JPS6099327A - Separation film for gas - Google Patents
Separation film for gasInfo
- Publication number
- JPS6099327A JPS6099327A JP20577883A JP20577883A JPS6099327A JP S6099327 A JPS6099327 A JP S6099327A JP 20577883 A JP20577883 A JP 20577883A JP 20577883 A JP20577883 A JP 20577883A JP S6099327 A JPS6099327 A JP S6099327A
- Authority
- JP
- Japan
- Prior art keywords
- oxahexene
- plasma
- perfluoro
- gas
- film
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は気体分離膜、％に膜分啼法により天然ガス中か
らヘリウムｋｉ１４択性よ（効率的に分嘔取得し得る分
離膜に係るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas separation membrane, which can efficiently obtain helium ki14 selectively from natural gas by a membrane separation method.
ヘリウムガスは例えば核融合反応、リニアモーター等の
超電導用の極を鉱媒体として有用でめシ、今後かなりの
葉の使用が見込まれる。Helium gas is useful as a mineral medium for superconducting poles in nuclear fusion reactions, linear motors, etc., and is expected to be widely used in the future.
かかるヘリウムは天然ガスや空気中に含まれ、特に天然
ガス中にはかなシ多量に含まれている。Such helium is contained in natural gas and air, and in particular, it is contained in ephemeral amounts in large amounts in natural gas.
従来ヘリウムは仁の様な天然ガスから深冷分離等の手段
により分離取得されてきたが、これは１、備的にかなシ
大規模となり、操作的にも保守案′されて鱒ない。Conventionally, helium has been separated and obtained from natural gas such as kerosene by means such as cryogenic separation, but this method requires a large scale in terms of preparation and requires operational maintenance.
、 ”ｐ７ｙ、混合ガス中からヘリウムを得る方法とり
、Ｌｔ膜分嗟法が提案されている。この方法は直接ヘリ
ウムガスが得られ、操作的に簡単で６シ、又経済的にも
有利でるる。この様な分離膜として代表賂れるものにオ
ルガノポリクロ中サン系の膜が糧々提案されてｉる。こ
のＭｕ一般に酸素に対する透過速度中酸素分離係数（Ｐ
ｏ、／Ｐｓ、）ｒこつすでは比較的満足し得るものの、
ヘリウムガスについては分離係数が小姑＜、実用性につ
いてろまシ期待し得るものでない。As a method for obtaining helium from a mixed gas, the Lt membrane fractionation method has been proposed. This method allows helium gas to be obtained directly, is operationally simple, and is economically advantageous. As a typical example of such a separation membrane, an organopolychloride-based membrane has been proposed.In general, the oxygen separation coefficient (P) in the permeation rate for oxygen is
o, /Ps,)r Although it is relatively satisfactory,
As for helium gas, the separation coefficient is less than that, so there is no hope for practicality.
本発明者はかかる点に鑑み、分離係数（ＰＨｅ／Ｂ、）
とヘリワムの透過速度が高いレベルでバランスし、しか
もその性能が安定して持続し得る分離ｍｔ−得ることを
目的として種々研究、検討した結果、特定のパーフルオ
ロ化合物を膜素材として用いることにより紡記目的を達
成し得ることを見出した。In view of this, the present inventor has determined that the separation coefficient (PHe/B,)
As a result of various studies and examinations aimed at obtaining a separation mt-type in which the permeation rates of heliwam and heliwam are balanced at a high level and whose performance is stable and long-lasting, we have found that by using a specific perfluorinated compound as a membrane material, we have developed a method for spinning. We have found that the above objectives can be achieved.
かくして本発明は多孔質膜上にパーフルオロ−３−オキ
サヘキセン−１ｔ−プラズマ重合せし慢性が平均細孔径
１０〜２０００ Ｍ、空気の透’−ｉ聯＞速度ａ ｘ
１０−４〜ａ ｘ ｔ Ｏ−”ｎｕ”／ｃｍ”ｅｅａ
０１１ ＨｇＩを′１有するのが適当である。Thus, the present invention provides perfluoro-3-oxahexene-1t-plasma polymerization on a porous membrane, which has an average pore diameter of 10 to 2000 M and an air permeation rate a x
10-4~a x t O-"nu"/cm"eea
It is suitable to have 011 HgI '1.
１これら物性が帥記範題を逸脱する場合には充分゛なガ
ス透過速度が得難く、又超薄膜を積層する際欠陥を生じ
易くなる虞れがあるので好ましくない。かかる膜の材質
としては、例えばポリスルホン、ポリアミド、ポリアク
リロニトリル、ポリエチレン、ポリビニルアルコール、
ポリテトラフルオロエチレン等が挙けられる。1. If these physical properties deviate from the standard range, it is not preferable because it is difficult to obtain a sufficient gas permeation rate and defects may easily occur when laminating ultra-thin films. Examples of the material for such a membrane include polysulfone, polyamide, polyacrylonitrile, polyethylene, polyvinyl alcohol,
Examples include polytetrafluoroethylene.
そして本発明においては前述の多孔質支持膜上にパーフ
ルオロ−３−オキサヘキセン−１ｆｔ薄膜状にプラズマ
重合せしめる。プラズマ重合に供せられるパーフルオロ
−３−オキサヘキセン−１の１製は例えば次に示す一連
の反応でヘキサフルオロプロペンより製造される。In the present invention, perfluoro-3-oxahexene is plasma-polymerized to form a 1 ft. thin film on the above-mentioned porous support membrane. Perfluoro-3-oxahexene-1 to be subjected to plasma polymerization is produced, for example, from hexafluoropropene through the following series of reactions.
又、プラズマ重合手段としては、モノマー供ｉ弁、電極
、アース電極、アース電極冷却部、−′周波電源、ガラ
ス製ペルジャー、排気系よシプラズマ重合条件としては
前記ペルジャー型プラズマ重合装置を用−れは圧力α０
１〜５ｔｏｒｒ 、バー２ルオロー３−オキサヘキセン
の流最１〜１０ Ｅｌ Ｏｍ”／ｍｉｎ 、高周波出力
１〜２００Ｗを任用するのが適当である。餉記以外□′
の重合装置を用いても、これらの条件を最適化してプ
ラズマ重合動行うのはこの技術に習熟している者にとっ
て比較的容易である。Further, as a plasma polymerization means, a monomer supply valve, an electrode, a ground electrode, a ground electrode cooling unit, a -' frequency power supply, a glass Pelger, and an exhaust system are used.As for the plasma polymerization conditions, the above-mentioned Pelger type plasma polymerization apparatus is used. is the pressure α0
It is appropriate to use a flow rate of 1 to 5 torr, a maximum flow rate of 1 to 10 El Om''/min, and a high frequency output of 1 to 200 W.
Even if a polymerization apparatus is used, it is relatively easy for a person skilled in this technology to optimize these conditions and perform a plasma polymerization operation.
プラズマ重合によ抄多孔１ｌｔｌｌＫ上に設けられるパ
ーフルオロ−３−オキサヘキセン−１膜の厚きけ、ａ０
１〜５０μ、好ましくは１０５〜ｔＯｐ：４’ｌＦ：を
採用するのが適当である。Thickness of perfluoro-3-oxahexene-1 film provided on paper porous 1ltllK by plasma polymerization, a0
It is appropriate to employ 1 to 50μ, preferably 105 to tOp:4'IF:.
膜の厚さが前記６６囲七吐脱する場合には膜に欠陥を生
じ易くなるか、又轄充分なガス透過速度が４′４＊１く
なる等の虞れかあるので好ましくなり。If the thickness of the membrane exceeds the above-mentioned 66 mm, it is not preferable because there is a risk that defects will occur in the membrane or that the sufficient gas permeation rate will be reduced to 4'4*1.
かくして得られた気体の分＠ａは、特にヘリ＝、’；！
’Ｎムに対するが択分噛透過性が診れて埴るが、ｊ′鴫
１等にも有用である。The gas fraction @a obtained in this way is especially Heli=,';!
It is useful for 'N' because of its selective permeability, but it is also useful for 'J' and the like.
１次に本発明を実施例によ！ｌｌ説明する。First, the present invention will be explained as an example! I will explain.
ペルジャー型プラズマ重合装置ｔを用−１空気の透過速
度がａ ｘ １０−” ｃｘｎ”／ｃｍ” Ｂｅｅ ｃ
ｍ Ｈｇ ｓ平均細孔径がｓｏＸ、直径８０−のポリス
ルホン多孔質膜をアース電極上に固定した。Using a Pelger type plasma polymerization apparatus, the permeation rate of air is a x 10-"cxn"/cm"Bee c
A polysulfone porous membrane with an average pore size of 80 mm and a diameter of 80 mm was fixed on a ground electrode.
真空ボンダによりペルジャー内を脱気し、排気を続けな
からモノマー供給バルブを通して／（−フルオロ−３−
オキサヘキセン−１を４０ｎｎ”／ ｙ３１ｎで供給し
た。ペルジャー内の圧力は０、３ ｔｏｒｒ となった
。電極間に１ 、％ ５６ Ｍｉｌ！ 。Degas the inside of the Pelger using a vacuum bonder, continue evacuation, and add /(-fluoro-3-
Oxahexene-1 was supplied at 40 nn"/y31n. The pressure inside the Pelger was 0.3 torr. 1.% 56 Mil! between the electrodes.
ＳＯＷの高周波出力を印加してパーフルオロ−５−オキ
サヘキセン−１を多孔質膜上へｔｏ分間プラズマ重合し
た。Perfluoro-5-oxahexene-1 was plasma-polymerized onto the porous membrane for to minutes by applying high-frequency power of SOW.
得られたグツズｉ重合膜の膜厚は（Ｌ２３μであった。The film thickness of the obtained Gutsuzu i polymer film was (L23μ).
Ｈｇ 、 ００１．８２の各ガスの透過性能を測定した
結果を以下に示す。The results of measuring the permeation performance of each gas, Hg and 001.82, are shown below.
Ｈｅノ透過速度 ９．５ Ｘ １０−’ ｃｒｔ？／ｅ
！ ｓｅａ ６１１ Ｈｇ１（ｅ Ｏ透過係数 Ｚ２８
１０−魯 １００２の透過速度 直ｌＸ１０−４ １Ｃ
ｏ、の透過係数 ｔ４Ｘ１０−’ ｚＮ！ の透過速度
Ｚ３Ｘ１０−’ ＃Ｎ３ の重過係数 １．７ ×１
０−１１１Ｈθ／Ｎ！の分嘔係数 １３
００＆／１１！ Ｏ分離係数 ａ４He permeation rate 9.5 x 10-' crt? /e
! sea 611 Hg1 (e O permeability coefficient Z28
10-Lu 1002 permeation rate Direct 1X10-4 1C
The transmission coefficient of o, t4X10-' zN! Transmission rate of Z3X10-' Loading coefficient of #N3 1.7 ×1
0-111Hθ/N! Minute coefficient of 13 00&/11! O separation factor a4
Claims (1)
／ｌｓ” ｓｅａ ｃｍ Ｈｇである端末の範囲（１）
の分離膜。 ニルアルコール、ポリテトラフルオロエチレンである請
求の範囲（１）又ｔｉｔ １２）の分離膜。 ４、バーフルオロ−５−オキサヘキセン−１１１合体の
膜厚は（ＬＯ１〜＆０μである請求の範囲（１）の分＠
１７４６[Claims] A membrane that separates. Porous yX mori average pore diameter 10-2000μ1, Im
/ls” sea cm Hg terminal range (1)
separation membrane. The separation membrane according to claim (1) or tit 12), which is made of alcohol or polytetrafluoroethylene. 4. The thickness of the combined barfluoro-5-oxahexene-111 is (LO1~&0μ) Claim (1) @
1746
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577883A JPH0236292B2 (en) | 1983-11-04 | 1983-11-04 | KITAIOBUNRISURUMAKU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577883A JPH0236292B2 (en) | 1983-11-04 | 1983-11-04 | KITAIOBUNRISURUMAKU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6099327A true JPS6099327A (en) | 1985-06-03 |
| JPH0236292B2 JPH0236292B2 (en) | 1990-08-16 |
Family
ID=16512510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20577883A Expired - Lifetime JPH0236292B2 (en) | 1983-11-04 | 1983-11-04 | KITAIOBUNRISURUMAKU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0236292B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03101817A (en) * | 1989-05-15 | 1991-04-26 | Pall Corp | Hydrophobic membrane |
| US5246743A (en) * | 1991-11-26 | 1993-09-21 | Ube Industries, Ltd. | Method of enhancing gas separation performance of an aromatic polyimide membrane |
-
1983
- 1983-11-04 JP JP20577883A patent/JPH0236292B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03101817A (en) * | 1989-05-15 | 1991-04-26 | Pall Corp | Hydrophobic membrane |
| US5246743A (en) * | 1991-11-26 | 1993-09-21 | Ube Industries, Ltd. | Method of enhancing gas separation performance of an aromatic polyimide membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0236292B2 (en) | 1990-08-16 |
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