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ID=4671235
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519316B (en) * | 2009-04-15 | 2012-07-25 | 北京师范大学 | Novel foam zeolite granule and preparation method thereof |
| CN103541031A (en) * | 2013-10-30 | 2014-01-29 | 苏州龙杰特种纤维股份有限公司 | Production process for textile filaments |
| CN104477935A (en) * | 2014-11-21 | 2015-04-01 | 常州大学 | Method for preparing hybrid porous molecular sieve by virtue of salt particle template method |
-
2001
- 2001-11-14 CN CN 01132197 patent/CN1418814A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519316B (en) * | 2009-04-15 | 2012-07-25 | 北京师范大学 | Novel foam zeolite granule and preparation method thereof |
| CN103541031A (en) * | 2013-10-30 | 2014-01-29 | 苏州龙杰特种纤维股份有限公司 | Production process for textile filaments |
| CN104477935A (en) * | 2014-11-21 | 2015-04-01 | 常州大学 | Method for preparing hybrid porous molecular sieve by virtue of salt particle template method |
| CN104477935B (en) * | 2014-11-21 | 2016-08-24 | 常州大学 | The method that salt particulate templates method prepares hydridization duct molecular sieve |
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