JPS62282619A - Composite membrane for separating gas - Google Patents
Composite membrane for separating gasInfo
- Publication number
- JPS62282619A JPS62282619A JP12604786A JP12604786A JPS62282619A JP S62282619 A JPS62282619 A JP S62282619A JP 12604786 A JP12604786 A JP 12604786A JP 12604786 A JP12604786 A JP 12604786A JP S62282619 A JPS62282619 A JP S62282619A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- gas separation
- cross
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 19
- 238000004132 cross linking Methods 0.000 abstract description 13
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001704 evaporation Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000010030 laminating Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000002250 progressing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 polysiloxane Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
産業上の利用分野
本発明は気体分離用複合膜に関し、特に酸素富化気体を
得る気体分離用複合膜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 composite membrane for gas separation, and more particularly to 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。たとえば燃焼システムにおいて、通常の空気の代り
に酸素富化空気を用いて燃焼を行な焼排ガス量の減少が
期待でき、省エネルギー燃焼システムが構築できる。こ
のような酸素富化空気を得るための気体分離膜は、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。It is expected that it will greatly contribute to waste treatment and medical fields. For example, in a combustion system, oxygen-enriched air is used instead of normal air to perform combustion, and the amount of combustion exhaust gas can be expected to be reduced, making it possible to construct an energy-saving combustion system. Gas separation membranes for obtaining such oxygen-enriched air must have a high ability to selectively separate oxygen from oxygen-containing gases such as air, and a high ability to efficiently transmit oxygen. It is required that the selection coefficient and oxygen permeability coefficient are large.
一般に有機高分子は選択係数が大きくなると、酸素透過
係数が小さくなる。燃焼においては酸素濃度が３０％程
度でも十分燃焼効率が向上する。Generally, as the selectivity coefficient of an organic polymer increases, the oxygen permeability coefficient decreases. In combustion, combustion efficiency is sufficiently improved even when the oxygen concentration is around 30%.
従って選択係数は２程度で十分であり、むしろ気体透過
係数の大きい材料が望ましい。このような材料としては
シリコーンが考えられる。しかしシリコーン、すなわち
オルガノポリシロキサンは機械的強度が十分でなく薄膜
として使用できない。Therefore, a selection coefficient of about 2 is sufficient, and a material with a large gas permeability coefficient is preferable. Silicone can be considered as such a material. However, silicone, ie, organopolysiloxane, does not have sufficient mechanical strength and cannot be used as a thin film.
そのため気体透過係数は低下するが膜の機械強度を向上
させ、製膜を可能ならしめるため他の高分子とのブロッ
ク共重合体が提案されている。たと ′えば特開
昭６１−１２１４８５号公報には、オルガノポリシロキ
サンとポリカーボネート共重合体が、また特開昭５６−
２８６０６号公報には、α。Therefore, block copolymers with other polymers have been proposed in order to improve the mechanical strength of the membrane and make membrane formation possible, although the gas permeability coefficient decreases. For example, JP-A-61-121485 discloses an organopolysiloxane and polycarbonate copolymer;
No. 28606 includes α.
ω−二官能性ポリシロキサンと側鎖に芳香環をもつスチ
レン系高分子との共重合体が提案されている。上記のよ
うなオルガノポリシロキサン共重合体を有機溶剤に溶解
し、多孔性支持膜上に塗布したり、水面上に溶液を展開
し、有機溶剤を蒸発させることにより製膜し、多孔性支
持体上に移し取り気体分離用複合膜を作成する方法等が
ある。A copolymer of an ω-bifunctional polysiloxane and a styrene polymer having an aromatic ring in the side chain has been proposed. The organopolysiloxane copolymer described above is dissolved in an organic solvent and coated on a porous support membrane, or the solution is spread on the water surface and the organic solvent is evaporated to form a film. There are methods of creating a composite membrane for gas separation by transferring the gas to the top.
発明が解決しようとする問題点
しかしながら、上記のようなオルガノポリシロキサン共
重合体は、当然のことながら有機溶剤に弱い。実用に供
される気体分離用複合膜は多孔性支持膜上に、０．１〜
０．５層程度の膜厚を有するオルガノポリンロキサン共
重合体気体分離膜が積層されている。この気体分離用複
合膜を用いて気体分離を行なう時、分離しようとする混
合気体中に有機溶剤が共存している場合は、有機溶剤に
より気体分離膜が侵かされ気体分離能を矢するという欠
点を有していた。従って有機溶剤が共存するような所で
は有機溶剤に可能な膜による気体分離は行なえず、行な
うとすれば有機溶剤を除去する必要がある。Problems to be Solved by the Invention However, the above organopolysiloxane copolymers are naturally sensitive to organic solvents. Composite membranes for gas separation used in practical use have a porous support membrane with a
Organoporinroxane copolymer gas separation membranes each having a thickness of about 0.5 layers are laminated. When performing gas separation using this composite membrane for gas separation, if an organic solvent coexists in the gas mixture to be separated, the organic solvent will attack the gas separation membrane and reduce its gas separation performance. It had drawbacks. Therefore, in places where organic solvents coexist, gas separation using a membrane, which is possible with organic solvents, cannot be performed, and if separation is to be performed, it is necessary to remove the organic solvents.
本発明は上記欠点に鑑み、分離しようとする混合気体中
に有機溶剤が共存していても、有機溶剤により気体分離
膜が侵かされない気体分離用複合膜を提供するものであ
る。In view of the above drawbacks, the present invention provides a composite membrane for gas separation in which the gas separation membrane is not attacked by the organic solvent even if an organic solvent coexists in the mixed gas to be separated.
問題点を解決するだめの手段
この目的を達成するために本発明の気体分離用複合膜は
、多孔性支持膜上に、ヒドロキン基を有する気体分離膜
を積層し、かつその気体分離膜を架橋重合させることに
より構成されている。Means for solving the problem In order to achieve this object, the composite membrane for gas separation of the present invention is produced by laminating a gas separation membrane having a hydroquine group on a porous support membrane, and cross-linking the gas separation membrane. It is constructed by polymerization.
作 用
この構成により、気体分離膜を網状組織体とすることが
でき、有機溶剤に不溶な気体分離膜を作成することがで
きる。ヒドロキシ基を有する気体分離膜を有機溶剤に溶
解し、水面上に展開し薄膜を作成し、多孔性支持膜上に
積層する。その後、ヒドロキシ基と架橋重合する多官能
試薬を溶解した溶液に浸漬し、溶剤を蒸発させると、気
体分離膜のヒドロキシ基と架橋重合が起こる。たとえば
アルコキシド基を有するアルコキンチタンの場合下記に
示すような架橋重合が進み綱状組織ができると考えられ
る。Function: With this configuration, the gas separation membrane can be formed into a network structure, and a gas separation membrane that is insoluble in organic solvents can be created. A gas separation membrane having hydroxyl groups is dissolved in an organic solvent, spread on the water surface to create a thin film, and laminated on a porous support membrane. Thereafter, when it is immersed in a solution containing a polyfunctional reagent that crosslinks and polymerizes with hydroxyl groups and evaporates the solvent, crosslinking and polymerization with the hydroxyl groups of the gas separation membrane occurs. For example, in the case of alkoxytitanium having an alkoxide group, it is thought that crosslinking polymerization as shown below progresses to form a wire-like structure.
（Ｒ：アルキル基、アリル基）
溶剤を蒸発させ、加熱等により架橋反応を進行させ架橋
重合させると、有機溶剤に不溶な網状組織体となる。(R: Alkyl group, allyl group) When the solvent is evaporated and the crosslinking reaction is proceeded by heating or the like to cause crosslinking polymerization, a network structure insoluble in organic solvents is formed.
また耐溶剤性を付与するばかりでなく、網状組織体であ
るため機械的強度も向上することとなる。Moreover, it not only provides solvent resistance but also improves mechanical strength because it is a network structure.
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.
（実施例１）
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）」（ポリプラスチック（ハ
）製）を、ヒドロキシ基を有する気体４Ｍ［Ｌ−１イ
ゼ１１しに一門也、ツク≦し・）しメ１１岬チレンとポ
リジメチルンロキサンとの共重合体をベンゼンに２％（
重量％）溶解し、約５％（重量％）のテトラヒドロフラ
ンを加えた溶液を水面上に展開し、溶剤を蒸発させ薄膜
を作成し、上記多孔性支持膜上に積層（２層）した後、
ヒドロキン基と架橋重合する多官能試薬としてアルコキ
ンチタンであるジー１−プロポキシφビス（アセチルア
セトナト）チタン、商品名「チタンボンドＩ◇」（日本
達（イ）製）をα−プロパツールに０．０１係（重量
％）溶解した溶液に浸漬し、α−プロパツールを蒸発さ
せた後、架橋重合を進行させるため、６０℃で１時間加
熱して気体分離用複合膜を作成した。(Example 1) A porous support membrane made of polypropylene under the trade name "Duraguard (Grade 2400)" (manufactured by Polyplastics (C)) was treated with a gas having a hydroxyl group of 4M [L-1
Ze11 and Ichimonya, Tsuku≦shi・) and Me11 Misaki 2% (
After dissolving (wt%) and adding about 5% (wt%) tetrahydrofuran on the water surface, the solvent was evaporated to create a thin film, which was then laminated (two layers) on the porous support membrane.
Di-1-propoxyφbis(acetylacetonato)titanium, which is an alkoxytitanium, as a polyfunctional reagent that crosslinks with hydroquine groups, trade name ``Titanium Bond I◇'' (manufactured by Nippon Tatsu (I)), is used as α-propatool. A composite membrane for gas separation was prepared by immersing it in a solution containing 0.01% (wt%) of α-propanol to evaporate and then heating it at 60° C. for 1 hour to promote crosslinking polymerization.
（実施例２）
実施例１と同様の多孔性支持膜上に実施例１と同様の気
体分離膜を積層（２層）した後、ヒドロキシ基と架橋重
合する多官能試薬としてアルコそンシランであるＮ−β
（アミノエチル）ｒ−アミンプロピルトリメトキシンラ
ン、商品名「’ＫＢＭら０３」（信越化学工業（社））
をα−ブロバノールに０．０１％ （重量％）溶解した
溶液に浸漬し、α−プロパツールを蒸発させた後、架橋
重合を進行させるため、５０゛Ｃで１時間加熱して気体
分離用複合膜を作成した。(Example 2) After laminating (two layers) the same gas separation membrane as in Example 1 on the same porous support membrane as in Example 1, alcoson silane was used as a polyfunctional reagent that crosslinked and polymerized with hydroxyl groups. N-β
(Aminoethyl) r-aminepropyltrimethoxine run, trade name "'KBM et al. 03" (Shin-Etsu Chemical Co., Ltd.)
was immersed in a solution containing 0.01% (wt%) of α-propanol, and after evaporating the α-propanol, it was heated at 50°C for 1 hour to promote cross-linking polymerization. A membrane was created.
なお多孔性支持膜やヒドロキン基を含む気体分離膜やヒ
ドロキン基と架橋重合する多官能試薬は本実施例に限定
されるものではない。Note that the porous support membrane, the gas separation membrane containing a hydroquine group, and the polyfunctional reagent that crosslinks and polymerizes with the hydroquine group are not limited to those in this example.
実施例１と同様の多孔性支持膜上に実施例１と同様の気
体分離膜を積層（２層）した気体分離用複合膜（従来例
）と実施例の気体分離用複合膜の初期性能と溶剤浸漬試
験（アセトン、テトラヒトフランに２０秒浸漬）後の性
能を表に表した。性能として酸素透過流量と選択係数を
測定した。酸素透過流量の測定方法は、３６朋φの気体
分離用複合膜に圧力１． ｏｋｑ／ｄの酸素ガスを加圧
し、酸素ガスが気体分離用複合膜を１０ｍ１透過するま
での時間を測定した。チン素ガスに関しても同様の方法
で測定し、選択係数を決定した。Initial performance of a composite membrane for gas separation (conventional example) in which a gas separation membrane similar to that of Example 1 is laminated (two layers) on a porous support membrane similar to that of Example 1, and a composite membrane for gas separation of this example. The performance after a solvent immersion test (immersion in acetone or tetrahydrofuran for 20 seconds) is shown in the table. The oxygen permeation flow rate and selectivity coefficient were measured as performances. The method for measuring the oxygen permeation flow rate is to apply a pressure of 1.5 mm to a 36 mm diameter composite membrane for gas separation. Oxygen gas of okq/d was pressurized, and the time required for the oxygen gas to permeate 10 ml of the composite membrane for gas separation was measured. Chin gas was measured in the same manner and the selectivity coefficient was determined.
この表より明らかなように、有機溶剤に可溶な気体分離
膜を網状組織にすることにより耐溶剤性の気体分離用複
合膜が作成できた。As is clear from this table, a solvent-resistant composite membrane for gas separation could be created by forming a gas separation membrane soluble in organic solvents into a network structure.
発明の効果
以上のように本発明は、多孔性支持膜上にヒドロキシ基
を有し有機溶剤に可溶な気体分離膜を、水面展開法など
により製膜し、積層した後、ヒドロキン基と架橋重合す
る多官能試薬を溶解した溶液に浸漬し、溶剤を蒸発させ
、加熱により反応を進行させ、架橋重合させ、網状組織
の気体分離膜を作成することにより、有機溶剤に不溶で
、機械的強度の向上した気体分離用複合膜を提供するこ
とができ、その実用的効果は犬なるものがある。Effects of the Invention As described above, the present invention provides a gas separation membrane having hydroxyl groups on a porous support membrane and soluble in organic solvents, which is formed by a water surface development method, laminated, and then cross-linked with hydroquine groups. By immersing it in a solution containing a polyfunctional reagent to be polymerized, evaporating the solvent, advancing the reaction by heating, and cross-linking polymerizing it to create a gas separation membrane with a network structure, it is insoluble in organic solvents and has mechanical strength. A composite membrane for gas separation with improved properties can be provided, and its practical effects are significant.
Claims (1)
積層し、かつその気体分離膜を架橋重合したことを特徴
とする気体分離用複合膜。A composite membrane for gas separation, characterized in that a gas separation membrane having hydroxyl groups is laminated on a porous support membrane, and the gas separation membrane is cross-linked and polymerized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12604786A JPS62282619A (en) | 1986-05-30 | 1986-05-30 | Composite membrane for separating gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12604786A JPS62282619A (en) | 1986-05-30 | 1986-05-30 | Composite membrane for separating gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62282619A true JPS62282619A (en) | 1987-12-08 |
Family
ID=14925333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12604786A Pending JPS62282619A (en) | 1986-05-30 | 1986-05-30 | Composite membrane for separating gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62282619A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4919694A (en) * | 1987-12-28 | 1990-04-24 | Idemitsu Kosan Company Limited | Selective gas permeation membranes and method of manufacturing them |
| US4932986A (en) * | 1989-05-09 | 1990-06-12 | Allied-Signal Inc. | Cross-linked gas selective membranes |
-
1986
- 1986-05-30 JP JP12604786A patent/JPS62282619A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4919694A (en) * | 1987-12-28 | 1990-04-24 | Idemitsu Kosan Company Limited | Selective gas permeation membranes and method of manufacturing them |
| US4932986A (en) * | 1989-05-09 | 1990-06-12 | Allied-Signal Inc. | Cross-linked gas selective membranes |
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