JPH0236293B2 - GASUNOBUNRIMAKU - Google Patents
GASUNOBUNRIMAKUInfo
- Publication number
- JPH0236293B2 JPH0236293B2 JP20577583A JP20577583A JPH0236293B2 JP H0236293 B2 JPH0236293 B2 JP H0236293B2 JP 20577583 A JP20577583 A JP 20577583A JP 20577583 A JP20577583 A JP 20577583A JP H0236293 B2 JPH0236293 B2 JP H0236293B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- separation
- perfluorobenzene
- cmhg
- sec
- 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
- 239000012528 membrane Substances 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 19
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 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
- 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
- 229920000642 polymer Polymers 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 13
- 229910052734 helium Inorganic materials 0.000 description 11
- 239000001307 helium Substances 0.000 description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000003345 natural gas Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010409 thin film Substances 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
- 239000010408 film Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】
本発明はガスの分離膜、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
取得し得る分離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 separation membrane that can efficiently separate and obtain helium from natural gas with good selectivity 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
ター等の超導電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。 Helium gas is useful as a cryogenic medium for superconductivity in nuclear fusion reactions, linear motors, etc., and is expected to be used in considerable 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り多量に含まれている。
従来ヘリウムはこ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つた。 Such helium is found in natural gas and air,
In particular, it is contained in considerable amounts in natural gas.
Conventionally, helium has been separated and obtained from such natural gas by means such as cryogenic separation, but this requires a fairly large-scale facility and is 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
の回収に当つては従来それ程有効な手段は提案さ
れていない。 Furthermore, no very effective means have been proposed so far for recovering the helium gas used for superconductivity as described above.
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、操作的に簡単であり、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
る透過速度や酸素分離系数（PO2／PN2）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
ては分離係数が小さく、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 allows helium gas to be obtained directly, is operationally simple, and is economically advantageous. Various organopolysiloxane membranes have been proposed as typical examples of such separation membranes. Although this membrane is generally relatively satisfactory in terms of oxygen permeation rate and oxygen separation system number (P O2 /P N2 ), it has a small separation coefficient for helium gas and cannot be expected to be very practical.
本発明者はかかる点に鑑み、分離係数（PHe／
PN2）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
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 determined the separation coefficient (P He /
As a result of various studies and examinations, we decided to use a specific perfluorinated compound as the membrane material with the aim of creating a separation membrane that has a high balance between the permeation rates of P N2 ) and helium, and whose performance is stable and long-lasting. It has been found that the above object can be achieved by the following.
かくして本発明は多孔質膜上にパーフルオロベ
ンゼンをプラズマ重合せしめて成るガスの分離膜
を提供するにある。 Thus, the present invention provides a gas separation membrane comprising perfluorobenzene plasma polymerized on a porous membrane.
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４×
10-4〜４×10-1cm3/cm2・sec・cmHgを有するのが
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×
10 -4 to 4×10 -1 cm 3 /cm 2 ·sec·cmHg is 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。 If these physical properties deviate from the above range, it is difficult to obtain a sufficient gas permeation rate, and defects may easily occur when laminating ultra-thin films, which is not preferable.
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
にパーフルオロベンゼンを薄膜状にプラズマ重合
せしめる。 In the present invention, perfluorobenzene 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パーフルオロベンゼ
ンの調製は、例えば次に示す一連の反応でベンゼ
ンより製造される。 Perfluorobenzene to be subjected to plasma polymerization is prepared from benzene by, for example, the following series of reactions.
C6H6CoF3
――――→
C6H3F9
C6H3F9KOH
――――→
C6F6
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、ガラス製ベルジヤー、排気系より構成さ
れる通常よく知られているベルジヤー型プラズマ
重合装置を用いることが出来る。 C 6 H 6 CoF 3 ――――→ C 6 H 3 F 9 C 6 H 3 F 9 KOH ――――→ C 6 F 6In addition, the plasma polymerization means includes a monomer supply valve, an electrode, a ground electrode, A well-known bergier-type plasma polymerization apparatus consisting of a ground electrode cooling section, a high-frequency power source, a glass bergier, and an exhaust system can be used.
プラズマ重合条件としては前記ベルジヤー型プ
ラズマ重合装置を用いれば圧力0.01〜5torr、パ
ーフルオロベンゼンの流量１〜1000cm3／min、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うのはこの技術に習
熟している者にとつて比較的容易である。 As for the plasma polymerization conditions, if the above-mentioned Bergier type plasma polymerization apparatus is used, it is appropriate to adopt a pressure of 0.01 to 5 torr, a flow rate of perfluorobenzene of 1 to 1000 cm 3 /min, and a high frequency output of 1 to 200 W.
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パ
ーフルオロベンゼン膜の厚さは0.01〜5.0μm、好
ましくは0.03〜1.0μm程度を採用するのが適当で
ある。 The thickness of the perfluorobenzene membrane provided on the porous membrane by plasma polymerization is suitably about 0.01 to 5.0 μm, preferably about 0.03 to 1.0 μm.
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.
かくして得られたガスの分離膜は、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 separation membrane thus obtained 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 useful for concentrating or separating these gases. is also useful.
次に本発明を実施例により説明する。 Next, the present invention will be explained by examples.
実施例
ベルジヤー型プラズマ重合装置を用い、空気の
透過速度が４×10-2cm3/cm2・sec・cmHg、平均細
孔径が30Å、直径80mmのポリスルホン多孔質膜を
アース電極上に固定した。Example A polysulfone porous membrane with an air permeation rate of 4×10 -2 cm 3 /cm 2 ·sec·cmHg, an average pore diameter of 30 Å, and a diameter of 80 mm was fixed on a ground electrode using a Bergier type plasma polymerization apparatus. .
真空ポンプによりベルジヤー内を脱気し、排気
を続けながらモノマー供給バルブを通してパーフ
ルオロベンゼンを200cm3／minで供給した。ベル
ジヤー内の圧力は0.4torrとなつた。電極間に
13.56MHz、20Wの高周波出力を印加してパーフ
ルオロベンゼンを多孔質膜上へ0.5分間プラズマ
重合した。 The inside of the bell gear was degassed using a vacuum pump, and perfluorobenzene was supplied at 200 cm 3 /min through a monomer supply valve while continuing to evacuation. The pressure inside the bell jar was 0.4 torr. between the electrodes
Perfluorobenzene was plasma polymerized onto the porous membrane for 0.5 minutes by applying a high frequency power of 13.56 MHz and 20 W.
得られたプラズマ重合膜は0.29μmであつた。 The plasma polymerized film obtained had a thickness of 0.29 μm.
He、CO2、N2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 He, CO 2 and N 2 gases are shown below.
Heの透過速度 3.5×10-4cm3/cm2・sec・cmHg Heの透過係数 1.0×10-8cm3/cm・sec・cmHg CO2の透過速度 6.1×10-5cm3/cm2・sec・cmHg CO2の透過係数 1.7×10-9cm3/cm・sec・cmHg N2の透過速度 1.6×10-5cm3/cm2・sec・cmHg N2の透過係数 4.5×10-10cm3/cm・sec・cmHg He／N2の分離係数 22 CO2／N2の分離係数 3.9He permeation rate 3.5×10 -4 cm 3 /cm 2・sec・cmHg He permeation coefficient 1.0×10 −8 cm 3 /cm・sec・cmHg CO 2 permeation rate 6.1×10 −5 cm 3 /cm 2・sec・cmHg Permeability coefficient of CO 2 1.7×10 -9 cm 3 /cm・sec・cmHg Permeation rate of N 2 1.6×10 −5 cm 3 /cm 2・sec・cmHg Permeability coefficient of N 2 4.5×10 − 10 cm 3 /cm・sec・cmHg He/N 2 separation factor 22 CO 2 /N 2 separation factor 3.9
Claims (1)
マ重合せしめて成るガスの分離膜。 ２ 多孔質膜は平均細孔径10〜2000Å、空気の透
過速度が４×10-4〜４×10-1cm3/cm2・sec・cmHg
である請求の範囲１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請
求の範囲１又は２の分離膜。 ４ パーフルオロベンゼン重合体の膜厚は0.01〜
5.0μmである請求の範囲１の分離膜。[Claims] 1. A gas separation membrane made by plasma polymerizing perfluorobenzene on a porous membrane. 2 Porous membrane has an average pore diameter of 10 to 2000 Å and an air permeation rate of 4 × 10 -4 to 4 × 10 -1 cm 3 /cm 2・sec・cmHg
The separation membrane according to claim 1. 3. The separation membrane according to claim 1 or 2, wherein the porous membrane is polysulfone, polyamide, polyacrylonitrile, polyethylene, polyvinyl alcohol, or polytetrafluoroethylene. 4 The film thickness of perfluorobenzene polymer is 0.01~
The separation membrane according to claim 1, which has a diameter of 5.0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577583A JPH0236293B2 (en) | 1983-11-04 | 1983-11-04 | GASUNOBUNRIMAKU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577583A JPH0236293B2 (en) | 1983-11-04 | 1983-11-04 | GASUNOBUNRIMAKU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6099324A JPS6099324A (en) | 1985-06-03 |
| JPH0236293B2 true JPH0236293B2 (en) | 1990-08-16 |
Family
ID=16512459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20577583A Expired - Lifetime JPH0236293B2 (en) | 1983-11-04 | 1983-11-04 | GASUNOBUNRIMAKU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0236293B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2671072B2 (en) * | 1991-11-26 | 1997-10-29 | 宇部興産株式会社 | Gas separation membrane manufacturing method |
-
1983
- 1983-11-04 JP JP20577583A patent/JPH0236293B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6099324A (en) | 1985-06-03 |
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