JPH0724743B2 - Method for producing molecular sieve carbon membrane - Google Patents
Method for producing molecular sieve carbon membraneInfo
- Publication number
- JPH0724743B2 JPH0724743B2 JP3122066A JP12206691A JPH0724743B2 JP H0724743 B2 JPH0724743 B2 JP H0724743B2 JP 3122066 A JP3122066 A JP 3122066A JP 12206691 A JP12206691 A JP 12206691A JP H0724743 B2 JPH0724743 B2 JP H0724743B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular sieve
- membrane
- sieve carbon
- carbon membrane
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 31
- 239000012528 membrane Substances 0.000 title claims description 31
- 239000002808 molecular sieve Substances 0.000 title claims description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 29
- 229910052799 carbon Inorganic materials 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 14
- 239000004642 Polyimide Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920006254 polymer film Polymers 0.000 claims 2
- 239000007789 gas Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- 229920005597 polymer membrane Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005371 permeation separation Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガス分離や異性体分離
などにおいて良好な分離性能および分離効率を示す分子
篩炭素膜に関するものである。TECHNICAL FIELD The present invention relates to a molecular sieve carbon membrane which exhibits good separation performance and separation efficiency in gas separation, isomer separation and the like.
【０００２】[0002]
【従来の技術】粒状の分子篩炭素は、樹脂の炭素化や活
性炭の後処理により作製され、吸着作用による空気中の
窒素の分離に一部実用化されている。この分子篩炭素は
その性質から、ゼオライトのような異性体分離作用も有
しており、成膜により様々な分離操作への利用が期待さ
れる。従来、ポリアクリロニトリルやポリフルフリルア
ルコール等から作成された分子篩炭素膜に関する研究例
があるが、これらは割れやピンホールのために、ガス透
過において、はっきりとした分子篩作用を示さなかっ
た。また、分離膜として実用化するには薄膜化が必要で
あるが、炭素化の際の収縮のため、多孔質の金属やガラ
スなどの支持基体への複合化が困難で、分離膜として未
だ実用に至っていない。2. Description of the Related Art Granular molecular sieve carbon is produced by carbonizing a resin or after-treating activated carbon, and is partially put into practical use for separating nitrogen in air by an adsorption action. Due to its nature, this molecular sieve carbon also has an isomer separation effect like zeolite, and is expected to be used for various separation operations by forming a film. Conventionally, there have been studies on molecular sieve carbon membranes made of polyacrylonitrile, polyfurfuryl alcohol, etc., but these did not show a clear molecular sieve action in gas permeation due to cracks and pinholes. In addition, it is necessary to make the film thinner to put it into practical use as a separation membrane, but due to shrinkage during carbonization, it is difficult to combine it with a supporting substrate such as porous metal or glass, and it is still practical as a separation membrane. Has not reached.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、透過におい
ての分子篩性能の妨げとなる割れがなく、しかも分離効
率の向上した分子篩炭素膜及びその工業的に有利な製造
方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a molecular sieve carbon membrane which is free from cracks which impede the performance of the molecular sieve during permeation and which has an improved separation efficiency, and an industrially advantageous production method thereof. .
【０００４】[0004]
【課題を解決するための手段】本発明によれば、第一
に、芳香族ポリイミド系高分子膜を炭素化してなる分子
篩炭素膜が提供され、第二に、芳香族ポリイミド系高分
子膜を単独で、もしくは多孔質基体に支持された複合膜
の形で、炭素化することを特徴とする分子篩炭素膜の製
造方法が提供される。According to the present invention, firstly, a molecular sieve carbon film obtained by carbonizing an aromatic polyimide-based polymer film is provided, and secondly, an aromatic polyimide-based polymer film is provided. There is provided a method for producing a molecular sieve carbon membrane, which comprises carbonizing the membrane alone or in the form of a composite membrane supported on a porous substrate.
【０００５】本発明の分子篩炭素膜は収縮はするものの
形状を保持したままで炭素化し得る芳香族ポリイミド系
高分子を原料として用いたことから、一般に、１０オン
グストローム以下の均質な微細孔を有し、しかも透過に
おいての分子篩性能の妨げとなる割れがなく、しかも分
離効率の向上したものである。すなわち、本発明品であ
る分子篩炭素膜は、通常の活性炭とは異なり、分子レベ
ルの大きさの細孔のみが存在するため、ガス分子を大き
さで篩い分けることができる。例えば実施例の図１に示
されるように、５オングストローム以下の細孔をもつも
のでは、それ以上の分子径をもったイソブタンが膜内部
に入ることがないので、イソブタンを分離することがで
きる。したがって、本発明の分子篩炭素膜の特徴は、第
一にある程度大きさの異なるガス分子については、適当
な細孔径に調製した分子篩炭素膜を用いることで、分子
篩作用によりほぼ完全に分離することができる点にあ
り、第二に、分子の大きさがそれほど違わない窒素、酸
素、二酸化炭素などについても、吸着−拡散機構によっ
て分離が行える点にある。本発明品である分子篩炭素膜
では、ヘリウムよりも分子運動が遅い二酸化炭素の方が
透過速度（透過係数）が速いことから、この機構でガス
の透過分離が起こることが裏づけられる。すなわち実施
例１に示したガス透過係数の比が透過速度比であり、Ｃ
Ｏ２／Ｏ２で１０倍、ＣＯ２／Ｎ２では５０倍となり、
従来の炭素膜による透過速度比と比較するとその性能の
違いは顕著である。Since the molecular sieve carbon film of the present invention uses as a raw material an aromatic polyimide polymer capable of being carbonized while retaining its shape although it shrinks, it generally has uniform fine pores of 10 angstroms or less. Moreover, there are no cracks that impede the performance of the molecular sieve in permeation, and the separation efficiency is improved. That is, unlike the conventional activated carbon, the molecular sieve carbon membrane which is the product of the present invention has only pores of a molecular level size, so that gas molecules can be sieved by size. For example, as shown in FIG. 1 of the example, with a pore having a pore size of 5 angstroms or less, isobutane having a molecular diameter larger than that does not enter the inside of the membrane, so isobutane can be separated. Therefore, the feature of the molecular sieve carbon membrane of the present invention is that, for gas molecules having different sizes to some extent, it can be almost completely separated by the molecular sieve action by using the molecular sieve carbon membrane prepared to have an appropriate pore size. Secondly, nitrogen, oxygen, carbon dioxide, etc., whose molecular sizes are not so different, can be separated by an adsorption-diffusion mechanism. In the molecular sieve carbon membrane of the present invention, carbon dioxide, which has a slower molecular motion than helium, has a higher permeation rate (permeation coefficient), which confirms that permeation separation of gas occurs by this mechanism. That is, the ratio of gas permeation coefficients shown in Example 1 is the permeation rate ratio, and C
O 2 / O 2 is 10 times, CO 2 / N 2 is 50 times,
The difference in the performance is remarkable when compared with the transmission rate ratio by the conventional carbon membrane.
【０００６】本発明の分子篩炭素膜は、芳香族ポリイミ
ド系高分子膜を単独で炭素化することにより、あるいは
芳香族ポリイミド系高分子膜を多孔質体に支持された複
合膜を炭素化することにより得られる。The molecular sieve carbon membrane of the present invention is obtained by carbonizing an aromatic polyimide polymer membrane alone or by carbonizing a composite membrane in which an aromatic polyimide polymer membrane is supported by a porous body. Is obtained by
【０００７】本発明において、原料として用いる芳香族
系ポリイミドとしては、従来公知のものがいずれも使用
できるが、好ましくはポリ−４，４’−オキシジフェニ
レンピロメリットイミド等が使用される。また、本発明
における炭素化は、通常の炭化条件が採用され、たとえ
ばアルゴン、窒素などの不活性ガス中において、５００
〜１５００℃前後まで電気炉を用いて焼成することによ
って行なわれる。In the present invention, as the aromatic polyimide used as a raw material, any conventionally known one can be used, but poly-4,4'-oxydiphenylenepyromellitimide is preferably used. For carbonization in the present invention, ordinary carbonization conditions are adopted. For example, in an inert gas such as argon or nitrogen, 500
It is carried out by firing in an electric furnace up to about 1500 ° C.
【０００８】本発明における分子篩炭素膜は、前記した
ように芳香族ポリイミド系高分子膜単独を炭素化するこ
とにより得られるが、好ましくは該芳香族ポリイミド高
分子膜と多孔質支持体との複合膜を炭素化することが好
ましい。この場合、多孔質支持体の材料として芳香族系
ポリイミドを用いると、支持体と炭素膜との炭素化時の
収縮率が同等となるから、分子篩性能の妨げとなる割れ
がなく、しかも非常に薄い分子篩炭素層を有する炭素膜
を得ることができる。The molecular sieve carbon membrane in the present invention is obtained by carbonizing the aromatic polyimide polymer membrane alone as described above, but preferably the composite of the aromatic polyimide polymer membrane and the porous support is used. It is preferred to carbonize the membrane. In this case, when an aromatic polyimide is used as the material of the porous support, the contraction rate at the time of carbonization of the support and the carbon film becomes equal, so there is no crack that hinders the molecular sieve performance, and very A carbon membrane having a thin molecular sieve carbon layer can be obtained.
【０００９】[0009]
【実施例】以下、実施例により本発明を更に詳細に説明
する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００１０】実施例１ ポリ−４，４’−オキシジフェニレンピロメリットイミ
ドフィルムから単独の分子篩炭素膜（２０μｍ）を製造
し、まずその特性値を決定した。炭素化は、８００℃ま
で昇温速度３℃／ｍｉｎの条件でアルゴン雰囲気下で行
った。その吸着等温線からこの膜には、ノルマルブタン
は進入できるが、イソブタンは進入できない大きさの孔
（５オングストローム以下）が発達していることが明ら
かである（図１）。そのガス透過係数（２０℃）は水
素、ヘリウム、窒素、酸素、二酸化炭素、イソブタンに
対して、それぞれ７．５×１０−９、５．１×１０
−１０、２．６×１０−１１、１．２×ｘ１０−１０、
１．３×１０−９、＜１０−１３（測定限界以下）ｃｍ
３（ＳＴＰ）・ｃｍ／ｃｍ２・ｓｅｃ・ｃｍＨｇであっ
た。この結果から、透過においても、イソブタンに対す
る明らかな分子篩作用を示しており、また水素、二酸化
炭素の透過が他のガスより速いという特徴を示してい
る。Example 1 A single molecular sieve carbon membrane (20 μm) was prepared from a poly-4,4'-oxydiphenylenepyromellitimide film, and its characteristic values were first determined. Carbonization was performed in an argon atmosphere at a temperature rising rate of 3 ° C / min up to 800 ° C. From the adsorption isotherm, it is clear that normal membranes (5 angstroms or less) are developed in this membrane, but normal butane can penetrate into the membrane (Fig. 1). Its gas permeability coefficient (20 ° C.) is 7.5 × 10 −9 and 5.1 × 10 with respect to hydrogen, helium, nitrogen, oxygen, carbon dioxide, and isobutane, respectively.
−10 , 2.6 × 10 −11 , 1.2 × x10 −10 ,
1.3 × 10 −9 , <10 −13 (below measurement limit) cm
It was 3 (STP) * cm / cm < 2 > * sec * cmHg. From these results, the permeation shows a clear molecular sieving action for isobutane, and the characteristic that hydrogen and carbon dioxide permeate faster than other gases.
【００１１】実施例２ 実施例１と同じポリマーを用いて、緻密なポリイミド薄
層が多孔質ポリイミド基体（厚さ０．１ｍｍ）に支持さ
れた複合高分子膜を作成した。上述と同様の条件で炭素
化し、緻密層を分子篩炭素層に変換した。この膜のガス
透過速度は、単独の膜よりおよそ１００倍速くなった
が、それぞれのガスの間での透過係数比は同等であり、
分子篩炭素層に複合化による割れ等は生じていないこと
が示された。Example 2 The same polymer as in Example 1 was used to prepare a composite polymer membrane in which a dense polyimide thin layer was supported on a porous polyimide substrate (thickness 0.1 mm). Carbonization was performed under the same conditions as above, and the dense layer was converted into a molecular sieve carbon layer. The gas permeation rate of this membrane was about 100 times faster than the single membrane, but the permeation coefficient ratio between each gas was the same,
It was shown that the molecular sieve carbon layer did not have cracks and the like due to compounding.
【００１２】[0012]
【発明の効果】本発明の分子篩炭素膜は、高い耐熱性、
耐蝕性を有する他に、水素、二酸化炭素の透過速度が他
のガスに比べて大きく、また分子篩作用により分子径の
大きなガスは透過しないという特性を示す。したがっ
て、高温で利用される化学工業廃ガス中の水素や二酸化
炭素の分離など、広範な用途に用いられる。The molecular sieve carbon membrane of the present invention has high heat resistance,
In addition to having corrosion resistance, it exhibits the characteristics that the permeation rate of hydrogen and carbon dioxide is higher than that of other gases, and that the gas having a large molecular diameter does not permeate due to the molecular sieving action. Therefore, it is used for a wide range of applications such as separation of hydrogen and carbon dioxide in waste gas of chemical industry used at high temperature.
【図１】実施例で得た分子篩炭素膜の二酸化炭素、ノル
マルブタン、イソブタンに対する、２５℃における吸着
等温線である。FIG. 1 is an adsorption isotherm at 25 ° C. for carbon dioxide, normal butane and isobutane of a molecular sieve carbon membrane obtained in an example.
Claims (3)
てなる分子篩炭素膜。1. A molecular sieve carbon film obtained by carbonizing an aromatic polyimide polymer film.
もしくは多孔質基体に支持された複合膜の形で、炭素化
することを特徴とする分子篩炭素膜の製造方法。2. An aromatic polyimide polymer film alone,
Alternatively, a method for producing a molecular sieve carbon membrane, which comprises carbonizing in the form of a composite membrane supported on a porous substrate.
製した多孔質体であることを特徴とする請求項２の分子
篩炭素膜の製造方法。3. The method for producing a molecular sieve carbon membrane according to claim 2, wherein the substrate is a porous body made of an aromatic polyimide polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3122066A JPH0724743B2 (en) | 1991-04-24 | 1991-04-24 | Method for producing molecular sieve carbon membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3122066A JPH0724743B2 (en) | 1991-04-24 | 1991-04-24 | Method for producing molecular sieve carbon membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04326930A JPH04326930A (en) | 1992-11-16 |
| JPH0724743B2 true JPH0724743B2 (en) | 1995-03-22 |
Family
ID=14826791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3122066A Expired - Lifetime JPH0724743B2 (en) | 1991-04-24 | 1991-04-24 | Method for producing molecular sieve carbon membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0724743B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5897915A (en) * | 1996-10-28 | 1999-04-27 | Corning Incorporated | Coated substrates, method for producing same, and use therefor |
| JP2000237562A (en) * | 1999-02-23 | 2000-09-05 | Kanebo Ltd | Molecular sieve carbon membrane and its production, and pervaporation separation method |
| EP1723999B1 (en) | 2004-03-12 | 2017-06-07 | NGK Insulators, Ltd. | Carbon film laminate and method for production thereof, and voc removing device |
| JP5516951B2 (en) * | 2007-10-12 | 2014-06-11 | 大陽日酸株式会社 | Gas purification method |
| CN101306327B (en) | 2008-07-08 | 2012-03-14 | 大连理工大学 | Spiral carbon membrane and preparation method thereof |
| JP5853530B2 (en) * | 2011-09-20 | 2016-02-09 | 東洋紡株式会社 | Hollow fiber carbon membrane, separation membrane module, and method for producing hollow fiber carbon membrane |
| JP5853529B2 (en) * | 2011-09-20 | 2016-02-09 | 東洋紡株式会社 | Hollow fiber carbon membrane and method for producing the same |
| JP5906674B2 (en) * | 2011-11-02 | 2016-04-20 | 東洋紡株式会社 | Hollow fiber carbon membrane and method for producing the same |
| CN106823821A (en) * | 2015-12-04 | 2017-06-13 | 中国科学院大连化学物理研究所 | The complementing method of Carbon Molecular Sieve Membrane defect |
| JP6935645B2 (en) * | 2017-03-02 | 2021-09-15 | 国立大学法人広島大学 | Gas separation membrane, gas separation module and gas separation device |
| CN110740804B (en) * | 2017-06-15 | 2022-05-27 | 陶氏环球技术有限责任公司 | Supported carbon molecular sieve diaphragm and forming method thereof |
| CN115414805B (en) * | 2022-08-16 | 2023-08-11 | 大连理工大学 | A kind of preparation method of high-throughput polyaryletherketone-based carbon membrane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60202703A (en) * | 1984-03-26 | 1985-10-14 | Toray Ind Inc | Carbon membrane |
| JPS6147827A (en) * | 1984-08-10 | 1986-03-08 | Kuraray Co Ltd | Hollow activated carbon fiber |
-
1991
- 1991-04-24 JP JP3122066A patent/JPH0724743B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04326930A (en) | 1992-11-16 |
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