JPS62204827A - Gas separating membrane - Google Patents
Gas separating membraneInfo
- Publication number
- JPS62204827A JPS62204827A JP4720086A JP4720086A JPS62204827A JP S62204827 A JPS62204827 A JP S62204827A JP 4720086 A JP4720086 A JP 4720086A JP 4720086 A JP4720086 A JP 4720086A JP S62204827 A JPS62204827 A JP S62204827A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- gas
- helium
- plasma
- porous
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 14
- DBNMHLDZMPEZCX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane-2-thione Chemical compound FC(F)(F)C(=S)C(F)(F)F DBNMHLDZMPEZCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 7
- -1 perfluoro compound Chemical class 0.000 claims abstract description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims abstract 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 19
- 239000001307 helium Substances 0.000 abstract description 16
- 229910052734 helium Inorganic materials 0.000 abstract description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 abstract description 16
- 230000035699 permeability Effects 0.000 abstract description 15
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、気体の分離膜に関し、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
得る分離膜に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a gas separation membrane, and particularly to a separation membrane that can efficiently separate and obtain helium from natural gas with good selectivity by a membrane separation method. be.
［従来の技術］
ヘリウムガスは例えば核融合反応、リニアモーター等の
超電導用の極低温媒体として有用であり、今後かなりの
量の使用が見込まれる。[Prior Art] Helium 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 considerable amounts 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
ガス中にはかなり多量に含まれている。従来ヘリウムは
このよう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、これは設備的にかなり大規模となり、
操作的にも保守管理的にもかなり煩雑なものであった。Such helium is contained in natural gas and air, and particularly in natural gas in a fairly large amount. Conventionally, helium has been separated and obtained from such natural gas by means such as cryogenic separation, but this requires a fairly large scale of equipment.
It was quite complicated in terms of operation and maintenance.
更に、前記の如き超電導に用いたヘリウムガスの回収に
当っては従来それ程有効な手段は提案されていない。Furthermore, no particularly effective means for recovering the helium gas used in superconductivity as described above has been proposed so far.
他方、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。この方法は直接ヘリウムガスが得
られ、操作的に筒車であり、又経済的にも有利である。On the other hand, a membrane separation method has been proposed as a method for obtaining helium from a mixed gas. This method provides direct access to helium gas, is operationally simple, and is economically advantageous.
このような分離膜として代表されるものにオルガノポリ
シロキサン系の膜が種々提案されている。この膜は一般
に酸素に対する透過速度や酸素透過係数比（ＰＯ２／Ｐ
Ｎ２）については比較的満足し得るものの、ヘリウムガ
スについては透過係数比が小さく、実用性についてあま
り期待し得るものでない。Various organopolysiloxane membranes have been proposed as representative separation membranes. This membrane generally has a permeation rate for oxygen and an oxygen permeability coefficient ratio (PO2/P
Although it is relatively satisfactory for N2), the permeability coefficient ratio for helium gas is small, and it is not very promising for practical use.
［発明の解決しようとする問題点］
本発明者はかかる点に鑑み、ヘリウム透過係数比（Ｐ＋
＋ｅ／ＰＮｚ ）とヘ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＃
、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累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。[Problems to be Solved by the Invention] In view of the above, the present inventor has determined the helium permeability coefficient ratio (P+
+e/PNz) and helium permeation rate are balanced at a high level, and the performance can be maintained stably #
As a result of various studies and examinations aimed at obtaining a membrane,
It has been found that the above object can be achieved by using a specific perfluorinated compound as a membrane material.
［問題点を解決するための手段］
かくして、本発明は、多孔質膜上にヘキサフルオロチオ
アセトンのプラズマ重合Ｎ膜を形成せしめてなることを
特徴とする気体の分離膜を新規に提供するものである。[Means for Solving the Problems] Thus, the present invention provides a novel gas separation membrane characterized by forming a plasma-polymerized N membrane of hexafluorothioacetone on a porous membrane. It is.
本発明に用いられる多孔質膜としては、その物性が平均
細孔径１０〜２０００Å、空気の透過速度が４ Ｘ １
０−４〜４ Ｘ １０−１ｃｍ３／ｃｍ２・ｓｅｃ−ｃ
ｒａＨｇを有するものが適当である。The porous membrane used in the present invention has physical properties such as an average pore diameter of 10 to 2000 Å and an air permeation rate of 4×1.
0-4~4 X 10-1cm3/cm2・sec-c
Those with raHg are suitable.
これら物性が前記範囲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。When these physical properties deviate from the above ranges, it is not preferable because it is difficult to obtain a sufficient gas permeation rate and there is a possibility that defects are likely to occur when laminating ultra-thin films.
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、前述の多孔質支持膜上にヘ
キサフルオロチオアセトンを薄膜状にプラズマ重合せし
める。In the present invention, hexafluorothioacetone is plasma-polymerized into a thin film on the above-mentioned porous support membrane.
プラズマ重合に供せられるヘキサフルオロチオアセトン
は１例えば、次に示す一連の反応でヘキサフルオロプロ
ペンより製造され得る。Hexafluorothioacetone to be subjected to plasma polymerization can be produced from hexafluoropropene, for example, by the following series of reactions.
又、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、高周波電源、ガラス
製へルジャー排気系より構成される通常よく知られてい
るペルジャー型プラズマ重合装置を用いることができる
。Further, as the plasma polymerization means, a well-known Pelger type plasma polymerization apparatus, which is composed of a monomer supply valve, an electrode, a ground electrode, a ground electrode cooling section, a high frequency power source, and a glass Herger exhaust system, can be used. can.
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
合装置を用いれば圧力０．０１〜５ｔ’ｏｒｒ、ヘキサ
フルオロチオアセトン流量１〜１０００ＣＩＩ３／１１
１１１ 、高周波出力１〜２００Ｗを採用するのが適当
である。前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を行な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。When using the Pelger type plasma polymerization apparatus, the plasma polymerization conditions are a pressure of 0.01 to 5 t'orr and a flow rate of hexafluorothioacetone of 1 to 1000 CII3/11.
111, it is appropriate to adopt a high frequency output of 1 to 200W. Even if a polymerization apparatus other than those described above is used, it is relatively easy for a person skilled in this technology to optimize these conditions and perform plasma polymerization.
プラズマ重合により多孔質膜上に設けられるヘキサフル
オロチオアセトン重合体薄膜の厚さは０．０１〜５ル、
好ましくは０．０３〜３ル程度を採用するのが適当であ
る。The thickness of the hexafluorothioacetone polymer thin film provided on the porous membrane by plasma polymerization is 0.01 to 5 μl,
Preferably, it is appropriate to employ about 0.03 to 3 liters.
膜の厚さが前記範囲を逸脱する場合には、膜に欠陥を生
じ易くなるか、又は充分なガス透過速度が得難くなる等
の虞れがあるので好ましくない。If the thickness of the membrane deviates from the above range, it is not preferable because there is a risk that the membrane will be more likely to be defective or that it will be difficult to obtain a sufficient gas permeation rate.
かくして得られた気体の分子！ａ膜は、特にヘリウムに
対する選択分離透過性が優れているが、その他酸素や炭
酸ガス等のガスに対する選択透過性も実用的であり、こ
れらガスの濃縮或は分離等にも有用である。The gas molecules thus obtained! The a-membrane has particularly excellent selective separation permeability for helium, but also has practical selective permeability for other gases such as oxygen and carbon dioxide, and is also useful for concentrating or separating these gases.
［実施例］ 次に本発明を実施例により説明する。[Example] Next, the present invention will be explained by examples.
実施例
ペルジャー型プラズマ重合装置を用い、空気の透過速度
が４ Ｘ １０１ｃａ＋３／ｃｍ２ ・ｓｅｃ−ｃｒａ
Ｈｇ、平均細孔径が３０Å、直径８０＋ａｍのポリスル
ホン多孔質ｎりをアース電極上に固定した。Example Using a Pelger type plasma polymerization apparatus, the air permeation rate was 4 x 101ca+3/cm2 sec-cra
A polysulfone porous substrate containing Hg, average pore size of 30 Å, and diameter of 80 am was fixed on a ground electrode.
真空ポンプによりペルジャー内を脱気し、排気を続けな
がら七ツマー供給バルブを通してヘキサフルオロチオア
セトンを１００ＣＩｌ１３／ｌ１ｉｎで供給した。ペル
ジャー内の圧力は０．４ ｔｏｒｒとなった。電極間に
１３．５６Ｎ）Ｉｚ、２０Ｗの高周波出力を印加してヘ
キサフルオロチオアセトンを多孔質１１９Ｅへ３分間プ
ラズマ重合した。The inside of the Pel jar was degassed using a vacuum pump, and while continuing the evacuation, hexafluorothioacetone was supplied at 100 Cl13/11 inch through a 7-mer supply valve. The pressure inside the Pelger was 0.4 torr. A high frequency power of 13.56 N) Iz and 20 W was applied between the electrodes to plasma polymerize hexafluorothioacetone onto the porous 119E for 3 minutes.
得られたプラズマ重合膜の膜厚は０．９川であった・
Ｈｅ、 ＧＯ２，０２，８２の各ガスの透過性能を測定
した結果を以下に示す。The thickness of the obtained plasma polymerized membrane was 0.9 mm. The results of measuring the permeability of He, GO2, 02, and 82 gases are shown below.
Ｈｅの透過速度 ８．４ Ｘ １（１’ｃｍ３／ｃｍ２
−ｓｅｃ−ｃｒｓＨｇＨｅの透過係数５．８ Ｘ １Ｏ
−８ＣＪＩ３ ・ｃｒａ／ｃｔａ２・ｓｅｃ−ｃｒａＨ
ｇＣ０２）透過速度１．３Ｘ １Ｏ−４ｃａ３／ａｍ２
−ｓｅｃ−ｃｒｒｒＨｇＣ０２の透過係数１．２Ｘ １
０−８ｃｍ３・ｃｍ／ｃｍ２ ・ｓｅｃ−ｃｒａＨｇ０
２の透過速度 ５．２Ｘ １Ｏ−５ｃ＋ａ３／ｃｍ２−
ｓｅｃ−ｃｒａＨｇ０２の透過係数 ４．７Ｘ １０−
９ ｃｌ１３・ｃｍ／ｃｍ２ ・ｓｅｃ−ｃｒｍＨｇＮ
２の透過速度 ２．ＯＸ １０−５ｃｍ３／ｃｍ２ ・
ｓｅｃ−ａｒｍＨｇＮ２の透過係数 １．８Ｘ １Ｏ
−９ｃ＋ａ３ ・ｃｏ／ｃｍ２ ・ｓｅＣ−ｃｒａＨｇ
Ｈｅ／Ｎ２の透過係数比 ３２
ＣＣｈ ／Ｎ２の透過係数比 ６．７
０２／Ｎ２の透過係数比 ２．８
［発明の効果］
本発明の特定パーフルオロ化合物のプラズマ重合薄膜を
有する気体分離膜は、特にヘリウム透過係数比とヘリウ
ム透過速度が高いレベルでバランスするという優れた効
果を有する。しかも、本発明の気体分ａｍは、この優れ
た性能を安定して持続し得るという効果も認められる。He permeation rate 8.4 x 1 (1'cm3/cm2
-sec-crsHgHe permeability coefficient 5.8 x 1O
-8CJI3 ・cra/cta2・sec-craH
gC02) Permeation rate 1.3X 1O-4ca3/am2
-sec-crrrHgC02 transmission coefficient 1.2X 1
0-8cm3・cm/cm2・sec-craHg0
Transmission rate of 2 5.2X 1O-5c+a3/cm2-
Permeability coefficient of sec-craHg02 4.7X 10-
9 cl13・cm/cm2・sec-crmHgN
2 permeation rate 2. OX 10-5cm3/cm2 ・
Permeability coefficient of sec-armHgN2 1.8X 1O
-9c+a3 ・co/cm2 ・seC-craHg
He/N2 permeability coefficient ratio: 32 CCh/N2 permeability coefficient ratio: 6.7 02/N2 permeability coefficient ratio: 2.8 [Effects of the invention] The gas separation membrane having a plasma-polymerized thin film of a specific perfluoro compound of the present invention has the following properties: In particular, it has an excellent effect in that the helium permeability coefficient ratio and the helium permeation rate are balanced at a high level. Furthermore, the gas component am of the present invention is also recognized to be effective in stably maintaining this excellent performance.
Claims (1)
マ重合薄膜を形成せしめてなることを特徴とする気体の
分離膜。 ２、多孔質膜は平均細孔径１０〜２０００Å、空気の透
過速度が４×１０＾−４〜４×１０＾−＾１ｃｍ＾３／
ｃｍ＾２・ｓｅｃ・ｃｍＨｇである特許請求の範囲第１
項記載の分離膜。 ３、多孔質膜はポリスルホン、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特許請求の範囲第１項
又は第２項のいずれかに記載の分離膜。 ４、ヘキサフルオロチオアセトン重合体の膜厚は０．０
１〜５μである特許請求の範囲第１項記載の分離膜。[Scope of Claims] 1. A gas separation membrane characterized by forming a plasma-polymerized thin film of hexafluorothioacetone on a porous membrane. 2. The porous membrane has an average pore diameter of 10 to 2000 Å and an air permeation rate of 4 x 10^-4 to 4 x 10^-^1 cm^3/
Claim 1 which is cm^2・sec・cmHg
Separation membrane described in section. 3. The separation membrane according to claim 1 or 2, wherein the porous membrane is made of polysulfone, polyamide, polyacrylonitrile, polyethylene, polyvinyl alcohol, or polytetrafluoroethylene. 4. The film thickness of hexafluorothioacetone polymer is 0.0
The separation membrane according to claim 1, which has a particle diameter of 1 to 5μ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4720086A JPS62204827A (en) | 1986-03-06 | 1986-03-06 | Gas separating membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4720086A JPS62204827A (en) | 1986-03-06 | 1986-03-06 | Gas separating membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62204827A true JPS62204827A (en) | 1987-09-09 |
| JPH0423573B2 JPH0423573B2 (en) | 1992-04-22 |
Family
ID=12768489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4720086A Granted JPS62204827A (en) | 1986-03-06 | 1986-03-06 | Gas separating membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62204827A (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 |
-
1986
- 1986-03-06 JP JP4720086A patent/JPS62204827A/en active Granted
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 |
|---|---|
| JPH0423573B2 (en) | 1992-04-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |