JPS6260932B2 - - Google Patents
Info
- Publication number
- JPS6260932B2 JPS6260932B2 JP58132857A JP13285783A JPS6260932B2 JP S6260932 B2 JPS6260932 B2 JP S6260932B2 JP 58132857 A JP58132857 A JP 58132857A JP 13285783 A JP13285783 A JP 13285783A JP S6260932 B2 JPS6260932 B2 JP S6260932B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- formula
- plasma
- composite membrane
- carbon monoxide
- 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
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
〔技術分野〕
本発明は、水素選択透過性複合膜およびその製
造方法に関し、更に詳しくは四弗化エチレン樹脂
多孔質膜にシリコン化合物が積層され、その表面
にグロー放電によるプラズマ重合薄膜が堆積され
ている水素選択透過性複合膜およびその製造方法
に関する。
〔発明の背景〕
近年、石油価格の高騰と石油資源の払底が叫ば
れるなかで化学工業の石油依存体質を改めるべ
く、石炭、天然ガス、オイルサンドといつた非石
油系原料を利用することが検討されている。具体
的には、非石油系原料に水蒸気改質や熱分解等の
処理を施すことにより得られる合成ガス、あるい
は製鉄所等におけるコークス炉の廃ガスなどを出
発原料とし、パラジウム等の特殊触媒を用いてメ
タノール、エタノール等の基礎化学品を製造する
試みである。炭素数１個の一酸化炭素を原料とす
ることからC1化学と名付けられているこの技術
分野は、新合成法のための触媒開発と、ガス濃度
調整のためのガス分離、精製技術の開発、特に水
素選択透過性膜の開発を必要とする。
また、水素選択透過性膜は、上記分野だけでは
なく、水電解やその他の水素含有ガスの分離精製
を最も省エネルギー的に実施するのにも有効であ
り、その有用性は極めて大きい。
優れた水素選択透過性膜とは、水素の他のガス
に対する高い選択透過性と、水素の高い透過性を
合わせ有し、かつ耐熱性、耐薬品性、高強度を持
つものである。
ここでいう高い選択透過性とは、例えば、一酸
化炭素に対し
α＝ＱＨ２／ＱＣＯ
〔ここで、ＱH2は水素の透過速度、ＱCOは一酸化
炭素の透過速度を表わす。〕
で定義される水素の選択透過性が大きいというこ
とである。また、高い透過性とは、ＱH2の絶対値
が大きいことを意味する。
ところが、市販されている高分子重合体または
共重合体の単一素材でこれら要求特性の全てを満
たすことは不可能である。従つて、これら要求特
性を満す材料を得るために現在まで種々の方法が
検討されてきた。その例として、相分離を利用
し、表面の活性スキン層の厚みを極力薄くした非
対称膜を用いる方法、あるいは活性スキン層に相
当する超薄膜を独立に製造して他の多孔性支持体
へ複合化しようとする方法などがある。しかしな
がら、いずれも上記要求特性全てを十分に満たし
た膜を得ることには成功していない。
本発明は、従来の膜に比べて上記要求特性を十
分に満たし特に、これまでに類をみない特性とし
て、高温においてすら高い性能を有する水素選択
透過性複合膜およびその製造方法を提供するもの
である。
〔発明の構成〕
本発明者は、耐熱性、耐薬品性、機械特性に優
れたものとして四弗化エチレン樹脂多孔質膜を支
持体とし、複合化素材として用いられることの多
いゴム系の材料に代え、機械特性、耐熱性、製膜
性にも優れ、かつガス透過性の大きいシリコン化
合物を複合化素材とし、さらには、グロー放電に
よるプラズマ重合薄膜を堆積させた構造とするこ
とにより、安定かつ均一な性能を有し、高温にお
いても高い選択透過性を有する水素選択透過性複
合膜が得られることを見い出した。
本発明で用いる四弗化エチレン樹脂多孔質膜
は、ポリスルホンやポリイミド等の耐熱性、耐薬
品性樹脂と比較しても特に優れた特性を有する材
料であり、しかも、その多孔化技術も進んでいる
ことから、安定した多孔性支持体として好適に用
いることができる。
一方、シリコン化合物はオルガノシロキサン
と、主鎖もしくは側鎖に少なくとも１個の芳香環
を有する有機物との縮合重合によつて得られ、そ
の構造式は次式で表わされる繰返し構造単位を持
つものである。
〔式中、Ｘは主鎖または側鎖に少なくとも１個の
芳香環を有する有機基、ＲおよびR1はそれぞれ
１価の官能基、ｍおよびｎは自然数を表わす。〕
本発明者は、四弗化エチレン樹脂多孔質膜の片
側表面に、このシリコン化合物の薄膜を積層する
ことにより、機械特性、耐熱性に優れ、ガス透過
性の大きい複合支持体が得られ、かつこの複合支
持体がプラズマ重合薄膜を堆積させるのに好適で
あることを見い出した。
具体的には、芳香環を主鎖または側鎖に少なく
とも１個を有する化合物と、オルガノシロキサン
化合物とのブロツク共重合体からなるシリコン化
合物はグロー放電によるプラズマ雰囲気における
分解が不思議な程に少なく、プラズマ重合とプラ
ズマスパツタリングとの競争反応となる通常の支
持体と比較して、専らプラズマ重合の方が優先的
に生じるため安定な重合薄膜の堆積が可能とな
り、結果として支持体の解重合や水素発生に起因
すると思われるクレーター状の欠陥や亀裂等の部
分がほとんど消滅する。芳香環を有しない化合物
としてたとえばジメチルポリシロキサンを支持体
としてグロー放電雰囲気にさらすと、プラズマ重
合による重量増加よりもプラズマスパツタリング
による重量減少の方が優先して進行し、結果とし
て安定な品質の水素選択透過性複合膜を得ること
が出来難くなる。
本発明で用いるシリコン化合物は、前記構造式
（）で示される繰り返し単位からなる重合体で
あつて、Ｘとしては、例えば
[Technical Field] The present invention relates to a hydrogen permselective composite membrane and a method for producing the same, and more specifically, a silicon compound is laminated on a porous tetrafluoroethylene resin membrane, and a plasma-polymerized thin film is deposited on the surface of the membrane by glow discharge. The present invention relates to a hydrogen selectively permeable composite membrane and a method for manufacturing the same. [Background of the Invention] In recent years, with soaring oil prices and concerns about the depletion of oil resources, it has become possible to use non-petroleum raw materials such as coal, natural gas, and oil sands in order to change the chemical industry's dependence on oil. It is being considered. Specifically, the starting materials are synthesis gas obtained by subjecting non-petroleum raw materials to treatments such as steam reforming and thermal decomposition, or waste gas from coke ovens at steel plants, etc., and special catalysts such as palladium are used as starting materials. This is an attempt to manufacture basic chemicals such as methanol and ethanol by using this method. This field of technology, named C1 chemistry because it uses carbon monoxide, which has one carbon, as a raw material, involves the development of catalysts for new synthesis methods, and the development of gas separation and purification technologies to adjust gas concentration. , especially requiring the development of hydrogen selectively permeable membranes. In addition, hydrogen selective permeability membranes are effective not only in the above-mentioned fields, but also in water electrolysis and separation and purification of other hydrogen-containing gases in the most energy-saving manner, and are extremely useful. An excellent hydrogen permselective membrane is one that has both high permselectivity for hydrogen against other gases and high permeability for hydrogen, and also has heat resistance, chemical resistance, and high strength. High selective permselectivity here means, for example, α=Q H2 /Q CO for carbon monoxide [where Q H2 represents the permeation rate of hydrogen and Q CO represents the permeation rate of carbon monoxide. ] This means that the selective permselectivity of hydrogen defined by the following is large. Moreover, high transparency means that the absolute value of Q H2 is large. However, it is impossible to satisfy all of these required properties with a single commercially available polymer or copolymer material. Therefore, various methods have been studied to date to obtain materials that satisfy these required characteristics. Examples include methods that utilize phase separation to use an asymmetric membrane with an active skin layer on the surface as thin as possible, or an ultra-thin membrane corresponding to the active skin layer that is manufactured independently and composited onto another porous support. There are ways to try to change it. However, none of these methods has succeeded in obtaining a film that fully satisfies all of the above-mentioned required characteristics. The present invention provides a selectively permeable hydrogen composite membrane that fully satisfies the above-mentioned required properties compared to conventional membranes, and in particular, has unprecedented properties such as high performance even at high temperatures, and a method for producing the same. It is. [Structure of the Invention] The present inventor uses a polytetrafluoroethylene resin porous membrane as a support because it has excellent heat resistance, chemical resistance, and mechanical properties, and developed a rubber-based material that is often used as a composite material. Instead, we used a composite material made of a silicon compound that has excellent mechanical properties, heat resistance, and film-forming properties, and has high gas permeability, and furthermore, we created a structure in which a plasma polymerized thin film was deposited using glow discharge. It has also been found that a hydrogen selectively permeable composite membrane having uniform performance and high permselectivity even at high temperatures can be obtained. The porous tetrafluoroethylene resin membrane used in the present invention is a material with particularly excellent properties compared to heat-resistant and chemical-resistant resins such as polysulfone and polyimide, and its porous technology is also advanced. Therefore, it can be suitably used as a stable porous support. On the other hand, silicon compounds are obtained by condensation polymerization of organosiloxane and an organic substance having at least one aromatic ring in the main chain or side chain, and have a repeating structural unit represented by the following formula: be. [Wherein, X represents an organic group having at least one aromatic ring in the main chain or side chain, R and R 1 each represent a monovalent functional group, and m and n represent natural numbers. ] The present inventor has discovered that by laminating a thin film of this silicon compound on one surface of a porous tetrafluoroethylene resin membrane, a composite support with excellent mechanical properties, heat resistance, and high gas permeability can be obtained. We have also found that this composite support is suitable for depositing plasma polymerized thin films. Specifically, a silicon compound made of a block copolymer of a compound having at least one aromatic ring in the main chain or side chain and an organosiloxane compound has a mysteriously low decomposition in a plasma atmosphere due to glow discharge. Compared to normal supports where plasma polymerization and plasma sputtering compete with each other, plasma polymerization occurs preferentially, making it possible to deposit a stable polymeric thin film, resulting in depolymerization of the support. Most of the crater-like defects and cracks that are thought to be caused by hydrogen generation have disappeared. When a compound without an aromatic ring, such as dimethylpolysiloxane, is used as a support and exposed to a glow discharge atmosphere, the weight decrease due to plasma sputtering takes precedence over the weight increase due to plasma polymerization, resulting in stable quality. It becomes difficult to obtain a hydrogen selectively permeable composite membrane. The silicon compound used in the present invention is a polymer consisting of repeating units represented by the above structural formula (), where X is, for example,
【式】【formula】
【式】などをあげることができる。
もちろんこれ以外のものであつても良い。Ｒ、
R1は、例えば−Ｈ、−CH3、[Formula] etc. can be given. Of course, it may be something other than this. R,
R 1 is, for example, -H, -CH 3 ,
耐熱性、耐薬品性、機械特性に優れた四弗化エ
チレン樹脂多孔質膜を支持体とし、機械特性、製
膜性、耐熱性に優れガス透過性の大きいシリコン
化合物を複合化素材とし、そのプラズマ雰囲気に
おける安定性を生かして、プラズマ重合薄膜を安
定して堆積させることにより、高性能かつ均一な
水素ガス選択透過性複合膜を得ることが可能とな
つた。また、この複合膜は、これまでの膜に比べ
て、高温においても高い水素選択透過性を維持で
きるため、水素の選択透過、特にC1化学等にお
ける高温のガスの分離・精製が可能となり、C1
化学プロセスにおける原料ガスの降温・昇温とい
つた莫大なエネルギーを要する工程を省略もしく
は縮小することを可能とするものである。従つ
て、水素の選択透過を、より省エネルギー的に実
施するために、極めて大きな効果が期待できる。
A porous tetrafluoroethylene resin membrane with excellent heat resistance, chemical resistance, and mechanical properties is used as a support, and a silicon compound with excellent mechanical properties, film formability, and heat resistance and high gas permeability is used as a composite material. By taking advantage of its stability in a plasma atmosphere and stably depositing a plasma-polymerized thin film, it has become possible to obtain a high-performance and uniform hydrogen gas permselective composite film. In addition, this composite membrane can maintain high hydrogen selective permeability even at high temperatures compared to conventional membranes, making it possible to selectively permeate hydrogen, especially for the separation and purification of high-temperature gases in C1 chemistry, etc. C 1
This makes it possible to omit or reduce steps that require enormous amounts of energy, such as lowering and increasing the temperature of raw material gas in chemical processes. Therefore, an extremely large effect can be expected in carrying out the selective permeation of hydrogen in a more energy-saving manner.
Claims (1)
芳香環を有する有機基、ＲおよびR1はそれぞれ
１価の官能基、ｍおよびｎは自然数を表わす。〕 で示されるシリコン化合物が積層され、その表面
に少なくとも１個の二重結合または三重結合を含
むオルガノシラン化合物のグロー放電によるプラ
ズマ重合薄膜が堆積されていることを特徴とする
水素選択透過性複合膜。 ２ 70℃を越える温度雰囲気において、 α＝ＱＨ２／ＱＣＯ 〔ここで、ＱH2は水素の透過速度、ＱCOは一酸化
炭素の透過速度を表わす。〕 で定義される水素の一酸化炭素に対する選択透過
性αが少なくとも20であることを特徴とする特許
請求の範囲第１項記載の複合膜。 ３ シリコン化合物が、ポリジメチルシロキサン
−ビスフエノールＡカーボネートブロツクコポリ
マーまたはポリジメチルシロキサン−α−メチル
スチレンブロツクコポリマーであることを特徴と
する特許請求の範囲第１項記載の複合膜。 ４ オルガノシラン化合物が、 式：Ｒ２ ｌ−Si−Ｙ4-l 〔式中、R2はビニル、エチニルまたはアリル、Ｙ
は水素、塩素、メチルまたはエチル、ｎは１〜４
の整数を表わす。〕 で示される化合物であることを特徴とする特許請
求の範囲第１項記載の複合膜。 ５ 構造式： 〔式中、Ｘは主鎖または側鎖に少なくとも１個の
芳香環を有する有機基、ＲおよびR1はそれぞれ
１価の官能基、ｍおよびｎは自然数を表わす。〕 で示されるシリコン化合物と溶剤とを含んで成る
溶液を四弗化エチレン樹脂多孔質膜表面に塗布
し、乾燥させた後、少なくとも１個の二重結合ま
たは三重結合を含むオルガノシラン化合物をモノ
マー蒸気として5torr以下の雰囲気に供給しなが
らグロー放電させてプラズマ重合薄膜を堆積させ
ることを特徴とする水素選択透過性複合膜の製造
方法。 ６ 70℃を越える温度雰囲気において、 α＝ＱＨ２／ＱＣＯ 〔ここで、ＱH2は水素の透過速度、ＱCOは一酸化
炭素の透過速度を表わす。〕 で定義される水素の一酸化炭素に対する複合膜の
選択透過性αが少なくとも20となる条件でプラズ
マ重合を行なうことを特徴とする特許請求の範囲
第５項記載の製造方法。 ７ ポリジメチルシロキサン−ビスフエノールＡ
カーボネートブロツクコポリマーまたはポリジメ
チルシロキサン−α−メチルスチレンブロツクコ
ポリマーと溶剤とを含んで成る溶液を四弗化エチ
レン樹脂多孔質膜表面に塗布し、乾燥させること
を特徴とする特許請求の範囲第５項記載の製造方
法。 ８ 式：Ｒ２ ｌ−Si−Ｙ4-l 〔式中、R2はビニル、エチニルまたはアリル、Ｙ
は水素、塩素、メチルまたはエチル、ｎは１〜４
の整数を表わす。〕 で示されるオルガノシラン化合物をモノマー蒸気
としてプラズマ重合することを特徴とする特許請
求の範囲第５項記載の製造方法。[Claims] 1. A porous tetrafluoroethylene resin membrane having the following structural formula: [Wherein, X represents an organic group having at least one aromatic ring in the main chain or side chain, R and R 1 each represent a monovalent functional group, and m and n represent natural numbers. ] A selectively permeable hydrogen composite, characterized in that silicon compounds shown in the formula are laminated, and a plasma-polymerized thin film formed by glow discharge of an organosilane compound containing at least one double bond or triple bond is deposited on the surface of the silicon compound. film. 2 In an atmosphere with a temperature exceeding 70°C, α=Q H2 /Q CO [where Q H2 represents the permeation rate of hydrogen and Q CO represents the permeation rate of carbon monoxide. ] The composite membrane according to claim 1, characterized in that the permselectivity α of hydrogen to carbon monoxide defined by: is at least 20. 3. The composite membrane according to claim 1, wherein the silicon compound is a polydimethylsiloxane-bisphenol A carbonate block copolymer or a polydimethylsiloxane-α-methylstyrene block copolymer. 4 The organosilane compound has the formula: R 2 l -Si-Y 4-l [wherein R 2 is vinyl, ethynyl or allyl, Y
is hydrogen, chlorine, methyl or ethyl, n is 1-4
represents an integer. ] The composite membrane according to claim 1, which is a compound represented by the following. 5 Structural formula: [Wherein, X represents an organic group having at least one aromatic ring in the main chain or side chain, R and R 1 each represent a monovalent functional group, and m and n represent natural numbers. ] A solution containing a silicon compound shown in the formula and a solvent is applied to the surface of a porous tetrafluoroethylene resin membrane, dried, and then an organosilane compound containing at least one double bond or triple bond is monomerized. A method for producing a selectively permeable hydrogen composite membrane, which comprises depositing a plasma-polymerized thin film by glow discharge while supplying vapor as vapor to an atmosphere of 5 torr or less. 6 In an atmosphere with a temperature exceeding 70°C, α=Q H2 /Q CO [where Q H2 represents the permeation rate of hydrogen and Q CO represents the permeation rate of carbon monoxide. ] The manufacturing method according to claim 5, characterized in that the plasma polymerization is carried out under conditions such that the composite membrane has a permselectivity α of at least 20 for hydrogen and carbon monoxide. 7 Polydimethylsiloxane-bisphenol A
Claim 5, characterized in that a solution containing a carbonate block copolymer or a polydimethylsiloxane-α-methylstyrene block copolymer and a solvent is applied to the surface of a polytetrafluoroethylene resin porous membrane and dried. Manufacturing method described. 8 Formula: R 2 l -Si-Y 4-l [wherein R 2 is vinyl, ethynyl or allyl, Y
is hydrogen, chlorine, methyl or ethyl, n is 1-4
represents an integer. ] The manufacturing method according to claim 5, characterized in that the organosilane compound represented by the following is plasma-polymerized as monomer vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13285783A JPS6025506A (en) | 1983-07-22 | 1983-07-22 | Hydrogen permselective composite membrane and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13285783A JPS6025506A (en) | 1983-07-22 | 1983-07-22 | Hydrogen permselective composite membrane and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6025506A JPS6025506A (en) | 1985-02-08 |
| JPS6260932B2 true JPS6260932B2 (en) | 1987-12-18 |
Family
ID=15091145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13285783A Granted JPS6025506A (en) | 1983-07-22 | 1983-07-22 | Hydrogen permselective composite membrane and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6025506A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10163168A1 (en) * | 2001-12-21 | 2003-07-03 | Degussa | volume aeration |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5969105A (en) * | 1982-10-12 | 1984-04-19 | Shin Etsu Chem Co Ltd | Composite molded body for gas separation |
-
1983
- 1983-07-22 JP JP13285783A patent/JPS6025506A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6025506A (en) | 1985-02-08 |
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