JPS62282618A - Production of composite membrane for separating gas - Google Patents
Production of composite membrane for separating gasInfo
- Publication number
- JPS62282618A JPS62282618A JP12604486A JP12604486A JPS62282618A JP S62282618 A JPS62282618 A JP S62282618A JP 12604486 A JP12604486 A JP 12604486A JP 12604486 A JP12604486 A JP 12604486A JP S62282618 A JPS62282618 A JP S62282618A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- gas separation
- separation membrane
- solvent
- gas
- 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 89
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000926 separation method Methods 0.000 claims abstract description 59
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010030 laminating Methods 0.000 claims abstract description 4
- -1 siloxane structure Chemical group 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 238000001704 evaporation Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 238000000034 method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101150056612 PPIA gene Proteins 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
飯業上の利用分野
本発明は酸素富化気体を得る気体分離用複合膜の製造方
法に関するものである。Detailed Description of the Invention 3. Detailed Description of the Invention Field of Industrial Application The present invention relates to a method for producing a composite membrane for gas separation for obtaining oxygen-enriched gas.
従来の技術
近年、有機高分子を用いた気体分離膜が数多く提案され
ている。この方法により空気中の酸素を安価に分離濃縮
できるならば、燃焼、製鉄、窯業。BACKGROUND OF THE INVENTION In recent years, many gas separation membranes using organic polymers have been proposed. If oxygen in the air could be separated and concentrated at low cost using this method, it would be useful in the combustion, iron and ceramic industries.
廃棄物処理、医療様関係に大いに貢献できると期待され
る。It is expected that it will greatly contribute to waste treatment and medical fields.
酸素の分離膜は、空気等の酸素含有気体から、選択的に
酸素を分離する機能が大きいこと、効率よく酸素を透過
させる機能が大きいこと、すなわち、酸素選択係数と酸
素透過係数が大きいことが要求される。このような気体
分離膜として、特開昭５１−１２１４８５号公報には、
オルガノキリシロキサンーボリカーボネト共重合体が提
示されている。また特開昭５６−２６５０θ号公報には
ポリオルガノシロキサンと不飽和結合を持つ炭化水素重
合体との共重合体が提示されている。Oxygen separation membranes have a high ability to selectively separate oxygen from oxygen-containing gases such as air, and a high ability to efficiently transmit oxygen, that is, have a high oxygen selection coefficient and oxygen permeability coefficient. required. As such a gas separation membrane, Japanese Patent Application Laid-open No. 121485/1985 describes
Organoxysiloxane-polycarbonate copolymers are presented. Further, JP-A-56-2650θ discloses a copolymer of polyorganosiloxane and a hydrocarbon polymer having unsaturated bonds.
酸素富化空気の利用の実現が早く、効果が著しいと思わ
れる燃焼炉や、窯業炉等は多量の酸素富化空気を必要と
する。Combustion furnaces, ceramic furnaces, etc., for which the use of oxygen-enriched air is expected to be realized quickly and have remarkable effects, require large amounts of oxygen-enriched air.
一般に気体分離膜を透過する量は次のような式％式％
従って膜の厚み＜ｌ）を薄くすればする程透過気体量を
多く得ることができる。このような薄膜の気体分離膜を
得る一つの方法として、水面上に有機高分子を展開し、
気体分離膜を形成し、これを多孔質支持膜に移し取る方
法が特開昭５６−９２９２６号公報や特願昭５５−１８
６３９５号に提示されている。In general, the amount of gas that permeates through a gas separation membrane is calculated using the following formula: One way to obtain such a thin gas separation membrane is to spread an organic polymer on the water surface.
A method of forming a gas separation membrane and transferring it to a porous support membrane is disclosed in Japanese Patent Application Laid-open No. 56-92926 and Japanese Patent Application No. 55-18.
No. 6395.
発明が解決しようとする問題点
しかし上記のような気体分離膜を、上記製膜方法で多孔
性支持膜上に積層した気体分離用複合膜を高温高湿中に
放置すると、数百時間内に酸素選択係数が低下してくる
。たとえばポリジメチルシロキサンとポリスルホンとポ
リヒドロキシスチレンの共重合体を気体分離膜材料に用
いて高温高湿中に放置しても、共重合体の分解は確認で
きず、物質変化は起こしていない。従ってもし均質な薄
膜が形成されているとするならば、当然酸素選択係数は
維持されていなければならない。しかし実際は酸素選択
係数が低下している。これは気体分離膜が部分的に破損
しているためである。Problems to be Solved by the Invention However, if a gas separation membrane as described above, which is laminated on a porous support membrane using the above membrane forming method, is left in a high temperature and high humidity environment, it will break down within several hundred hours. The oxygen selectivity coefficient decreases. For example, even if a copolymer of polydimethylsiloxane, polysulfone, and polyhydroxystyrene is used as a gas separation membrane material and left in high temperature and high humidity, no decomposition of the copolymer can be confirmed and no substance change occurs. Therefore, if a homogeneous thin film is to be formed, the oxygen selectivity coefficient must be maintained. However, the oxygen selectivity coefficient actually decreases. This is because the gas separation membrane is partially damaged.
気体分離膜と多孔性支持膜が完全に密着せず、部分的べ
気体分離膜が浮いた状態にあると、高温高湿中に放置さ
れた場合、気体分離膜が吸湿し、浮いた状態にある部分
の機械的強度が低下し、気体分離膜の破損が起こる。If the gas separation membrane and porous support membrane do not come into close contact with each other and the gas separation membrane is partially floating, if left in a high temperature and high humidity environment, the gas separation membrane will absorb moisture and become floating. The mechanical strength of a certain part decreases and damage to the gas separation membrane occurs.
このように水面展開し溶剤を蒸発させ薄膜化した気体分
離膜を多孔性支持膜に移し取ち積層する方法では、高温
高湿中で数百時間内に酸素選択係数が低下するという欠
点を有していた。This method of spreading the gas separation membrane on the water surface, evaporating the solvent, and transferring it to a porous support membrane to form a thin film and stacking the membrane has the disadvantage that the oxygen selectivity coefficient decreases within several hundred hours in high temperature and high humidity. Was.
本発明は上記欠点に鑑み、気体分離膜と多孔性支持膜と
を完全に密着させ、気体分離膜が吸湿しても機械的強度
の゛低下を防止し、気体分離膜の破損を抑制して信頼性
の高い気体分離用複合膜の製造方法を提供するものであ
る。In view of the above-mentioned drawbacks, the present invention brings a gas separation membrane and a porous support membrane into complete contact with each other, prevents a decrease in mechanical strength even if the gas separation membrane absorbs moisture, and suppresses damage to the gas separation membrane. The present invention provides a method for manufacturing a highly reliable composite membrane for gas separation.
問題点を解決するための手段
この目的を達成するため本発明の気体分離用複合膜の製
造方法は、気体分離膜を多孔性支持膜上に積層した後、
気体分離膜を溶解しない有機溶剤に浸漬し、乾燥させる
ことから構成されている。Means for Solving the Problems In order to achieve this object, the method for manufacturing a composite membrane for gas separation of the present invention includes: after laminating a gas separation membrane on a porous support membrane,
It consists of immersing the gas separation membrane in an insoluble organic solvent and drying it.
作 用
この構成により、気体分離膜と多孔性支持膜が完全に密
着した気体分離用複合膜を得ることができる。気体分離
膜材料を溶剤に溶解した液を水面に展開し溶剤が蒸発す
ると薄膜の気体分離膜が得られる。これを多孔性支持膜
に移し取ると、多孔性支持膜の微小な凹凸のため気体分
離膜と完全には密着していない気体分離用複合膜となる
。これを気体分離膜を溶解しない溶剤に浸漬すると、溶
剤は気体分離膜と多孔性支持膜との間隙にも浸透する。Function: With this configuration, it is possible to obtain a composite membrane for gas separation in which the gas separation membrane and the porous support membrane are in complete contact with each other. When a solution of gas separation membrane material dissolved in a solvent is spread on the water surface and the solvent evaporates, a thin gas separation membrane is obtained. When this is transferred to a porous support membrane, a composite membrane for gas separation is obtained, which is not in complete contact with the gas separation membrane due to minute irregularities in the porous support membrane. When this is immersed in a solvent that does not dissolve the gas separation membrane, the solvent also permeates the gap between the gas separation membrane and the porous support membrane.
この状態から溶剤を蒸発させると、蒸発に住−ｐＰＩＡ
翔Ｌ１を嘔拳仕昨吉−はり、了ＩＭプγ食年箔Ｗ
Ｅｌ 遊 ダマｊト乙れ、溶剤が完全に蒸発すると、多
孔性支持膜と密着することとなる。When the solvent is evaporated from this state, the evaporation causes the pPIA to evaporate.
Sho L1 is a fist fight yesterday - Hari, Ryo IM Pu γ Eating New Year's foil W
When the solvent completely evaporates, it comes into close contact with the porous support membrane.
本発明における多孔性支持膜は気体透過性を有し、気体
分離膜を支持し補強するものであれば特に限°定されな
いが、一般に、ポリプロピレン、セルロースエステル、
ポリエステル、ポリスルホン。The porous support membrane in the present invention is not particularly limited as long as it has gas permeability and supports and reinforces the gas separation membrane, but generally polypropylene, cellulose ester,
Polyester, polysulfone.
等の有機高分子の多孔性膜である。It is a porous membrane of organic polymer such as.
実施例 以下本発明の実施例について説明する。Example Examples of the present invention will be described below.
気体分離膜材料として、ポリジメチルノロキサンとポリ
スルホンとポリヒドロキシスチレンの共重合体の２チ（
重量係）ベンゼン溶液にテトラヒドロフランを１０％（
重量％）加えた溶液を水面上に展開し、溶剤を蒸発させ
、多孔性支持膜としてポリプロピレン製の商品名「ジュ
ラガード（グレード２４００）Ｊ （ポリプラスチッ
ク■製）上に移し取る。この製膜された気体分離用複合
膜を、有機溶剤として、エタノール（特級）に浸漬し、
完全に乾燥して気体分離用複合膜を作成した。As a gas separation membrane material, two-layer copolymers of polydimethylnoroxane, polysulfone, and polyhydroxystyrene (
Weight) Add 10% (by weight) of tetrahydrofuran to a benzene solution.
% by weight) is spread on the water surface, the solvent is evaporated, and the porous support membrane is transferred onto a polypropylene product name "Duraguard (Grade 2400) J (manufactured by Polyplastic ■)". The resulting composite membrane for gas separation is immersed in ethanol (special grade) as an organic solvent.
After complete drying, a composite membrane for gas separation was prepared.
有機溶剤として他に、２−グロパノール、１−プロパツ
ール、２−メチル−１−プロパツール。Other organic solvents include 2-glopanol, 1-propatol, and 2-methyl-1-propatol.
１−ブタノールで同様に処理して気体分離用複合膜を作
成した。A composite membrane for gas separation was prepared by the same treatment with 1-butanol.
作成した気体分離用複合膜の性能は酸素透過流量として
は０．８３〜１．０ｃｃ／ｓｅｃ 、 （有効面積１１
．３ｃｒｄ ｇ測定圧力１．０に９．ｌ ｃｒｌ ）選
択係数は２．０〜２．１であった。The performance of the prepared composite membrane for gas separation is as follows: oxygen permeation flow rate is 0.83 to 1.0 cc/sec (effective area 11
．． 3crd g measurement pressure 1.0 to 9. l crl ) selection coefficient was 2.0-2.1.
実施例と、従来例である有機溶剤に浸漬処理しない気体
分離用複合膜を温度６０’Ｃ，湿度９５チＲＨ中に放置
し、酸素透過流量変化率と選択係数を測定した。図の結
果より明らかなように、選択係数２．０以下になる時間
は従来例に比べ、２倍以上も長くなっていることがわか
る。また酸素透過流量変化のグラフから明らかなように
、従来例の場合、３ｏｏ〜５０Ｑ時間よシ酸素透過流量
が増加し始める。すなわちこの時間より気体分離膜が破
損し始めたと考えることができる。本実施例では１００
０時間まで気体分離膜は十分その機能を維持している。Composite membranes for gas separation, which were not immersed in an organic solvent and were not immersed in an organic solvent, were left in a temperature of 60'C and a humidity of 95 degrees RH, and the rate of change in oxygen permeation flow rate and selectivity coefficient were measured. As is clear from the results in the figure, it can be seen that the time for the selection coefficient to become 2.0 or less is more than twice as long as in the conventional example. Further, as is clear from the graph of the change in oxygen permeation flow rate, in the case of the conventional example, the oxygen permeation flow rate begins to increase from 3oo to 50Q time. In other words, it can be considered that the gas separation membrane started to be damaged from this time. In this example, 100
The gas separation membrane sufficiently maintains its function up to 0 hours.
発明の効果
以上のように本発明は、気体分離膜を多孔性支持膜に積
層した後、気体分離膜を溶解しない溶剤に浸漬し、乾燥
することにより、気体分離膜と多孔性支持膜の密着性を
向上させ、高温高湿中における気体分離用複合膜の寿命
を著しく改善し、高信頼性の気体分離用複合膜を提供で
き、その実用的効果は大なるものがある。Effects of the Invention As described above, the present invention is capable of achieving close contact between the gas separation membrane and the porous support membrane by laminating the gas separation membrane on the porous support membrane, immersing the gas separation membrane in a solvent that does not dissolve the membrane, and drying it. The present invention can significantly improve the life of the composite membrane for gas separation in high temperature and high humidity conditions, and provide a highly reliable composite membrane for gas separation, which has great practical effects.
図は６０″Ｃ−９６％ＲＨ放置気体分離膜の選択係数の
変化と酸素透過流量の変化率を示す特性図である。The figure is a characteristic diagram showing the change in the selectivity coefficient and the rate of change in the oxygen permeation flow rate of a 60''C-96% RH gas separation membrane.
Claims (3)
剤に浸漬し、乾燥することを特徴とする気体分離用複合
膜の製造方法。(1) A method for producing a composite membrane for gas separation, which comprises laminating a gas separation membrane on a porous support membrane, immersing it in an organic solvent, and drying it.
溶剤がアルコール系溶剤であることを特徴とする特許請
求の範囲第１項記載の気体分離用複合膜の製造方法。(2) The method for producing a composite membrane for gas separation according to claim 1, wherein the gas separation membrane has a hydroxyl group in the molecule, and the organic solvent is an alcohol solvent.
シル基を有し、有機溶剤がアルコール系溶剤であること
を特徴とする特許請求の範囲第１項記載の気体分離用複
合膜の製造方法。(3) The method for producing a composite membrane for gas separation according to claim 1, wherein the gas separation membrane has a siloxane structure and a hydroxyl group in the molecule, and the organic solvent is an alcohol solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61126044A JPH0761425B2 (en) | 1986-05-30 | 1986-05-30 | Method for producing composite membrane for gas separation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61126044A JPH0761425B2 (en) | 1986-05-30 | 1986-05-30 | Method for producing composite membrane for gas separation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62282618A true JPS62282618A (en) | 1987-12-08 |
| JPH0761425B2 JPH0761425B2 (en) | 1995-07-05 |
Family
ID=14925266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61126044A Expired - Lifetime JPH0761425B2 (en) | 1986-05-30 | 1986-05-30 | Method for producing composite membrane for gas separation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761425B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63294908A (en) * | 1987-04-08 | 1988-12-01 | ユニオン・カーバイド・コーポレーション | Improved composite separation membrane, and its production and use |
| CN102974228A (en) * | 2012-10-25 | 2013-03-20 | 贵阳时代沃顿科技有限公司 | Nanofiltration membrane with nanometer hybridized desalination layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60216811A (en) * | 1984-04-13 | 1985-10-30 | Sumitomo Bakelite Co Ltd | Manufacture of dry separation membrane |
-
1986
- 1986-05-30 JP JP61126044A patent/JPH0761425B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60216811A (en) * | 1984-04-13 | 1985-10-30 | Sumitomo Bakelite Co Ltd | Manufacture of dry separation membrane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63294908A (en) * | 1987-04-08 | 1988-12-01 | ユニオン・カーバイド・コーポレーション | Improved composite separation membrane, and its production and use |
| JPH0679657B2 (en) * | 1987-04-08 | 1994-10-12 | ユニオン・カーバイド・コーポレーション | Improved composite separation membrane and its manufacture and use |
| CN102974228A (en) * | 2012-10-25 | 2013-03-20 | 贵阳时代沃顿科技有限公司 | Nanofiltration membrane with nanometer hybridized desalination layer |
| CN102974228B (en) * | 2012-10-25 | 2015-04-22 | 贵阳时代沃顿科技有限公司 | Nanofiltration membrane with nanometer hybridized desalination layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0761425B2 (en) | 1995-07-05 |
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