CN100393398C - Granular type integral membrane reactor for catalysis-separation and its synthesis method - Google Patents
Granular type integral membrane reactor for catalysis-separation and its synthesis method Download PDFInfo
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Abstract
The invention relates to a particle catalysis-separate membrane reactor with selective catalysis particle catalyst support molecule screen membrane, wherein the membrane of inventive molecule membrane screen reactor is uniform and dense with high catalysis, selectivity and mechanical strength. Said reactor comprises particle catalyst carrier, loaded active component and molecule screen membrane loaded on the catalyst particles, while the catalyst carrier is metal oxide, the active component is the transition metals and oxides in forth or fifth period of periodic table of elements and the molecule screen molecule is NaA molecule screen mmembrane.
Description
Technical field
The present invention relates to a kind of molecular film reactor and synthetic method thereof, particularly a kind of have the shape selective catalysis optionally granular type integral membrane reactor for catalysis-separation and a synthetic technology thereof of pellet type catalyst supported molecular-sieve film.
Background technology
Molecular sieve not only has high chemical stability, heat endurance and the mechanical stability of general inoranic membrane as inorganic material film, and pore-size distribution is single, has molecule screening function, and separation process is realized under situation about not undergoing phase transition, significantly energy savings, simplification technological process and operation is the important inorganic material film of realizing separating and realizing on the molecular level membrane reactor.The Japan scientist is in the eighties in last century, at first aluminum oxide substrate and Pyrex surface preparation the ZSM-5 molecular screen membrane, after this people have carried out the research and development of a large amount of molecular screen membranes, by the synthetic method One's name is legion of the disclosed molecular screen membrane of domestic and international patent documentation, for example:
Japan Patent discloses a kind of Y zeolite film method that synthesizes on the tubulose porous supporting body in the patent of patent No. JP 08257301.This method is soaked in the system film with in the alumino-silicate colloidal sol with porous carrier, the hydrothermal crystallizing film forming, and this film has separating power to mixed systems such as alcohol-water, alcohol-cyclohexanes.
Chinese patent discloses a kind of method of microwave heating to synthesize molecular sieve film in the patent of patent No. 99112751.X, the synthesizing molecular sieve film that this method can be rapidly and efficiently.Its method is: with a certain proportion of Na
2O, Al
2O
3, SiO
2And H
2O is made into the synthetic liquid of molecular sieve, and the porous basement membrane with tubulose or sheet places synthetic liquid then, utilize heating using microwave in 50～100 ℃ synthetic, the molecular screen membrane of washing and drying then.This molecular screen membrane is to H
2/ C
4H
10Has good separating property.
Chinese patent discloses a kind of MnO in the patent of the patent No. 01109223.8
2Nm-class sieve-membrane reactor and technology of preparing scheme thereof.This membrane reactor by the supporter of ceramic material and on supporter sintering and MnO
2Sieve membrane constitutes, and the film average pore size is 2-3nm, and thicknesses of layers is 10-15 μ m; Have catalytic activity preferably, under the situation that CO or sulfide exist, be difficult for causing poisoning, and permeation flux and selectivity are all higher.
ZSM-5, Silicalite-1, A type, Y type, L type, SAPO-34, AlPO4-5, UTD-1 equimolecular sieve membrane have been synthesized on the variety carrier such as tubulose and flake porous material now, but owing to synthesizing molecular sieve film complex process on graininess matrix, prepared molecular screen membrane rete easily produces defective, inhomogeneous, and restricted the development of such molecular screen membrane, especially in the research of synthetic NaA type equimolecular sieve membrane reactor on the pellet type catalyst, do not see that report is arranged.
Summary of the invention
The objective of the invention is at existing on graininess matrix the existing complex process of synthesizing molecular sieve film, prepared molecular screen membrane rete easily produces defective, uneven weak point, provide a kind of technology simple, prepared molecular film reactor rete is fine and close evenly continuously and have the graininess catalysis of high catalytic activity, selectivity and mechanical strength-separate one from type integral membrane reactor and synthetic method thereof.
Granular type integral membrane reactor for catalysis-separation of the present invention, comprise pelleted substrate, load thereon catalyst activity component and be attached to molecular screen membrane on the catalyst granules, wherein pelleted substrate adopts metal oxides such as aluminium oxide or titanium dioxide; Catalyst activity component is more than one of period 4 of the periodic table of elements and transition metal in the period 5 and oxide thereof; Molecular screen membrane is a NaA type molecular screen membrane, and its molecular formula is: Na
96[Al
96Si
96O
384] 216H
2O, its effective aperture is 0.42nm, and is suitable with little molecular dynamics diameter, so NaA type molecular screen membrane has very high separation selectivity to the molecule of different dynamic diameter.
The step of the synthetic method of granular type integral membrane reactor for catalysis-separation of the present invention is as follows:
(1) Preparation of catalysts
Take by weighing a through 1～6 hour graininess γ of 400～1200 ℃ of roastings-Al
2O
3Or TiO
2Deng metal oxide, its immersion is contained in the precursor solution of 0.001～0.020 part of active constituent, ageing 0.5～24 hour, dry back was in 400～700 ℃ of roastings 1～8 hour, get pellet type catalyst, wherein, the predecessor of active constituent is more than one of solubility salt of period 4 of the periodic table of elements and the transition metal in the period 5.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Silicon source solution: the water-soluble and silicon source of NaOH is mixed, and ageing is 0.5～24 hour then, silicon source solution.Wherein the silicon source is sodium metasilicate or Ludox.
Aluminium source solution: the water-soluble and aluminium source of NaOH is mixed, and ageing is 0.5～24 hour then, aluminium source solution.Wherein the aluminium source is more than one in aluminium oxide, aluminium foil, aluminum sulfate, sodium aluminate, boehmite, the sodium silicoaluminate.
With the colloidal sol that silicon source solution and aluminium source solution mix transparently, finally obtain prescription and be aSiO
2: Al
2O
3: bNa
2O:cH
2The synthesis mother liquid of O, a=1～8 wherein, b=11～19, c=400～1000.
(3) membrane reactor is synthetic
The catalyst granules that step (1) obtains is put into the synthesis mother liquid that step (2) obtains, ageing 0.5～24 hour, in 70～120 ℃ of crystallization 0.5～8 hour, filtration washing was to neutral then, 70～120 ℃ of dryings 4～24 hours.
Repeating step (2) and (3) several times obtain granular type integral membrane reactor for catalysis-separation of the present invention then.
The granular type integral membrane reactor for catalysis-separation that the present invention synthesizes with existing on graininess matrix the synthesis of molecular sieve membrane reactor compare, it is simple to have technology, and prepared molecular film reactor rete is fine and close evenly continuously and have characteristics of high catalytic activity, selectivity and mechanical strength.The granular type integral membrane reactor for catalysis-separation that the present invention synthesizes is particularly suitable for using in shape selective catalysis.
Description of drawings
The graininess Pt/Al that Fig. 1 makes after 1000 ℃ of roastings for catalyst carrier
2O
3The XRD figure of synthetic NaA type molecular film reactor on the catalyst.
The graininess Pt/Al that Fig. 2 makes after 600 ℃ of roastings for catalyst carrier
2O
3The surperficial electron microscope photo scanning (SEM) of synthetic NaA type molecular film reactor figure on the catalyst.
The graininess Pt/Al that Fig. 3 makes after 800 ℃ of roastings for catalyst carrier
2O
3The surperficial electron microscope photo scanning (SEM) of synthetic NaA type molecular film reactor figure on the catalyst.
The graininess Pt/Al that Fig. 4 makes after 1000 ℃ of roastings for catalyst carrier
2O
3The surperficial electron microscope photo scanning (SEM) of synthetic NaA type molecular film reactor figure on the catalyst.
The graininess Pt/Al that Fig. 5 makes after 1200 ℃ of roastings for catalyst carrier
2O
3The surperficial electron microscope photo scanning (SEM) of synthetic NaA type molecular film reactor figure on the catalyst.
Accompanying drawing 6 is that catalyst system therefor carrier of the present invention is through the XRD figure of different temperatures roasting after 4 hours.
Accompanying drawing 7 is graininess Pt/Al
2O
3On the catalyst through the SEM of the synthetic membrane reactor of 1 hour hydrothermal crystallizing figure.
Accompanying drawing 8 is graininess Pt/Al
2O
3On the catalyst through the SEM of the synthetic membrane reactor of 4 hours hydrothermal crystallizings figure.
Accompanying drawing 9 is graininess Pt/Al
2O
3On the catalyst through the SEM of the synthetic membrane reactor of 6 hours hydrothermal crystallizings figure.
The specific embodiment
Below by embodiment granular type integral membrane reactor for catalysis-separation of the present invention and synthetic method thereof are described further, but the present invention is not limited to these embodiment.
Embodiment 1:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
Graininess γ-Al
2O
3(particle diameter 1～1.5mm) after 4 hours, takes by weighing 4.00g through 600 ℃ of roastings, its immersion contained in the platinum acid chloride solution of 0.0200g Pt, and ageing 2 hours, dry back gets graininess Pt/Al in 500 ℃ of roastings 6 hours
2O
3Catalyst.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Take by weighing 9.15g NaOH and 9.64g Na
2SiO
39H
2O and 55.8g deionized water fully mix, and ageing is 1 hour then, get silicon source solution.Take by weighing 6.85g NaOH and 2.48g NaAlO
2Fully mix with the 55.50g deionized water, ageing is 1 hour then, gets aluminium source solution.The colloidal sol that mixes silicon source solution and aluminium source solution transparent finally obtains prescription and is 2SiO then
2: Al
2O
3: 15Na
2O:450H
2The synthesis mother liquid of O.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 3.98g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 4 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.
Embodiment 2:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
Graininess γ-Al
2O
3(particle diameter 1～1.5m) after 4 hours, takes by weighing 4.02g through 800 ℃ of roastings, its immersion contained in the platinum acid chloride solution of 0.0200g Pt, and ageing 2 hours, dry back gets graininess Pt/Al in 500 ℃ of roastings 6 hours
2O
3Catalyst.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Take by weighing 9.15g NaOH and 9.64g Na
2SiO
39H
2O and 55.6g deionized water fully mix, and ageing is 1 hour then, get silicon source solution.Take by weighing 6.86g NaOH and 2.49g NaAlO
2Fully mix with the 55.6g deionized water, ageing is 1 hour then, gets aluminium source solution.The colloidal sol that mixes silicon source solution and aluminium source solution transparent finally obtains prescription and is 2SiO then
2: Al
2O
3: 15Na
2O:450H
2The synthesis mother liquid of O.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 4.05g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 4 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.
Embodiment 3:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
Graininess γ-Al
2O
3(particle diameter 1～1.5mm) after 4 hours, takes by weighing 4.03g through 1000 ℃ of roastings, its immersion contained in the platinum acid chloride solution of 0.0200g Pt, and ageing 2 hours, dry back gets graininess Pt/Al in 500 ℃ of roastings 6 hours
2O
3Catalyst.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Take by weighing 9.15g NaOH and 9.64g Na
2SiO
39H
2O and 55.7g deionized water fully mix, and ageing is 1 hour then, get silicon source solution.Take by weighing 6.85g NaOH and 2.48g NaAlO
2Fully mix with the 55.6g deionized water, ageing is 1 hour then, gets aluminium source solution.The colloidal sol that mixes silicon source solution and aluminium source solution transparent finally obtains prescription and is 2SiO then
2: Al
2O
3: 15Na
2O:450H
2The synthesis mother liquid of O.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 4.00g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 4 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.Thicknesses of layers 15～17 μ m.
Embodiment 4:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
Graininess γ-Al
2O
3(particle diameter 1～1.5mm) after 4 hours, takes by weighing 3.96g through 1200 ℃ of roastings, its immersion contained in the platinum acid chloride solution of 0.0200g Pt, and ageing 2 hours, dry back gets graininess Pt/Al in 500 ℃ of roastings 6 hours
2O
3Catalyst.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Take by weighing 9.15g NaOH and 9.64g Na
2SiO
39H
2O and 55.7g deionized water fully mix, and ageing is 1 hour then, get silicon source solution.Take by weighing 6.85g NaOH and 2.48g NaAlO
2Fully mix with the 55.6g deionized water, ageing is 1 hour then, gets aluminium source solution.The colloidal sol that mixes silicon source solution and aluminium source solution transparent finally obtains prescription and is 2SiO then
2: Al
2O
3: 15Na
2O:450H
2The synthesis mother liquid of O.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 4.03g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 4 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.
Embodiment 5:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
With (1) among the embodiment 3.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
With (2) among the embodiment 3.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 4.00g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 4 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours, granular type integral membrane reactor for catalysis-separation.Thicknesses of layers 5～6 μ m.
Embodiment 6:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
With (1) among the embodiment 3.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
With (2) among the embodiment 3.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 3.94g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 1 hour, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.
Embodiment 7:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
With (1) among the embodiment 3.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
With (2) among the embodiment 3.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 3.99g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 6 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.
Embodiment 8:
A kind of step of synthetic method of granular type integral membrane reactor for catalysis-separation is as follows:
(1) Preparation of catalysts
Take by weighing 8.50g graininess TiO
2(particle diameter ca.0.5mm) contains its immersion in the platinum acid chloride solution of 0.0429g Pt, ageing 2 hours, and dry back gets graininess Pt/TiO in 500 ℃ of roastings 4 hours
2Catalyst.
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Take by weighing 2.31g NaOH and 2.41g Na
2SiO
39H
2O and 14.0g deionized water fully mix, and ageing is 1 hour then, get silicon source solution.Take by weighing 1.70g NaOH and 0.620g NaAlO
2Fully mix with the 14.1g deionized water, ageing is 1 hour then, gets aluminium source solution.The colloidal sol that mixes silicon source solution and aluminium source solution transparent finally obtains prescription and is 2SiO then
2: Al
2O
3: 15Na
2O:450H
2The synthesis mother liquid of O.
(3) membrane reactor is synthetic
Take by weighing the pellet type catalyst 1.01g that (1) obtain and put into the synthesis mother liquid that (2) obtain, ageing 1 hour, in 80 ℃ of crystallization 4 hours, cooling back suction filtration, washing be to neutral, in 80 ℃ of dryings 12 hours.
Repeat (2) and (3), carry out second time hydro-thermal and synthesize, must granular type integral membrane reactor for catalysis-separation.
This membrane reactor is carried out the section morphology analysis find that thicknesses of layers is 3～7 μ m.
Embodiment 9:
Embodiment 3 prepared membrane reactors are carried out XRD analysis know, except Pt/Al
2O
3Outside the diffraction maximum of catalyst substrates, typical NaA molecular sieve characteristic diffraction peak has appearred.
Embodiment 10:
Membrane reactor among embodiment 1～embodiment 4 is carried out the surface topography analysis, and its SEM figure that amplifies 2000 times sees Fig. 2～Fig. 5 respectively.As seen, catalyst carrier is after 800 ℃ and 1000 ℃ of roastings, and the NaA molecular screen membrane that is synthesized is evenly continuous; Catalyst carrier is after 600 ℃ of roastings, and the molecular screen membrane that is synthesized is not as the former two; Catalyst carrier is unfavorable for film forming after 1200 ℃ of roastings.
Embodiment 11:
To catalyst carrier used among embodiment 1～embodiment 4 XRD analysis after 600 ℃, 800 ℃, 1000 ℃, 1200 ℃ roastings respectively, see Fig. 6.As seen through the Al of 800 ℃ and 1000 ℃ roastings
2O
3Mainly show as γ-Al
2O
3And θ-Al
2O
3The stack of diffraction maximum is beneficial to the growth of NaA molecular screen membrane.The catalyst carrier of 1200 ℃ of roastings is unfavorable for film forming, may be because phase structure mainly is α-Al at this moment
2O
3Cause.
Embodiment 12:
To carrying out the surface topography analysis through 1 hour, 4 hours and the synthetic membrane reactor (corresponding embodiment 6, embodiment 3 and embodiment 7 prepared membrane reactors respectively) of the synthetic crystallization of 6 hours hydro-thermals, its SEM figure that amplifies 8000 times sees Fig. 7, Fig. 8 and Fig. 9 respectively.As seen, through 4 hours synthetic formed membrane reactor the bests of crystallization of hydro-thermal, rete was fine and close evenly continuously, and stray crystal then appears in crystallization time long (6 hours).
Embodiment 13:
The membrane reactor that embodiment 3 is synthesized carries out the ultrasonic wave cleaning, cleans power 140W, scavenging period 40 minutes.The SEM of membrane reactor figure and quality were as can be known before and after contrast was cleaned, membrane reactor rete after ultrasonic wave cleans does not produce the crack, peels off, the rete firm supporting of the granular type integral membrane reactor for catalysis-separation that the present invention synthesizes is described, has very high mechanical strength.
The above embodiment of the present invention 3 prepared granular type integral membrane reactor for catalysis-separation are used for CO and n-C
4H
10Selective oxidation reaction, the reaction selectivity of CO and conversion ratio reach 100% and 94.5% respectively under 210 ℃ of reaction temperatures, reaction selectivity and conversion ratio at successive reaction CO after 12 hours there is no downward trend, the granular type integral membrane reactor for catalysis-separation that the present invention synthesizes is described, be able to take 210 ℃ of reaction temperatures and do not cause molecular screen membrane defectives such as crack to occur, and membrane reactor has very high catalytic selectivity and activity.
Claims (2)
1. granular type integral membrane reactor for catalysis-separation, it comprise pelleted substrate, load thereon catalyst activity component and be attached to molecular screen membrane on the catalyst granules, it is characterized in that described catalyst activity component is more than one of period 4 of the periodic table of elements and transition metal in the period 5 and oxide thereof, described pelleted substrate adopts particle-shaped metal oxide, molecular screen membrane is a NaA type molecular screen membrane, and wherein: described metal oxide particle shape catalyst carrier adopts aluminium oxide or titanium dioxide to make.
2. the synthetic method of a granular type integral membrane reactor for catalysis-separation is characterized in that this synthetic method may further comprise the steps:
(1) Preparation of catalysts
Take by weighing a through 1～6 hour graininess γ of 400～1200 ℃ of roastings-Al
2O
3Or TiO
2Metal oxide, its immersion is contained in the precursor solution of 0.001～0.020 part of active constituent, ageing 0.5～24 hour, dry back was in 400～700 ℃ of roastings 1～8 hour, get pellet type catalyst, wherein, the predecessor of active constituent is more than one of solubility salt of period 4 of the periodic table of elements and the transition metal in the period 5;
(2) preparation of the synthesis mother liquid of synthesizing molecular sieve film
Silicon source solution: the water-soluble and silicon source of NaOH is mixed, and ageing is 0.5～24 hour then, silicon source solution; Wherein the silicon source is sodium metasilicate or Ludox;
Aluminium source solution: the water-soluble and aluminium source of NaOH is mixed, and ageing is 0.5～24 hour then, aluminium source solution; Wherein the aluminium source is more than one in aluminium oxide, aluminium foil, aluminum sulfate, sodium aluminate, boehmite, the sodium silicoaluminate;
With the colloidal sol that silicon source solution and aluminium source solution mix transparently, finally obtain prescription and be aSiO
2: Al
2O
3: bNa
2O:cH
2The synthesis mother liquid of O, a=1～8 wherein, b=11～19, c=400～1000;
(3) membrane reactor is synthetic
The catalyst granules that step (1) obtains is put into the synthesis mother liquid that step (2) obtains, ageing 0.5～24 hour, in 70～120 ℃ of crystallization 0.5～8 hour, filtration washing was to neutral then, 70～120 ℃ of dryings 4～24 hours;
Repeating step (2) and (3) several times obtain described granular type integral membrane reactor for catalysis-separation then.
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| CN103203249B (en) * | 2012-01-12 | 2014-12-17 | 中国科学院大连化学物理研究所 | Preparation method of H type beta molecular sieve membrane packaged capsule catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618435A (en) * | 1992-03-31 | 1997-04-08 | Inrad | Synthesis of inorganic membranes including metals |
| CN1267566A (en) * | 1999-03-17 | 2000-09-27 | 中国科学院大连化学物理研究所 | Microwave heating to synthesize molecular sieve film |
| JP2004051397A (en) * | 2002-07-17 | 2004-02-19 | Japan Fine Ceramics Center | Amorphous silica porous material, method of manufacturing the same, molecular sieve membrane, catalyst carrier, and adsorbent |
| CN1597072A (en) * | 2004-08-04 | 2005-03-23 | 南京工业大学 | Preparation method of high performance permeation evaporation permeable membrane |
-
2005
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618435A (en) * | 1992-03-31 | 1997-04-08 | Inrad | Synthesis of inorganic membranes including metals |
| CN1267566A (en) * | 1999-03-17 | 2000-09-27 | 中国科学院大连化学物理研究所 | Microwave heating to synthesize molecular sieve film |
| JP2004051397A (en) * | 2002-07-17 | 2004-02-19 | Japan Fine Ceramics Center | Amorphous silica porous material, method of manufacturing the same, molecular sieve membrane, catalyst carrier, and adsorbent |
| CN1597072A (en) * | 2004-08-04 | 2005-03-23 | 南京工业大学 | Preparation method of high performance permeation evaporation permeable membrane |
Non-Patent Citations (2)
| Title |
|---|
| A型分子筛膜的研究进展. 陈晓波等.化学进展，第13卷第5期. 2001 |
| A型分子筛膜的研究进展. 陈晓波等.化学进展，第13卷第5期. 2001 * |
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