CN1418815A - Method for prepn. of porous material mordenite membrane - Google Patents
Method for prepn. of porous material mordenite membrane Download PDFInfo
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- CN1418815A CN1418815A CN 01132198 CN01132198A CN1418815A CN 1418815 A CN1418815 A CN 1418815A CN 01132198 CN01132198 CN 01132198 CN 01132198 A CN01132198 A CN 01132198A CN 1418815 A CN1418815 A CN 1418815A
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Abstract
The present invention relates to a method for preparing mordenite membrane on porous material, and is characterized by that it adopts the ammonium tetraethyl bromide as template agent, and utilizes thiner crystallization mother liquor to implement synthesis of mordenite membrane on the porous material. It can be used in industrial production of porous material membrane.
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 how lonely L 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.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 to exist stray crystal or molecular screen membrane not fine and close in the document, has a large amount of defectives; And synthetic defect of high cost provides a kind of preparation method of new porous material mordenite membrane.It is low that this method has a synthetic cost, and the synthetic mordenite membrane covers complete, crosslinked well on porous material, 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 preparation method of porous material mordenite membrane, with aluminium source, sodium source, tetraethylammonium bromide, silicon source and water is raw material, and the feed molar composition of reaction system is counted with oxide compound: aNa
2OAl
2O
3BSiO
2CH
2OdTEABr, the span of a is 10～14, the span of b is 10～80, the span of c is 1500～2750, and the span of d is 1～5, and TEABr is a tetraethylammonium bromide, with the aperture is that the porous material of 40～10000 dusts is dipped in the reaction system, raw material is 140～200 ℃ in temperature of reaction, and crystallization time is under 36～168 hours conditions, grows silica alumina ratio and be 10～80 mordenite membrane on porous material.
The preferred version in aluminium source is selected from the aluminium alcoholates of metal aluminum foil, 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 or aluminum isopropylate; 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, silicon sol or positive tetraethyl orthosilicate.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 b is 15～50, and the value preferable range of c is 2000～2500, and the value preferable range of d is 1～3.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 that the present invention describes, is template with the tetraethylammonium bromide of cheapness, the one deck of on porous material, growing evenly, the successive mordenite membrane.The covering of synthetic mordenite membrane is complete, crosslinked well, adhesion strength is high, and does not have the existence of stray crystal, and silica alumina ratio can be regulated in certain scope.Adopt rarer crystallization mother liquor, 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 porous material.
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, Fig. 5 and Fig. 6 are the surface scan electron micrograph of mordenite membrane.
From Fig. 1 a and Fig. 1 b, can find out, because the growing environment basically identical of the collected powdery product in crystallizing kettle bottom and the film of on porous material, growing, so they have similar composition.Compare with the mordenite XRD figure spectrum of standard, they have consistent diffraction peak.On the XRD figure of porous material spectrum, have only the diffraction peak of mordenite, and do not have the diffraction peak of alumina supporter, this explanation is only synthetic through a hydro-thermal, carrier surface just can form one deck continuous, cover mordenite rete completely.Fig. 2 a and Fig. 2 b are powdered products at the bottom of the still
27Al and
29The Si nuclear magnetic resonance spectrum.By
27As seen the Al nuclear magnetic resonance spectrum has sharp-pointed unimodal at the 54ppm place, this is the characteristic resonances peak of four-coordination aluminium atom.By
29The Si nuclear magnetic resonance spectrum as seen-100 (acromions) ,-106 and-there are three resonance peaks 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 crystallization
2O
3The electron scanning micrograph of basement membrane internal surface.From electron micrograph as can be seen, 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.From the section electron micrograph of Fig. 3 as can be seen, synthesize molecular screen membrane and basement membrane mortise in membrane surface, the junction does not have the hole to exist, and the line of delimitation 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 (8)
1, a kind of preparation method of porous material mordenite membrane is a raw material with aluminium source, sodium source, tetraethylammonium bromide, silicon source and water, and the feed molar composition of reaction system is counted with oxide compound: aNa
2OAl
2O
3BSiO
2CH
2OdTEABr, the span of a is 10～14, the span of b is 10～80, the span of c is 1500～2750, and the span of d is 1～5, and TEABr is a tetraethylammonium bromide, with the aperture is that the porous material of 40～10000 dusts is dipped in the reaction system, raw material is 140～200 ℃ in temperature of reaction, and crystallization time is under 36～168 hours conditions, grows silica alumina ratio and be 10～80 mordenite membrane on porous material.
2,, it is characterized in that the aluminium source is selected from the aluminium alcoholates of metal aluminum foil, sodium aluminate, Tai-Ace S 150, pseudo-boehmite, silico-aluminate or 2～4 carbon atoms according to the preparation 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, silicon sol or positive tetraethyl orthosilicate.
3,, it is characterized in that the aluminium source is selected from sodium aluminate or aluminum isopropylate according to the preparation method of the described porous material mordenite membrane of claim 2.
4,, it is characterized in that porous material is selected from pottery, glass or stainless steel according to the preparation method of the described porous material mordenite membrane of claim 1.
5, according to the preparation 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 b is 15～50, and the span of c is 2000～2500, and the span of d is 1～3.
6,, it is characterized in that temperature of reaction is 160～180 ℃ according to the preparation 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 preparation method of the described porous material mordenite membrane of claim 1.
8, according to the preparation 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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|---|---|---|---|
| CN 01132198 CN1418815A (en) | 2001-11-14 | 2001-11-14 | Method for prepn. of porous material mordenite membrane |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519217B (en) * | 2008-02-28 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Preparation method of microcrystal mordenites |
| CN108854946A (en) * | 2018-06-07 | 2018-11-23 | 太原理工大学 | A kind of hierarchical porous structure zeolite absorption/catalyst and its construction method |
-
2001
- 2001-11-14 CN CN 01132198 patent/CN1418815A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519217B (en) * | 2008-02-28 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Preparation method of microcrystal mordenites |
| CN108854946A (en) * | 2018-06-07 | 2018-11-23 | 太原理工大学 | A kind of hierarchical porous structure zeolite absorption/catalyst and its construction method |
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