CN1061900C - SAPO-34/ceramic composite separation film and preparation thereof - Google Patents
SAPO-34/ceramic composite separation film and preparation thereof Download PDFInfo
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- CN1061900C CN1061900C CN96106353A CN96106353A CN1061900C CN 1061900 C CN1061900 C CN 1061900C CN 96106353 A CN96106353 A CN 96106353A CN 96106353 A CN96106353 A CN 96106353A CN 1061900 C CN1061900 C CN 1061900C
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- molecular sieve
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Abstract
The present invention relates to a molecular sieve / ceramic composite separation membrane and a preparation method thereof. The composite separation membrane is composed of a flat plate porous ceramic base material and a thin layer of an SAPO-34 molecular sieve which is homogeneously, firmly and densely compounded on one surface of the base material. The SAPO-34 molecular sieves in the thin layer of the molecular sieve are mutually and densely connected into an integral whole, and except structural holes of the molecular sieve, other bigger intercrystalline holes do not exist. The composite separation membrane not only can be used as a membrane separation element but also can be used in a membrane catalytic reactor.
Description
The present invention relates to molecular sieve/ceramic composite separation film, the specifically compound and diffusion barrier that obtains by SAPO-34 molecular sieve and ceramic base material.
Inoranic membrane has characteristics such as high temperature resistant, anticorrosive, all obviously is better than organic film at aspects such as structure, heat and chemical stabilities, thereby becomes the hot topic that recent two decades comes the research of membrane science technical field.But up to the present, the average pore size of most of inoranic membrane of bibliographical information is more than about 30 dusts, and the pore size distribution broad, is used for being mainly when gas separates the gloomy diffusion of promise.Be difficult to the gas molecule that molecular weight is approaching or identical separately with the gloomy film that is diffused as separating mechanism of promise, and the film that is divided into separating mechanism with molecular sieve also has higher separation selectivity for the approaching gas of molecular size, and therefore needing a kind of aperture of exploitation is molecular level (less than 8 dusts) and the uniform inoranic membrane of pore size distribution.
Although the purposes of molecular sieve is more and more wider, with regard to its commercial Application form, be still based on particle, up to the present, its field that is most widely used is adsorbing separation and catalysis.Molecular sieve had both had good molecule sieve performance, can be used as the good catalyst of some reaction again, if molecular sieve is made inorganic separating film, both can be used for film separately and separate and obtain high separation selectivity, can be used for again in the catalytic film reactor and improve reaction efficiency.
The patent of film has appearred zeolite molecular sieve is made in early eighties.For example described a kind of method of synthetic self-supporting ZSM-5 zeolite membrane among USP5019263 and the USP5069794, but self-supporting film strength and compactness are difficult to guarantee.
The method that Suzuki etc. describe in JP83-125155 and USP 4699892 is that silica-alumina gel is poured over porous stainless steel, nickel porous, fine and close nickel alumin(i)um alloy and porous VYCOK7930 glass surface, it is synthetic to put into airtight container again, has made the A type zeolite membrane of thickness from tens dusts to the hundreds of dust.The another kind of method of propositions such as Suzuki is that the solution that will contain ultra micro zeolite (as ZSM-5, Silicalite, A type etc.) particle sees through porous substrate under certain pressure, thereby zeolite granular is filled in the duct of porous substrate, in solution, put into silicon source, aluminium source, template agent and water again, under certain temperature and stirring condition, made ZSM-5, Silicalite, A type zeolite membrane (EP 180200A1).But there is report (EP 481660A1) that two kinds of methods more than the Suzuki are queried, points out to adopt these two kinds of methods can not obtain the alleged zeolite membrane of Suzuki.The method that Miyazaki etc. provide (JP60-129119) be earlier with 4A zeolite powder and bentonite and water at 10Kg/cm
2Be pressed in Al under the pressure
2O
3On the thin plate, again this thin plate is put into the aqueous solution of waterglass and alkali, obtained A type zeolite membrane in 120 ℃ of crystallization.
Described a kind of synthetic film that has zeolite crystal among the EP0511739A1, its preparation process comprises: (1) preparation aperture is approximately the porous substrate of 0.1～3 μ m, Al wherein
2O
3Content is at least 90%; (2) at least one surface of this base material is immersed in the slurries of being formed by zeolite crystal and its precursor (making) by silicon source such as sodium metasilicate or waterglass; (3) at least once with base material and this slurry water thermal crystallisation.Forming high-density layer in this membrane material mesolite crystal duct He on the surface at base material, thus can be used for separating and refining mixture in useful component.
A kind of method for preparing molecular screen membrane from colloidal sol has been described among the WO 93/17781, this method comprises a kind of the water base of zeolite or alcohol radical sol composition of forming of formation, this sol composition is deposited on a kind of porous carrier, this porous carrier and sol composition is exposed in the water vapour atmosphere under temperature is enough to make the condition of sol composition hydrothermal crystallizing forms zeolite membrane.
People such as Bratton in EP 0481660A1, described a kind of on porous substrate load the film of zeolite type material is arranged, base material be shaped as flat plate, tubular or coiled, porous substrate can be porous metals, pottery, cermet, glass mineral matter, charcoal or polymer, and wherein available porous ceramics, glass, charcoal or mineral intermediate comprise poroid charcoal, carborundum, adobe or other silicate minerals.The preparation method of this film be with porous substrate (aperture can be 1～2000 μ m) but at least one surface be immersed in crystallization and become in the synthesized gel rubber of zeolite type material, make zeolite type material on the substrate surface crystallization, repeat these steps of one or many after the taking-up again, obtain the membrane material of zeolite type material direct crystallization on base material.Porous substrate is being immersed before synthesized gel rubber carries out crystallization, can be earlier at substrate surface in conjunction with last layer Ni, Co, Mo metal or its oxide (EP0481658A1), and/or, perhaps base material is carried out sour preliminary treatment (EP0481659A1) in conjunction with the oligomer (WO 93/19840) of last layer silicic acid.
Although reported many zeolite molecular sieve films in the above-mentioned patent, up to the present also the SAPO-34 molecular sieve is not grown on the porous substrate to prepare the bibliographical information of composite membrane.The SAPO-34 molecular sieve was succeeded in developing (USP 4440871) and through updating afterwards, had been obtained application in many chemical processes by Union Carbide Corporation from 1984.Because the shape separation selectivity if be made into membrane material, will be selected preferably in the aperture less (about 4 dusts) of SAPO-34 molecular sieve, might be applied as a kind of outstanding gas separation membrane.
The purpose of this invention is to provide a kind of new molecular screen membrane and preparation method thereof, make the SAPO-34 molecular sieve directly be grown on the permeability ceramic base material densely, in the hope of obtaining higher gas separation selectivity, for high temperature membrane is separated and membrane reactor provides new membrane material.
SAPO-34/ ceramic composite separation film provided by the present invention is made up of dull and stereotyped porous ceramics base material and the SAPO-34 molecular sieve thin layer that is compound in a surface of this base material evenly, firmly, densely, molecular sieve in this molecular sieve thin layer is connected to an integral body mutually densely, does not have intracrystalline pore to exist except the structure hole of molecular sieve itself.
SAPO-34 molecular sieve in the composite separating film provided by the present invention can be a various SAPO-34 molecular sieve of the prior art, its thickness is less than 5 microns, but also can carry out various modifications to the SAPO-34 molecular sieve on this composite separating film to enlarge its range of application.
The material of said porous ceramics base material does not have specific (special) requirements in the composite separating film provided by the present invention, it can be cermet, oxysalt (as silicate, titanate, zirconates etc.) pottery, also can be oxide, nitride and carbide pottery etc., but preferably at (under higher alkalisation and the higher temperature) more stable material under the synthesis condition of molecular sieve, as cermet, α-Al
2O
3Pottery etc.The average pore size of said porous ceramics base material is preferably 0.1～2 μ m
The preparation method of said composite separating film provided by the present invention is included in to pack in the synthesis reactor and can synthesizes the synthetic liquid of SAPO-34 molecular sieve, with average pore size is the top that the dull and stereotyped porous ceramics base material of 0.1～2 μ m is placed on this synthetic liquid, ceramic base material one side down is immersed in the synthetic liquid, one side up is exposed to outside the liquid level or with inert substance wraps up, hydrothermal crystallizing is at least three times according to a conventional method, the SAPO-34 molecular sieve is grown on the base material one side down, passes through bakes to burn the article at last.
The said synthetic liquid that can synthesize the SAPO-34 molecular sieve can select it to form and the molar ratio scope by prior art among the preparation method provided by the present invention, but the water yield is big when more synthetic than routine, and wherein preferable molar ratio scope is:
SiO
2/Al
2O
3=0.1～10
P
2O
5/Al
2O
3=0.1～10
R
+/P
2O
5=0.2～5
H
2O/Al
2O
3=40～400
R wherein
+Used organic ammonium template agent when expression is synthetic is generally tetraethyl ammonium hydroxide or tetraethylammonium bromide.
Said hydrothermal crystallizing and washing and drying are carried out according to a conventional method among the preparation method provided by the present invention, and the general hydrothermal crystallizing temperature that adopts is 150～230 ℃, and crystallization time is 0.5～10 day.Said roasting is used for removing the organic formwork agent of the molecular sieve that synthesizes, can be according to a conventional method in 300～500 ℃ of roastings 2～48 hours, but the heating rate during roasting preferably be controlled at 2 ℃/below the min, to prevent the fracture of molecular sieve thin layer.
Composite separating film provided by the present invention has the following advantages:
(1), thereby less gas molecule had higher separation selectivity because the duct less (about 4 Izod right sides) of SAPO-34 molecular sieve;
(2) the SAPO-34 molecular sieve is distributed in substrate surface equably, and there is not intracrystalline pore in intercrystalline, thereby guarantees that only there is the duct of molecular sieve in diffusion barrier in conjunction with closely;
(3) can carry out modulation or modification to the character of SAPO-34 molecular layer and do not influence the intensity of molecular sieve layer, make the range of application of this membrane material wider.
SAPO-34/ ceramic composite separation film provided by the present invention both can be used as the film resolution element and had used, and can be used in the membrane catalytic reactor again.
Fig. 1 is a schematic representation of apparatus used when preparing the SAPO-34/ ceramic composite separation film among the embodiment 1～3.
Fig. 2 is the schematic diagram of the used gas fractionation unit of the stalling characteristic of estimating molecular screen membrane.
X-ray diffraction (XRD) the crystalline phase figure of the unfired SAPO-34 ceramic composite separation film that Fig. 3 goes out for embodiment 1 is prepared, wherein a represents the ceramic base material sample before the composite molecular screen not, b represents the sample behind the composite molecular screen.
Fig. 4 is ESEM (SEM) photo before and after the ceramic base material surface recombination SAPO-34 molecular sieve among the embodiment 1, and wherein a represents compound preceding sample surfaces, and b represents the surface behind the compound upward SAPO-34 molecular sieve.
The following examples will the present invention is described further, but used preparation facilities etc. does not limit the scope of the invention among these embodiment and the embodiment.
Embodiment 1
Getting a slice diameter is 35mm, and thickness is 3mm, and average pore size is that (Dalian Chemical Physics Research Institute's commodity, material are α-Al for the ceramic base material of 0.3 μ m
2O
3), with thinner abrasive paper for metallograph one side is wherein polished smooth.
In beaker, add 5.055 gram aluminium isopropoxides (The British Drug HousesLtd), 18.23 gram concentration is the tetraethyl ammonium hydroxide (TEAOH of 10 heavy %, chemically pure reagent) aqueous solution and 2.854 gram phosphoric acid (85 heavy %, Red Star chemical plant, Beijing), after mixing, add 13.01 gram water and 1.8 gram Ludox (25 heavy %SiO2 again, state-run Wenzhou catalyst plant is produced), must synthesize liquid after stirring, by shown in Figure 1 this synthetic liquid 5 is poured in the synthesis reactor 7 of inner liner polytetrafluoroethylene then, the one side that above-mentioned ceramic base material 3 is not polished with polytetrafluoroethylraw raw material band 1 parcel in case molecular sieve in this length of looking unfamiliar, then ceramic base material 3 is fixed in the polytetrafluoroethylene (PTFE) fixed mount 2, polytetrafluoroethylene (PTFE) carriage 6 and fixed mount 2 are put into synthesis reactor 7, the one side 4 of the molecular sieve of will growing that making polishes gets well is positioned at the top of liquid 5 and contacts with liquid 5, another side is exposed to outside the liquid 5 up, behind the sealing synthesis reactor, put it in the baking oven that has been warming up to 180 ℃ in advance crystallization three days, ceramic base material is taken out in the cooling back, after spending deionised water and drying, again by above-mentioned steps crystallization secondary again, the one side of molecular sieve is carried out X-ray diffraction (XRD) and ESEM (SEM) is analyzed on compound then, and it the results are shown among Fig. 3 and Fig. 4.The result of XRD has shown on this ceramic base material surface recombination the SAPO-34 molecular sieve, and the SEM photo shows that the growth of SAPO-34 molecular sieve is comparatively even.
Embodiment 2
Molecular screen membrane preparation process in the present embodiment is identical with embodiment 1.
Getting a slice diameter is 35mm, and thickness is 5mm, and average pore size is that (Dalian Chemical Physics Research Institute's commodity, material are α-Al for the ceramic base material of 0.8 μ m
2O
3), it is simultaneously polished smooth with thinner abrasive paper for metallograph, another side with the polytetrafluoroethylraw raw material band parcel in case molecular sieve in this length of looking unfamiliar.
In beaker, add 5.055 gram aluminium isopropoxides, 18.23 restrain the TEAOH aqueous solution and the 2.854 gram phosphoric acid of 10 heavy %, after mixing, add 8.55 gram water and 1.8 gram Ludox again, must synthesize liquid after stirring, this synthetic liquid is poured in the synthesis reactor of inner liner polytetrafluoroethylene, by Fig. 1 above-mentioned ceramic base material is fixed, the sealing synthesis reactor, put it in the baking oven that has been warming up to 200 ℃ in advance crystallization three days, ceramic base material is taken out in the cooling back, after spending deionised water and drying, again by above-mentioned steps crystallization secondary again, get the SAPO-34/ ceramic composite separation film, the XRD figure of this diffusion barrier is identical with Fig. 3, and SEM photo and Fig. 4 are similar.
Embodiment 3
Method by embodiment 1 prepares the SAPO-34/ ceramic composite separation film, and the amount that different is adds entry is 56.26 grams, and crystallization time is four days.The XRD figure of resulting composite separating film is identical with Fig. 3, and SEM photo and Fig. 4 are similar.
Embodiment 4
Present embodiment illustrates the compactness of molecular screen membrane of the present invention.
The test of present embodiment is carried out in device shown in Figure 2, and wherein 11 is drier, and 12 is needle valve, 13 is pressure maintaining valve, and 14 is precision pressure gauge, and 15 is counterbalance valve, 16 is stop valve, 17 is soap film flowmeter, and 18 is thermocouple and temperature indicator, and 19 is heating furnace, 20 is the gas separate tank, 21 are O shape circle, and 22 is molecular screen membrane, and 23 is temperature controller.
When measuring the permeability of one-component gas, close stop valve 16, will when measuring the permeability of single-component gas, close stop valve 16, needle valve 12 is reached maximum, with pressure maintaining valve 13 pressure of gas is adjusted to set-point p (gauge pressure).Like this, the pressure of feed side remains on p (gauge pressure).See through side directly and the atmosphere pressure (gauge pressure) that promptly sees through side that communicates be zero, so the pressure reduction of film both sides is p.See through the flow (Vt) of the gas of film
iMeasure with soap-foam flowmeter.When measured value keeps constant basically, show that the transit dose of gas has reached stable state.The flow (Vt) of the gas of at this moment measuring that sees through film
iPromptly can be used to calculate the transmitance P of gas
iP
iValue is calculated as follows.
P
i=(Vt)
i/pA
In the following formula, A is effective area that sees through of zeolite membrane.Employed ceramic base material is the disk of φ 35mm, and used sealing ring is the O shape circle of φ 35mm * 3.5mm, and therefore, the area that effectively sees through of film equals the area of a circle that diameter is 28mm, i.e. A=6.158 * 10
4m
2, seeing through the flow (mol/s) of the gas of film when (V/t) i is for stable state, p is the pressure reduction (Pa) of film both sides gas, P
iTransmitance (mol/m for gas
2.s.Pa).
Densification is grown, do not had the molecular screen membrane of intracrystalline pore should be air-locked before the roasting removed template method, because the agent of organic ammonium template has occupied the duct of molecular sieve.
Respectively ceramic base material and the embodiment 1 resulting composite separating film of embodiment 1 described not composite S APO-34 are measured their transmitances to nitrogen, feed side N in gas fractionation unit shown in Figure 2
2Atmospheric pressure is 1.2Kg/cm
2, temperature is a room temperature, and the results are shown in Table 1 for it, and as can be seen, composite separating film provided by the present invention is airtight before roasting, and illustrating does not have intracrystalline pore.
Table 1
| Transmitance (the mol/m of nitrogen 2.s.Pa) | |
| Ceramic base material before compound | 6.58×10 -6 |
| Embodiment 1 gained composite membrane | 0 |
Embodiment 5
Present embodiment illustrates the gas separation selectivity of composite separating film provided by the present invention.
But the unfired SAPO-34/ ceramic composite separation film that embodiment 1 obtains is put into the muffle furnace of temperature programming, be warming up to 400 ℃ with 0.1 ℃/minute speed, this roasting temperature 24 hours, obtain the SAPO-34/ ceramic composite separation film of removed template method.
The composite separating film of above-mentioned removed template method is installed in the device shown in Figure 2, feeds hydrogen, carbon dioxide, nitrogen and normal butane respectively, be 323K that feed side pressure is 1.2Kg/cm in temperature
2Condition under measure the transmitance of film to these gases, that measures film thus selects the shape separation selectivity, the result is as shown in table 2, SAPO-34/ ceramic composite separation film provided by the present invention as can be seen has good shape selectivity energy, the transmitance of gas reduces along with the increase of the kinetic diameter of gas molecule, and normal butane can not see through this film because of its kinetic diameter greater than the channel diameter of SAPO-34/ molecular sieve.
Table 2
| Gas type | H 2 | CO 2 | N 2 | n-C 4H 10 |
| Transmitance (mol/m 2.s.Pa) | 1.35×10 -7 | 6.40×10 -8 | 1.54×10 -8 | 0 |
| Relative N 2Selectivity | 8.77 | 4.16 | 1 | 0 |
Embodiment 6
Present embodiment illustrates the separation selectivity of composite separating film provided by the invention to the two component gases of hydrogen-normal butane.
Press Fig. 2 when measuring the through performance of bi-component gas, at first feed the mist of pressing the definite composition preparation, by pressure maintaining valve 13 and counterbalance valve 15 pressure of feed side gas is adjusted to set-point p, and make the feed side gas outlet keep certain flow, be unlikely to change with the composition of guaranteeing feed side gas because of a certain component penetrated preferably film wherein.Seeing through the side gas vent communicates with atmosphere.Therefore the pressure reduction of film both sides gas is p, and when the flow of exit gas reached constant, sample analysis saw through the composition of side gas.
In device shown in Figure 2 the SAPO-34/ ceramic composite separation film of removed template method is measured its separation selectivity to two component gases according to the method identical with embodiment 5, feed side feeds hydrogen-normal butane gaseous mixture, and to make its pressure be 1.2Kg/cm
2, under different temperature, measure its separation selectivity, the composition gas chromatographic analysis of gas, the results are shown in Table 3 for gained, and separation selectivity wherein is calculated as follows:
Table 3
| Temperature (K) | 373 | 423 | 473 | |||
| Component | H 2 | n-C 4H 1 | H 2 | C 4H 10 | H 2 | n-C 4H 10 |
| Feed side is formed (mole %) | 73.11 | 26.89 | 73.11 | 26.89 | 73.11 | 26.89 |
| See through side and form (mole %) | 94.57 | 5.43 | 95.72 | 4.28 | 98.63 | 1.37 |
| H 2Selectivity | 6.41 | 8.23 | 26.48 | |||
Embodiment 7
Present embodiment illustrates the separation selectivity of composite separating film provided by the invention to the two component gases of hydrogen-iso-butane.
Measure the separation selectivity of the SAPO-34 ceramic composite separation film of removed template method to the two component gases of hydrogen-iso-butane according to the method identical with embodiment 6, the results are shown in Table 4 for gained.
Have from the result of table 3 and table 4 SAPO-34 ceramic composite separation film provided by the present invention as can be seen and well to select the shape separation selectivity.
Table 4
| Temperature (K) | 373 | 423 | 473 | |||
| Component | H 2 | i-C 4H 10 | H 2 | i-C 4H 10 | H 2 | i-C 4H 10 |
| Feed side is formed (mole %) | 73.50 | 26.50 | 73.50 | 26.50 | 73.50 | 26.50 |
| See through side and form (mole %) | 78.52 | 21.48 | 99.20 | 0.80 | 99.21 | 0.79 |
| H 2Selectivity | 1.32 | 44.71 | 45.23 | |||
Claims (5)
1. molecular sieve/ceramic composite separation film, it is characterized in that this composite separating film is made up of dull and stereotyped porous ceramics base material and the SAPO-34 molecular sieve thin layer that is compound in a surface of this base material evenly, firmly, densely, molecular sieve in this SAPO-34 molecular sieve thin layer connects as a whole mutually densely, does not have intracrystalline pore to exist except the structure hole of molecular sieve itself.
2. according to the composite separating film of claim 1, wherein said its thickness of SAPO-34 molecular sieve is less than 5 microns.
3. according to the composite separating film of claim 1, the average pore size of wherein said porous ceramics base material is 0.1～2 micron.
4. the preparation method of the molecular sieve/ceramic composite separation film of a claim 1 is characterized in that this method is included in to pack in the synthesis reactor and can synthesize the H of SAPO-34 molecular sieve
2O/Al
2O
3Mol ratio is 40～400 synthetic liquid, with average pore size is the top that 0.1～2 micron dull and stereotyped porous ceramics base material is placed on this synthetic liquid, ceramic base material one side down is immersed in the said synthetic liquid, one side up is exposed to outside the liquid level or with inert substance wraps up, hydrothermal crystallizing at least three times, the SAPO-34 molecular sieve is grown on the base material one side down, passes through bakes to burn the article at last.
5. according to the preparation method of claim 4, the heating rate that it is characterized in that said roasting is less than 2 ℃/minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106353A CN1061900C (en) | 1996-06-05 | 1996-06-05 | SAPO-34/ceramic composite separation film and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106353A CN1061900C (en) | 1996-06-05 | 1996-06-05 | SAPO-34/ceramic composite separation film and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1167005A CN1167005A (en) | 1997-12-10 |
| CN1061900C true CN1061900C (en) | 2001-02-14 |
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ID=5119094
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| CN96106353A Expired - Fee Related CN1061900C (en) | 1996-06-05 | 1996-06-05 | SAPO-34/ceramic composite separation film and preparation thereof |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7316727B2 (en) | 2004-03-19 | 2008-01-08 | The Regents Of The University Of Colorado | High-selectivity supported SAPO membranes |
| CN101443298A (en) | 2006-05-15 | 2009-05-27 | 科罗拉多州立大学董事会 | High flux and selectivity SAPO-34 membranes for CO/CH4 separations |
| WO2008112520A1 (en) | 2007-03-09 | 2008-09-18 | The Regents Of The University Of Colorado, A Body Corporate | Synthesis of zeolites and zeolite membranes using multiple structure directing agents |
| US8679227B2 (en) | 2010-04-29 | 2014-03-25 | The Regents Of The University Of Colorado | High flux SAPO-34 membranes for CO2/CH4 separation and template removal method |
| CN102336414B (en) * | 2011-06-29 | 2012-12-05 | 同济大学 | Method for preparing high quality SAPO-34 zeolite membrane by clear sol method |
| CN104043314B (en) * | 2014-06-17 | 2016-04-27 | 北京埃夫信环保科技有限公司 | A kind of mesopore molecular sieve coating processes |
| CN104888617A (en) * | 2015-05-08 | 2015-09-09 | 大连理工大学 | Method for preparing Pd/SAPO-34 composite membrane on macroporous carrier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| EP0481660A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Membranes |
| EP0511739A1 (en) * | 1991-03-29 | 1992-11-04 | Ngk Insulators, Ltd. | Synthetic films with zeolite crystal bodies, and methods of making and using them |
| CN1077658A (en) * | 1992-04-20 | 1993-10-27 | 太原工业大学 | The method of preparation of molecular sieve membrane on porous silicate material surface |
-
1996
- 1996-06-05 CN CN96106353A patent/CN1061900C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| EP0481660A1 (en) * | 1990-10-19 | 1992-04-22 | The British Petroleum Company P.L.C. | Membranes |
| EP0511739A1 (en) * | 1991-03-29 | 1992-11-04 | Ngk Insulators, Ltd. | Synthetic films with zeolite crystal bodies, and methods of making and using them |
| CN1077658A (en) * | 1992-04-20 | 1993-10-27 | 太原工业大学 | The method of preparation of molecular sieve membrane on porous silicate material surface |
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|---|---|
| CN1167005A (en) | 1997-12-10 |
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