JPS6099323A - Gas separation film - Google Patents
Gas separation filmInfo
- Publication number
- JPS6099323A JPS6099323A JP20577483A JP20577483A JPS6099323A JP S6099323 A JPS6099323 A JP S6099323A JP 20577483 A JP20577483 A JP 20577483A JP 20577483 A JP20577483 A JP 20577483A JP S6099323 A JPS6099323 A JP S6099323A
- Authority
- JP
- Japan
- Prior art keywords
- plasma
- perfluoro
- film
- porous
- methyl
- 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】
本発明はガス分離膜、特に膜分離法により天然ガス中か
らヘリウムを選択性よく効率的に分離取得し得る分＠膜
に係るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas separation membrane, and particularly to a membrane that can efficiently separate and obtain helium from natural gas with good selectivity by a membrane separation method.
ヘリクムガスは例えば核融合反応、リニアモーター等の
超電導用の極低温媒体として有用であシ、今後かなシの
量の使用が見込まれる。Helicum gas is useful as a cryogenic medium for superconducting devices such as nuclear fusion reactions and linear motors, and is expected to be used in large quantities 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
ガス中にはかなカ多量に含まれている。Such helium is contained in natural gas and air, and in particular, natural gas contains a fleeting amount of helium.
従来ヘリウム酸この様な天然ガスから深冷分畦恒關）手
段により分離取得されてきたが、これは＋ｎ＋８１１備
的にかな）大規模となシ、操作的にも保守’；、ｉａ−
的にもがなり煩雑なものであった。Conventionally, helium acid has been separated and obtained from such natural gas by means of cryogenic separation ridges, but this is difficult to do on a large scale and operationally maintenance-free.
It was difficult and complicated.
更に、前記の如き超電導に用いたヘリウムガ″スの回収
に当っては従来それ桿有効な手段は提、５
、案されていなめ。Furthermore, in the recovery of the helium gas used in superconductivity as described above, no effective means have been proposed so far.
’ｊイ也方、混合ガス中からヘリウムを得る方法として
膜分離法が提案されている。この方法＃ｉ直接ヘリウム
ガスが得られ、操作的に簡単で７ｂシ、又経済的にも有
利である。この様な分離膜として代表されるものにオル
ガノボリア０キサン系の膜が種々提案されている。この
膜は一般に敵素に対する透過速度や酸素分離係数（ＰＯ
，／ＰＮ、 ）９について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ｌトさく、実用性に
ついてあまり期待し得るものでない。On the other hand, a membrane separation method has been proposed as a method for obtaining helium from a mixed gas. This method #i directly obtains helium gas, is operationally simple, and is also economically advantageous. Various organoboria xane-based membranes have been proposed as typical examples of such separation membranes. This membrane generally has a permeation rate and an oxygen separation coefficient (PO
, /PN, )9 is relatively satisfactory, but
As for helium gas, the separation coefficient is low, so it is not very promising for practical use.
本発明者はかかる点に鑑み、分岐係数（ＰＥｅ／ＰＮ、
）と５リウ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膜を得ることを
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前記目的を達
成し得ることを見出した。In view of this point, the present inventor has determined that the branching coefficient (PEe/PN,
) and 5-lium permeation rate at a high level, and whose performance can be maintained stably and sustainably.As a result of various studies and examinations, we decided to use a specific perfluorinated compound as the membrane material. It has been found that the above object can be achieved.
かくして本発明は多孔質膜）：ｒｃパーフルオロｆ’Ａ
！ｌ、ドロージオキサ（５メチル）ノネン−１をブイ岬
、！−１ｒマ重合せしめて成るガス分離膜を提供する１
１ｆ−２姫る・
本発明に用いられる多孔質膜としては、その網（Ｐが平
均細孔径１０〜２０００Ｘ、空気の透−導度４ Ｘ １
０−’♂／儒２８０Ｃ儒Ｈｇ を有するの１ｆｉｊ Ｐ
当である。Thus, the present invention provides a porous membrane): rc perfluoro f'A
! l, drodioxa (5 methyl) nonene-1 at Cape Bui,! -Providing a gas separation membrane formed by polymerizing a 1r polymer 1
1f-2 Himeru・The porous membrane used in the present invention has a network (P is an average pore diameter of 10 to 2000X, and an air permeability of 4X1).
1fij P with 0-'♂/Fu280CFuHg
That's true.
これら物性が前記範囲を逸脱する場合には充−’−−級
洲ガス透過速度が得難く、又超薄膜を積層す、４ ％ｈ
、、ＩＩＡ欠陥を生じ易くなる虞れがあるので好ましく
ない。If these physical properties deviate from the above range, it will be difficult to obtain a high-grade gas permeation rate, and it will be difficult to obtain a high gas permeation rate of 4% h.
, , is undesirable because it may easily cause IIA defects.
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げら
れる。Examples of the material for such a membrane include polysulfone, polyamide, polyacrylonitrile, polyethylene, polyvinyl alcohol, and polytetrafluoroethylene.
そして本発明においては萌述の多孔質支持膜上にパーフ
ルオロ−４６−ジオキサ（５メチル）ノネン−１（ＰＨ
ＶＩと略称する）を薄膜状にプラズマ重合せしめる。In the present invention, perfluoro-46-dioxa(5-methyl)nonene-1 (PH
(abbreviated as VI) is plasma polymerized into a thin film.
；’ラズーｒ重合に供せられるＰＨＶＨｔｖ ＩＩ＃
１ｌｉｌ ｉｄ、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。;'PHVHtv II# subjected to lazu r polymerization
1liil id, for example, is produced from hexafluoropropene in the following reaction series.
（三量体） ＯＦ −ＯＦ −０−ＯＦ！−ＯＦ −０−０３Ｆ。(trimer) OF -OF -0-OF! -OF -0-03F.
１Ｆｍ
又１、プラズマ重合手段としては、モノマー供給弁、電
極、アース電極、アース電極冷却部、高周波Ｗ源、ガラ
ス製ペルジャー、排気系より構成される。通常よく知ら
れているベルジャー型プラズマ重合装Ｒｅ用いることが
出来る。1Fm Also, 1. The plasma polymerization means is composed of a monomer supply valve, an electrode, a ground electrode, a ground electrode cooling section, a high frequency W source, a glass Pel jar, and an exhaust system. A well-known bell jar type plasma polymerization system Re can be used.
プラズマ重合φ件としてＦｉ繭記ペルジャー型プラズマ
重合装置ｔ用いれば圧力［Ｌ０１〜５ｔｏｒｒ ％ＰＨ
ＶＢの流ＦＩＬ １〜１０ Ｃ１Ｏｃｍ”／ ｍｉｎ
、高周波出力１〜２００Ｗ％−採用するのが適当でらる
。前記以外の歌合装＃を用いても、これらの条件を最適
化してプラズマ重合を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める。If plasma polymerization is used in a Pelger type plasma polymerization device, the pressure [L01~5 torr %PH
VB flow FIL 1~10 C1Ocm”/min
, it is appropriate to adopt a high frequency output of 1 to 200 W%. Even if a combination # other than those described above is used, it is relatively easy for a person familiar with this technique to optimize these conditions and perform plasma polymerization.
プラズマ重合によシ多孔質幌上に設けられるＰＨＩ！！
１１１１Ｏ厚さは［Ｌ０１〜５．０μ、好まシくハα０
５〜１．０μ程度を採用するのカニ１１ｒ１当である。PHI installed on a porous canopy by plasma polymerization! !
1111O thickness is [L01~5.0μ, preferably Haα0
It is per crab 11r that adopts about 5 to 1.0μ.
膜の厚さが繭紀範囲を逸脱する場合には塀に欠陥を生じ
易くなるか、又は充分なガス透過速１１；”Ｎｉｉ峠得
難くなる等の虞れがあるので好ましくな・や゛ろｌ
の、１１ハ酸素や炭酸ガス等のガスに対する選択透過畦
も実用的であり、これらガスの濃縮或は分噸ｔ、等にも
有用である。If the thickness of the film deviates from the range, it is not preferable because there is a risk that defects may occur in the wall or it may be difficult to obtain a sufficient gas permeation rate. A selective permeation ridge for gases such as oxygen and carbon dioxide gas is also practical, and is also useful for concentrating or separating these gases.
茨に本発明を実施例により説明する。The present invention will be further explained by way of examples.
実施例
ベルジャー型プラズマ重合装ａを用い、空気の透過速度
が４８１０−”３ゾロＢ” ８８０ （ＭＩ Ｈｇ ｓ
平均細孔径が５ＯＫ、直径８０ｍ＋のポリス゛ルホン
多孔質膜ケアース電極上に固定した。Example A bell jar type plasma polymerization apparatus a was used, and the air permeation rate was 4810-"3 zoro B" 880 (MI Hg s
It was fixed on a polysulfone porous membrane care electrode with an average pore diameter of 5 OK and a diameter of 80 m+.
真空ポンプによりペルジャー内を脱気Ｌ、４Ｊｌｉ気を
続けなからモノマー供給〕くルブを通してｐｎｖＪ！！
を４０ ｔｖｎ”７ ｍｉｎで供給した。ペルジャー内
の圧力は９．２．ｔｏｒｒ となった。電極１１１１に
１５５６Ｍｎ２，５０Ｗの高周波出力を印加してｐＨｖ
ｘを多孔質膜上へ１．０分間プラズマ重合した。The inside of the Pel jar is deaerated with a vacuum pump, and the monomer is supplied through the lube. !
was supplied at a rate of 40 tvn"7 min. The pressure inside the Pelger was 9.2 torr. A high frequency output of 1556Mn2, 50W was applied to the electrode 1111 to adjust the pHv.
x was plasma polymerized onto the porous membrane for 1.0 minutes.
得られたプラズマ重合膜の膜厚は０．２２μであった。The thickness of the obtained plasma polymerized film was 0.22μ.
Ｈｅ 、 ００２ 、 Ｈ２の各ガスの透過性能を測作
した結果を以下に示す。The results of measuring the permeability of He, 002, and H2 gases are shown below.
Ｈｅ の透過速度 １．２Ｘ １０−” ａａｌｔｙｌ
ｓｅｅｍ ＨｇＨｅの透過係数 ２．８Ｘ１０−’
ａｏ２の透過速度 ５．５Ｘ１０−４
００、の透過係数 １．２Ｘ１０’
Ｎ２ の透過速度 ６．７Ｘ １０−’Ｎコ、の透過係
数 １．５Ｘ Ｉ Ｑ−９Ｈｅ／Ｎ！の分離係数 ′１
８
００、／Ｎ２の分離係数 ８．３He permeation rate 1.2X 10-” aaltyl
seem HgHe permeability coefficient 2.8X10-' ao2 permeation rate 5.5X10-4 00, permeation coefficient 1.2X10' N2 permeation rate 6.7X 10-'N2 permeation coefficient 1.5X I Q- 9He/N! Separation factor ′1
8 00, /N2 separation factor 8.3
Claims (1)
Ｆ （５メチル）ノネン−１ｔ−プラズマ重合セユ・
多孔＊模はポリスルホン、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である請求の範囲（１）又は（２
）の分離膜。 ４、 パーフルオロ−４６−ジオキサ（５メチルフノネ
ン−１重合体の膜厚は０．０１〜５．０μである請求の
範１ｆｆ１（１）の分４１[Claims] 11% perfluoro-3,6-thioxy on porous s)
F (5-methyl)nonene-1t-plasma polymerization
Claim (1) or (2) the porous pattern is polysulfone, polyamide, polyacrylonitrile, polyethylene, polyvinyl alcohol, polytetrafluoroethylene.
) separation membrane. 4. The film thickness of perfluoro-46-dioxa(5-methylfunonene-1 polymer is 0.01 to 5.0μ) Claim 1ff1(1) 41
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577483A JPH0236290B2 (en) | 1983-11-04 | 1983-11-04 | GASUBUNRIMAKU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577483A JPH0236290B2 (en) | 1983-11-04 | 1983-11-04 | GASUBUNRIMAKU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6099323A true JPS6099323A (en) | 1985-06-03 |
| JPH0236290B2 JPH0236290B2 (en) | 1990-08-16 |
Family
ID=16512444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20577483A Expired - Lifetime JPH0236290B2 (en) | 1983-11-04 | 1983-11-04 | GASUBUNRIMAKU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0236290B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 JP20577483A patent/JPH0236290B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|---|
| JPH0236290B2 (en) | 1990-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5288304A (en) | Composite carbon fluid separation membranes | |
| CA1326116C (en) | Fluoro-oxidized polymeric membranes for gas separation and process for preparing them | |
| EP3307422B1 (en) | Amorphous fluorinated copolymer gas separation membranes | |
| JP3685289B2 (en) | Liquid degassing module | |
| JPS6099323A (en) | Gas separation film | |
| US6726840B1 (en) | Membranes of (per)fluorinated amorphous polymers | |
| JPH0252527B2 (en) | ||
| JPH0423572B2 (en) | ||
| JPH0236291B2 (en) | KITAIBUNRIMAKU | |
| JPH0236292B2 (en) | KITAIOBUNRISURUMAKU | |
| JPH0423573B2 (en) | ||
| JPH0423570B2 (en) | ||
| JPH0236293B2 (en) | GASUNOBUNRIMAKU | |
| JP2805794B2 (en) | Manufacturing method of gas separation membrane | |
| Higuchi et al. | Permselectivities through artificial membranes at a non‐steady state | |
| Yamasaki et al. | Effect of evaporation time on the pervaporation characteristics through homogeneous aromatic polyamide membranes. II. Pervaporation performances for ethanol/water mixture | |
| JPS5959214A (en) | Gas separating composite membrane | |
| JPH057049B2 (en) | ||
| JP2000042342A (en) | External pressure type composite hollow fiber membrane for gas separation and its production | |
| JPH0456653B2 (en) | ||
| JPH01123618A (en) | Composite gas separation membrane | |
| JPH0559775B2 (en) | ||
| JPH055531B2 (en) | ||
| JPH04305234A (en) | Production of gas permeable composite film | |
| JPH06116436A (en) | Method for treating porous polymer membrane |