JPH0440223A - Gas separation composite membrane - Google Patents
Gas separation composite membraneInfo
- Publication number
- JPH0440223A JPH0440223A JP14477890A JP14477890A JPH0440223A JP H0440223 A JPH0440223 A JP H0440223A JP 14477890 A JP14477890 A JP 14477890A JP 14477890 A JP14477890 A JP 14477890A JP H0440223 A JPH0440223 A JP H0440223A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- porous support
- gas separation
- pmsp
- separation composite
- 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
- 238000000926 separation method Methods 0.000 title claims description 20
- 239000002131 composite material Substances 0.000 title claims description 16
- 239000012528 membrane Substances 0.000 title abstract description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- -1 polysiloxane Polymers 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 6
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims description 18
- 230000035699 permeability Effects 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 6
- DCGLONGLPGISNX-UHFFFAOYSA-N trimethyl(prop-1-ynyl)silane Chemical compound CC#C[Si](C)(C)C DCGLONGLPGISNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 238000010030 laminating Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000009751 slip forming Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002834 transmittance Methods 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】
産業上の利用分野
本発明は、２種以上の混合気体を分離濃縮する気体分離
複合膜に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a gas separation composite membrane for separating and concentrating two or more types of mixed gases.
従来の技術
近年、有機高分子を用いた気体分離膜力；数多く提案さ
れている。気体分離膜を用いて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、廃棄物処理、
健康、医療の各分野で多大な貢献をすることができると
期待されている。BACKGROUND OF THE INVENTION In recent years, many proposals have been made for gas separation membranes using organic polymers. If oxygen in the air can be separated and concentrated at low cost using a gas separation membrane, what about combustion and iron manufacturing? Ceramics, waste treatment,
It is expected that it will be able to make significant contributions in the fields of health and medicine.
気体分離膜には、空気などのような酸素を含む気体から
選択的に酸素を分離する機能が大きいこと、および効率
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。空
気中から酸素を分離濃縮する場合、酸素選択係数αは酸
素透過係数／窒素透過係数の値で表わされる。また実用
上から言えば、気体分離膜の強度も必要となり、そのた
めに多孔質支持体に強度をもたせ、これに有機高分子の
薄膜を付着させて気体分離複合膜として用いられている
。しかし従来の多孔質支持体では、ポリ−１−トリメチ
ルシリル−プロピン（以下ＰＭＳＰと略す）を水面展開
により形成した薄膜を直接その多孔質支持体に付着させ
ることは難しく連続製膜が困難であった。そのためポリ
シロキサンの接着層を設け、その上にＰＭＳＰの薄膜を
製膜する方法（特開昭６１−１２９ｃｃ８号公報）が提
案されている。Gas separation membranes have a large ability to selectively separate oxygen from oxygen-containing gases such as air, and a large ability to efficiently transmit oxygen, that is, they have a large oxygen selection coefficient and oxygen permeability coefficient. This is required. When separating and concentrating oxygen from air, the oxygen selection coefficient α is expressed by the value of oxygen permeability coefficient/nitrogen permeability coefficient. Furthermore, from a practical point of view, the strength of the gas separation membrane is also required, and for this purpose, a porous support is provided with strength, and a thin organic polymer film is attached to this to provide a gas separation composite membrane. However, with conventional porous supports, it has been difficult to directly attach a thin film of poly-1-trimethylsilyl-propyne (hereinafter referred to as PMSP) formed by spreading on the water surface to the porous support, and continuous film formation has been difficult. . Therefore, a method has been proposed in which a polysiloxane adhesive layer is provided and a PMSP thin film is formed thereon (Japanese Unexamined Patent Publication No. 129CC8/1983).
発明が解決しようとする課題
しかしなから上記従来の構成では、ＰＭＳＰよ９も酸素
透過係数が小さいポリシロキサンを接着層として用いて
いるため多孔質支持体に直接、吸引法によりＰＭＳＰ薄
膜を積層した気体分離複合膜と比べ酸素透過流量、酸素
選択係数がともに小さくなる。すなわち膜性能が低くな
るという課題を有していた。Problems to be Solved by the InventionHowever, in the conventional configuration described above, polysiloxane, which has an oxygen permeability coefficient 9 lower than that of PMSP, is used as an adhesive layer, so a PMSP thin film is laminated directly onto a porous support by a suction method. Compared to gas separation composite membranes, both the oxygen permeation flow rate and oxygen selection coefficient are smaller. In other words, the problem was that the membrane performance deteriorated.
本発明は上記課題を解決するものであり、酸素透過流量
を酸素選択係数ともに高い、すなわち膜性能の高い気体
分離複合膜を提供することを目的とするものである。The present invention is intended to solve the above problems, and aims to provide a gas separation composite membrane with high oxygen permeation flow rate and high oxygen selectivity coefficient, that is, high membrane performance.
課題を解決するための手段
本発明は上記目的を達成するために、疎水度が１０秒以
下で、透気度が２０秒／６ 、４５ （２遥、５６７ｆ
Ｔ１ｃｃ０以下であるポリエーテルスルホン多孔質支持
体にＰＭＳＰの薄膜を積層し、さらにその上にポリシロ
キサンとスチレンの共重合体の薄膜を積層したものであ
る。Means for Solving the Problems In order to achieve the above objects, the present invention has a hydrophobicity of 10 seconds or less and an air permeability of 20 seconds/6, 45 (2 Haruka, 567f
A thin film of PMSP is laminated on a polyethersulfone porous support having T1cc0 or less, and a thin film of a copolymer of polysiloxane and styrene is further laminated thereon.
作用
したがって本発明によれば、疎水度が１０秒以下の多孔
質支持体を使用しており、その表面は平滑であるため水
面展開により形成したＰＭＳＰ薄膜と接触させると接触
面積が増大し、多孔質支持体とＰＭＳＰ薄膜が接着しや
すくなり、多孔質支持体の上にＰＭＳＰ薄膜を直接連続
製膜することが可能となる。得られた気体分離複合膜は
、従来の気体分離複合膜と比べ酸素透過流量、酸素選択
係数ともに高い値を示す。一方、透過度が２０秒／６−
４５ ｃ４＋ ５６７ ｆ ｔ １ｃｃ Ｃ以下である
と多孔質支持体の圧力の損失が小さく、気体分離複合膜
に一定の圧力を与えると、ＰＭＳＰ薄膜にかかる圧力差
、圧力比ともに大きくなり、気体分離複合膜の酸素透過
流量と酸素選択係数が高い値となる。またポリシロキサ
ンとスチレンとの共重合体の薄膜を積層することにより
耐湿特性が向上し信頼性が高くなる。Effect Therefore, according to the present invention, a porous support with a hydrophobicity of 10 seconds or less is used, and since its surface is smooth, when it is brought into contact with a PMSP thin film formed by spreading on a water surface, the contact area increases and the porous support is This facilitates adhesion between the porous support and the PMSP thin film, making it possible to directly and continuously form the PMSP thin film on the porous support. The obtained gas separation composite membrane exhibits higher values of both oxygen permeation flow rate and oxygen selection coefficient than conventional gas separation composite membranes. On the other hand, the transmittance is 20 seconds/6-
45 c4+ 567 f t 1cc C or less, the pressure loss of the porous support is small, and when a constant pressure is applied to the gas separation composite membrane, both the pressure difference and pressure ratio applied to the PMSP thin membrane become large, and the gas separation composite membrane The oxygen permeation flow rate and oxygen selectivity coefficient of the membrane become high values. Furthermore, by laminating a thin film of a copolymer of polysiloxane and styrene, moisture resistance is improved and reliability is increased.
実施例 以下本発明の一実施例について説明する。Example An embodiment of the present invention will be described below.
ビニル基を含むジメチルポリシロキサン（トーレマシリ
コーン（株）、商品名「５Ｈ−４１０」）５０．０ ｉ
Ｐをモノクロロベンゼン７ｃｃ−に溶解し、これにスチ
レンモノマーを１０．Ｏｐ添加し、さらに過酸化物とし
て、２．６ジメチル２．６ジ（ターシャリブチルパーオ
キシ）ヘキサン（日本油脂側、商品名「バーへキサ２５
ＢＪ ）を０．２５ｙ−添加した後、窒素雰囲気中で温
度１２０’Ｃ，で１２時間重合反応を行い、この重合溶
液を６１のメタノールに投入して沈殿物を得た。この沈
殿物を精製し、ジメチルポリシロキサンとスチレンの共
重合体を得た。つぎにＰＭＳＰ（平均分子量：２ｃｃ万
）を０．５重量％含有させたベンゼン溶液を作製し、こ
のベンゼン溶液に対して６重量％のテトラヒドロ７ラン
を添加し、水面展開用製膜溶液とした。Dimethylpolysiloxane containing vinyl groups (Torema Silicone Co., Ltd., trade name "5H-410") 50.0 i
Dissolve P in 7 cc of monochlorobenzene, and add 10 cc of styrene monomer to it. 2.6 dimethyl 2.6 di(tert-butylperoxy)hexane (NOF side, product name "Bahexa 25") was added as a peroxide.
After adding 0.25y of BJ), a polymerization reaction was carried out at a temperature of 120'C in a nitrogen atmosphere for 12 hours, and the polymerization solution was poured into 61 methanol to obtain a precipitate. This precipitate was purified to obtain a copolymer of dimethylpolysiloxane and styrene. Next, a benzene solution containing 0.5% by weight of PMSP (average molecular weight: 2cc, 0,000) was prepared, and 6% by weight of tetrahydro7ran was added to this benzene solution to prepare a film forming solution for water surface development. .
この製膜溶液を水面上に滴下して薄膜を形成し、ポリプ
ロピレン不織布上に形成したポリエーテルスルホン多孔
質支持体（疎水度６秒、透気度２０秒／６．４５（？Ｊ
、５６７ｆ、１０１）Ｃ）上に１層形成し、さらにその
上にジメチルポリシロキサンとスチレンとの共重合体の
４重量％ベンゼン溶液に６重量％のテトラヒドロフラン
を添加した保護膜溶液を水面上に滴下して得た薄膜を１
層積層し、気体分離複合膜を形成した。This film-forming solution was dropped onto the water surface to form a thin film, and a polyether sulfone porous support (hydrophobicity 6 seconds, air permeability 20 seconds/6.45 (?J
, 567f, 101) C), and on top of that, a protective film solution made by adding 6% by weight of tetrahydrofuran to a 4% by weight benzene solution of a copolymer of dimethylpolysiloxane and styrene was placed on the water surface. The thin film obtained by dropping 1
The layers were laminated to form a gas separation composite membrane.
比較例
ビニル基を含むジメチルポリシロキサン（トーン・シリ
コーン（株）、商品名「Ｓ Ｈ−４１０Ｊ ）の４重量
％ベンゼン溶液に６重量％のテトラヒドロフランを添加
した溶液を水面上に滴下して薄膜を形成し、ポリプロピ
レン不織布上に形成したポリエーテルスルホン多孔質支
持体（疎水度５秒、透気度２０秒／６．４５Ｃ４＋
５６７ ｆ ＋ １０ ＣＣ）上に１層形成し、さらに
その上に上記実施例において得たＰＭＳＰの製膜溶液を
水面上に滴下して得た薄膜を１層積層した。さらにその
上に同じく上記実施例で得た保護膜溶液を水面上に滴下
して得た薄膜を１層積層し、気体分離複合膜を形成した
。Comparative Example A solution of dimethylpolysiloxane containing vinyl groups (Tone Silicone Co., Ltd., trade name "SH-410J") in benzene with 6% tetrahydrofuran added was dropped onto the water surface to form a thin film. Polyether sulfone porous support (hydrophobicity 5 seconds, air permeability 20 seconds/6.45C4+) formed on a polypropylene nonwoven fabric.
567 f + 10 CC), and on top of that, one layer of a thin film obtained by dropping the PMSP film-forming solution obtained in the above example onto the water surface was laminated. Furthermore, one layer of a thin film obtained by dropping the protective film solution obtained in the above example onto the water surface was laminated thereon to form a gas separation composite membrane.
なお、疎水度とは、５０＋＋ｏｎＸ５０ｍ＋の多孔質支
持体の試験片を試験場所の温湿度状態に６時間以上放置
し、２０℃の温度に保持した純水の水面上に、その表面
を２秒間浸漬して、多孔質支持体表面に水が付着した状
態を形成し、その後ただちに取シ出し、水平に静止した
状態において水が多孔質支持体表面から動かなくなるま
での時間の値であり、単位は秒で表わす。In addition, hydrophobicity is defined as a test piece of a porous support of 50++ on x 50 m+ left for 6 hours or more in the temperature and humidity conditions of the test location, and then immersed for 2 seconds on the surface of pure water maintained at a temperature of 20 ° C. This is the time it takes for water to adhere to the surface of the porous support, then immediately take it out, and to stop the water from moving from the surface of the porous support when it is held still horizontally.The unit is Expressed in seconds.
また透気度とは、多孔質支持体の試験片５０ａ＋Ｘ１３
０ｍをＢ型ガーレ式デンソメータ（ＴＯＴＯ８ＩＣＩＫ
Ｉ ５ＫＩＳＡＫＵ−３ＨＯ，ＬＴＤ−）［より測定し
た値である。単位は（秒／６．４５ｃ４１６６７ｆ ｌ
１ｃｃ０ ）で表わす。In addition, air permeability refers to test piece 50a+X13 of porous support.
0m with B type Gurley densometer (TOTO8ICIK)
I 5KISAKU-3HO, LTD-) [This is a value measured from. The unit is (second/6.45c41667f l
1cc0).
つぎにこのようにして得られた実施例および比較例の気
体分離複合膜の膜性能を次の表に示す。Next, the membrane performances of the gas separation composite membranes of Examples and Comparative Examples thus obtained are shown in the following table.
また温度４０℃、相対湿度９６チに１ｃｃ０時間放置し
た後の膜性能も併せてその表に示した。測定条件は有効
面積１ｌ−３ｅＪ、測定圧力１．０＃／ｃ遥。The table also shows the membrane performance after 1 cc was left for 0 hours at a temperature of 40° C. and a relative humidity of 96° C. The measurement conditions were an effective area of 1l-3eJ and a measurement pressure of 1.0#/c.
測定温度２６℃とした。The measurement temperature was 26°C.
表
このように実施例によれば、酸素透過流量において大き
な酸素透過機能を示し、さらに長時間の温度湿度試験後
においても大きな劣化がないという優れた気体分離複合
膜を得ることができた。As shown in the table, according to the examples, it was possible to obtain an excellent gas separation composite membrane that exhibited a large oxygen permeation function in terms of oxygen permeation flow rate and did not show any major deterioration even after a long time temperature and humidity test.
発明の効果
以上の実施例から明らかなように本発明によれば、表面
の疎水度が１ｏ（ｓｅａ）以下で透気度が２０ ｓｅａ
／６．４６ Ｊ ＋ ６６７７ ＋ １ｃｃ０以下であ
る多孔質支持体を用いるため水面展開によシ形成したＰ
ＭＳＰ薄膜を直接連続製膜が可能であり、製膜して得た
気体分離複合膜は酸素透過流量、酸素選択係数ともに高
い値、すなわち高い膜性能を示ス。またポリシロキサン
とスチレンの共重合体の薄膜を積層することによシ耐湿
特性に優れた気体分離複合膜を得ることができるもので
ある。Effects of the Invention As is clear from the above examples, according to the present invention, the surface hydrophobicity is 1 o (sea) or less and the air permeability is 20 sea.
/6.46 J + 6677 + P formed by water surface development to use a porous support of 1cc0 or less
It is possible to directly and continuously form an MSP thin film, and the resulting gas separation composite membrane exhibits high values for both oxygen permeation flow rate and oxygen selectivity coefficient, that is, high membrane performance. Furthermore, by laminating thin films of a copolymer of polysiloxane and styrene, a gas separation composite membrane with excellent moisture resistance can be obtained.
Claims (1)
＾２、５６７ｇ、１０ｃｃ以下であるポリエーテルスル
ホン多孔質支持体にポリ−１−トリメチルシリル−プロ
ピンの薄膜を積層し、さらにその上にポリシロキサンと
スチレンの共重合体の薄膜を積層した気体分離複合膜。Hydrophobicity is 10 seconds or less, air permeability is 20 seconds/6.45cm
^2 A gas separation composite in which a thin film of poly-1-trimethylsilyl-propyne is laminated on a polyethersulfone porous support weighing less than 567 g and 10 cc, and a thin film of a copolymer of polysiloxane and styrene is further laminated thereon. film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14477890A JPH0440223A (en) | 1990-06-01 | 1990-06-01 | Gas separation composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14477890A JPH0440223A (en) | 1990-06-01 | 1990-06-01 | Gas separation composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0440223A true JPH0440223A (en) | 1992-02-10 |
Family
ID=15370216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14477890A Pending JPH0440223A (en) | 1990-06-01 | 1990-06-01 | Gas separation composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0440223A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811196A (en) * | 1996-02-23 | 1998-09-22 | Nitto Denko Corporation | Laminated asymmetric membrane and method for manufacturing the same |
| US5882382A (en) * | 1995-10-31 | 1999-03-16 | Nitto Denko Corporation | Polyimide semipermeable membrane |
| US6781654B2 (en) | 2001-01-13 | 2004-08-24 | Lg Electronics, Inc. | Liquid crystal display apparatus and mobile terminal using same |
-
1990
- 1990-06-01 JP JP14477890A patent/JPH0440223A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5882382A (en) * | 1995-10-31 | 1999-03-16 | Nitto Denko Corporation | Polyimide semipermeable membrane |
| US5811196A (en) * | 1996-02-23 | 1998-09-22 | Nitto Denko Corporation | Laminated asymmetric membrane and method for manufacturing the same |
| US6781654B2 (en) | 2001-01-13 | 2004-08-24 | Lg Electronics, Inc. | Liquid crystal display apparatus and mobile terminal using same |
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