CN105080360B - A kind of pure silicon molecular sieve film preparation method using Woelm Alumina as carrier - Google Patents
A kind of pure silicon molecular sieve film preparation method using Woelm Alumina as carrier Download PDFInfo
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Abstract
The present invention relates to pure silicon molecular sieve film preparing technical field, it is a kind of pure silicon molecular sieve film preparation method using Woelm Alumina as carrier, is characterised by：Using porous alumina ceramic as carrier, preparing surface has the pure silicon molecular sieve film of MFI crystal structures, and the average pore size of porous alumina ceramic carrier is 0.1~2 μm, and mean porosities are 10~60%；The porous alumina ceramic carrier is tubular carrier, chip carrier, doughnut or multichannel carrier ceramic monolith；Using TPAOH as template, with secondary Hydrothermal Synthesiss pure silicon molecular sieve film；Step includes：With Synthesis liquid 3TPAOH：1Na2O：10SiO2：150H2O synthesizes spherical crystal seed；Coat on carrier the crystal seed layer of 2~10 μm of load using vacuum method, and solidify afterwards；Synthesis liquid is configured, constitutes and is：aTPAOH：bNa2O：10SiO2：cH2O, wherein a=0.1~2, b=0.05~5, c=100~200；It is coated with crystal seed layer carrier to be placed in Synthesis liquid, is put into reactor and is placed in rotary oven, Hydrothermal Synthesiss is carried out together；Drying, pure silicon molecular sieve film is obtained after removing template TPAOH.
Description
Technical field
It is a kind of pure silicon molecule using Woelm Alumina as carrier the present invention relates to pure silicon molecular sieve film preparing technical field
Sieve membrane preparation method, is specifically to provide a kind of preparation side that pure silicon molecular sieve film is synthesized on porous alumina ceramic pipe carrier
Method.
Background technology
Molecular screen membrane has advantages below compared with other membrane materials:(1) molecular screen membrane has regular pore passage structure, hole
Footpath distribution is homogeneous, can be with many important raw materials of industry of adsorbing separation by molecule screening or shape-selective diffusion；(2) molecular screen membrane has
There are good heat endurance, chemical stability, biological stability and mechanical stability.Compared with organic film, oozed with higher
Saturating flux and selectivity, with longer service life；(3) different molecular screen membranes has different hydrophilic and hydrophobics, can basis
The requirement for separating component selects suitable molecular screen membrane, and organics dehydration can be utilized to be contained in hydrophilic A type molecular sieve film, water
The separation of a small amount of organic matter can use hydrophobic high-silica zeolite film.
With the increase of energy demand, the exploitation of regenerative resource has important strategic importance, and countries in the world are all given
Enough attention.Chinese Government is fully recognized that importance of the exploitation using regenerative resource, will produce the project of alcohol fuel
It is classified as national " 15 " demonstration project major project.The production of current ethanol is main using batch (-type) and the producer of semibatch
Formula, not only limit the unit volume yield of ethanol, the production cost of ethanol is remained high, greatly limit alcohol fuel
Further genralrlization and use.Constantly product ethanol is separated to improve fermentation tank using needs during Ethanol Production by Fermentation
Production capacity, the concentration of product ethanol is located generally 5% or so using conventional distillating method during Ethanol Production by Fermentation
The ethanol of reason low concentration is economically the absence of competitiveness, and the alcohol fermentation liquid that low concentration is handled using membrane separation technique can
To say the being feasible isolation technics of a comparison.
High-silica zeolite film being used the low-concentration ethanol seperation film reported at present, 1994, Sano et al. was reported first more
The high-silica zeolite film of synthesized high-performance, selectively reaches 60, permeation flux reaches 0.76kg/m2.h on stainless steel, is real
The separation of existing low-concentration ethanol provides brand-new separation means；Patent CN200410100453.8 reports one kind in titanium dioxide
The preparation method of high performance silicon molecular screen membrane is loaded on silicon ceramics, at 60 DEG C, selectivity is up to 75, and permeation flux is
0.43kg/m2.h。
Although people's oneself achievement in research certain through achieving in terms of low concentration organic aqueous solution separation, how
Existing high flux can be prepared the molecular screen membrane of high separation factor again, is still an extremely challenging job.For reality
This existing target, it is necessary to which synthesized molecular screen membrane possesses these three following features:(1) molecular sieve film layer has higher dredge
Aqueous, (2) molecular sieve film layer is thin as far as possible, and the intracrystalline pore in (3) molecular sieve film layer is few and small as far as possible.From the text of report
From the point of view of offering, high performance high-silica zeolite film is difficult to be mainly the influence of Synthesis liquid the reason for preparation.Good formula is that synthesis is high
The key of silicon molecular sieve film, for using for alumina support, when basicity is too high, easily causes overflowing for Al elements in carrier
Go out, eventually reduce the hydrophobicity of high-silica zeolite film.Hydrothermal synthesis method synthesizes high property on porous alumina carrier at present
Energy pure silicon molecular sieve film is still a challenge.
The content of the invention
Instant invention overcomes deficiency of the prior art, there is provided a kind of pure silicon molecular sieve using Woelm Alumina as carrier
Membrane preparation method.
In order to realize above-mentioned purpose, adopt the following technical scheme that：
One kind is using Woelm Alumina as carrier, and surface has the pure silicon molecular sieve film of MFI crystal structures, and Woelm Alumina is carried
Body average pore size is 0.1~2 μm, and mean porosities are 10~60%.Preparation method be using Woelm Alumina as carrier, with
TPAOH is template, secondary Hydrothermal Synthesiss pure silicon molecular sieve film.Molecular screen membrane of the present invention is uniform, fine and close, without big hole defect
In the presence of, with very high selectivity, permeability and repeatability.And present invention considerably reduces generated time, and improve institute
The performance of the pure silicon molecular sieve film of synthesis, with very high repeatability, suitable for industry amplification.
The present invention is a kind of pure silicon molecular sieve film preparation method using Woelm Alumina as carrier, it is characterised in that：
Using porous alumina ceramic as carrier, preparing surface has the pure silicon molecular sieve film of MFI crystal structures, porous oxidation
The average pore size of aluminium ceramic monolith is 0.1~2 μm, and mean porosities are 10~60%；The porous alumina ceramic carrier is
Tubular carrier, chip carrier, doughnut or multichannel carrier ceramic monolith；Using TPAOH as template, with secondary water heat seal
Into pure silicon molecular sieve film；
Concrete technology step is as follows：
1) according to Synthesis liquid 3TPAOH：1Na2O：10SiO2：150H2O ratios synthesize 100~400nm's
The spherical crystal seeds of Silicalite-1；
2) crystal seed is coated, using vacuum method in the crystal seed layer of 2~10 μm of porous alumina ceramic supported on carriers, is then existed
Solidify 1~5h at 150~200 DEG C；
3) Synthesis liquid is configured, constitutes and is：aTPAOH：bNa2O：10SiO2：cH2O, wherein a=0.1~2, b=0.05~5,
C=100~200；
4) alumina ceramic carrier for being coated with crystal seed layer is placed in Synthesis liquid, is put into reactor and is placed in rotary oven
In, Hydrothermal Synthesiss are carried out together, and temperature is 150~200 DEG C, and the time is 2~4h；
5) washing and drying after synthesizing, in removing template TPAOH at 450~550 DEG C；
6) ethanol/water separation test condition：Temperature 60 C, atmospheric pressure 101kPa, material rubs
Your composition ethanol content is 5~10%, with gas-chromatography SP-3420A types gas-chromatography point
Analyse the gas composition of per-meate side.
Beneficial effects of the present invention：
(1) compared with prior art, this method is, using cheap Woelm Alumina as carrier, to have expanded support material
Source so that pure silicon molecular sieve film of the present invention has relatively low cost.(2) present invention reduces in carrier Al elements overflow
Go out, improve the hydrophobicity that pure silicon molecular sieve film is prepared on porous alumina carrier, it is logical with higher selectivity and infiltration
Amount, and the repeatability prepared is very high.
(3) preparation method generated time is short, and simple possible, price is relatively low, is adapted to commercial Application.
Brief description of the drawings
The present invention is further detailed explanation with embodiment below in conjunction with the accompanying drawings：
Fig. 1 is the SEM (scanning electron microscope (SEM) photograph) for implementing the crystal seed in 1；
Fig. 2 is the surface SEM figures of the pure silicon molecular sieve film in embodiment 1；
Fig. 3 is the section SEM figures of the pure silicon molecular sieve film in embodiment 1；
Embodiment
The present invention, but not limited to this are described in detail with reference to specific embodiment.
Embodiment 1
1st, according to Synthesis liquid 3TPAOH：1Na2O：10SiO2：150H2O synthesizes the 300nm spherical crystalline substances of Silicalite-1
Kind；
2nd, crystal seed is coated, 10 μm of crystal seed layer is loaded on porous alumina carrier using vacuum method, then at 200 DEG C
Solidify 3h；
3rd, Synthesis liquid is configured, constitutes and is：aTPAOH：1SiO2：bH2O, wherein a=0.17, b=120；
4th, the carrier for being coated with crystal seed layer is placed in Synthesis liquid, is put into reactor and is placed in rotary oven, is carried out together
Hydrothermal Synthesiss, temperature is 200 DEG C, and the time is 4h；
5th, washing and drying after synthesizing, in removing template TPAOH at 550 DEG C；
6th, ethanol/water separation test condition：Temperature 60 C, atmospheric pressure 101kPa, material mole constitutes ethanol content and is
5%, the gas for analyzing per-meate side with gas-chromatography (SP-3420A types gas-chromatography) is constituted.
Membrane tube test result is as shown in the table：
Embodiment 2
1st, according to Synthesis liquid 3TPAOH：1Na2O：10SiO2：150H2O synthesizes the 300nm spherical crystalline substances of Silicalite-1
Kind；
2nd, crystal seed is coated, 5 μm of crystal seed layer is loaded on porous alumina carrier using vacuum method, then at 180 DEG C
Solidify 3h；
3rd, Synthesis liquid is configured, constitutes and is：aTPAOH：1SiO2：bH2O, wherein a=0.17, b=120；
4th, the carrier for being coated with crystal seed layer is placed in Synthesis liquid, is put into reactor and is placed in rotary oven, is carried out together
Hydrothermal Synthesiss, temperature is 150 DEG C, and the time is 4h；
5th, washing and drying after synthesizing, in removing template TPAOH at 450 DEG C；
6th, ethanol/water separation test condition：Temperature 60 C, atmospheric pressure 101kPa, material mole constitutes ethanol content and is
5%, the gas for analyzing per-meate side with gas-chromatography (SP-3420A types gas-chromatography) is constituted.
Membrane tube test result is as shown in the table：
Embodiment 3
1st, according to Synthesis liquid 3TPAOH：1Na2O：10SiO2：150H2O synthesizes the 300nm spherical crystalline substances of Silicalite-1
Kind；
2nd, crystal seed is coated, 2 μm of crystal seed layer is loaded on porous alumina carrier using vacuum method, then at 180 DEG C
Solidify 3h；
3rd, Synthesis liquid is configured, constitutes and is：aTPAOH：1SiO2：bH2O, wherein a=0.17, b=200；
4th, the carrier for being coated with crystal seed layer is placed in Synthesis liquid, is put into reactor and is placed in rotary oven, is carried out together
Hydrothermal Synthesiss, temperature is 180 DEG C, and the time is 2h；
5th, washing and drying after synthesizing, in removing template TPAOH at 550 DEG C；
6th, ethanol/water separation test condition：Temperature 60 C, atmospheric pressure 101kPa, material mole constitutes ethanol content and is
10%, the gas for analyzing per-meate side with gas-chromatography (SP-3420A types gas-chromatography) is constituted.
Membrane tube test result is as shown in the table：
Claims (1)
1. a kind of pure silicon molecular sieve film preparation method using Woelm Alumina as carrier, it is characterised in that：
Using porous alumina ceramic as carrier, preparing surface has the pure silicon molecular sieve film of MFI crystal structures, Woelm Alumina pottery
The average pore size of ceramic carrier is 0.1~2 μm, and mean porosities are 10~60%；The porous alumina ceramic carrier is tubulose
Carrier, chip carrier, doughnut or multichannel carrier ceramic monolith；It is pure with secondary Hydrothermal Synthesiss using TPAOH as template
Silicon molecular sieve film；
Concrete technology step is as follows：
1) according to Synthesis liquid 3TPAOH：1Na2O：10SiO2：150H2O ratios synthesize 100~400nm Silicalite-1 balls
Shape crystal seed；
2) coat crystal seed, using vacuum method 2~10 μm of porous alumina ceramic supported on carriers crystal seed layer, then 150
Solidify 1~5h at~200 DEG C；
3) Synthesis liquid is configured, constitutes and is：aTPAOH：bNa2O：10SiO2：cH2O, wherein a=0.1~2, b=0.05~5, c=
100~200；
4) alumina ceramic carrier for being coated with crystal seed layer is placed in Synthesis liquid, is put into reactor and is placed in rotary oven, and one
Rise and carry out Hydrothermal Synthesiss, temperature is 150~200 DEG C, the time is 2~4h；
5) washing and drying after synthesizing, in removing template TPAOH at 450~550 DEG C；
6) ethanol/water separation test condition：Temperature 60 C, atmospheric pressure 101kPa, material mole composition ethanol content be 5~
10%, constituted with the gas of gas-chromatography SP-3420A type gas chromatographic analysis per-meate sides.
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| WO2017142056A1 (en) * | 2016-02-19 | 2017-08-24 | 日立造船株式会社 | Zeolite separation membrane and production method therefor |
| CN106378013B (en) * | 2016-11-10 | 2020-02-07 | 南京工业大学 | Preparation method and application of hierarchical pore molecular sieve membrane |
| CN111330455B (en) * | 2020-02-20 | 2022-01-18 | 华南理工大学 | MFI zeolite membrane for efficient dehydration of biological oil and preparation method and application thereof |
| CN115036547A (en) * | 2022-05-06 | 2022-09-09 | 黄山学院 | Preparation method of ion-conducting membrane for all-vanadium redox flow battery |
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| CN101327934A (en) * | 2008-07-17 | 2008-12-24 | 连云港三吉利化学工业有限公司 | Preparation of titanium silicon molecular sieve having MFI structure |
| CN101648712A (en) * | 2009-09-21 | 2010-02-17 | 江西师范大学 | Method for preparing high-performance Silicalite-1 molecular sieve membrane by using TPABr as template agent |
| WO2010138692A1 (en) * | 2009-05-29 | 2010-12-02 | Shell Oil Company | Method of making a gas separation molecular sieve membrane |
| CN103846018A (en) * | 2012-12-06 | 2014-06-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing NaA molecular sieve membrane by spraying crystal seeds |
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| CN1795971A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | High performance molecular sieve membrane of silicon by using ceramics of silicon dioxide as carrier, and preparation method |
| CN101837991B (en) * | 2010-05-24 | 2012-07-04 | 江西师范大学 | Preparation method of fluorine-containing MFI zeolite membrane |
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| CN101327934A (en) * | 2008-07-17 | 2008-12-24 | 连云港三吉利化学工业有限公司 | Preparation of titanium silicon molecular sieve having MFI structure |
| WO2010138692A1 (en) * | 2009-05-29 | 2010-12-02 | Shell Oil Company | Method of making a gas separation molecular sieve membrane |
| CN101648712A (en) * | 2009-09-21 | 2010-02-17 | 江西师范大学 | Method for preparing high-performance Silicalite-1 molecular sieve membrane by using TPABr as template agent |
| CN103846018A (en) * | 2012-12-06 | 2014-06-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing NaA molecular sieve membrane by spraying crystal seeds |
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