JPH06172557A - New bipolar film - Google Patents
New bipolar filmInfo
- Publication number
- JPH06172557A JPH06172557A JP4350988A JP35098892A JPH06172557A JP H06172557 A JPH06172557 A JP H06172557A JP 4350988 A JP4350988 A JP 4350988A JP 35098892 A JP35098892 A JP 35098892A JP H06172557 A JPH06172557 A JP H06172557A
- Authority
- JP
- Japan
- Prior art keywords
- bipolar
- membrane
- exchange membrane
- film
- cation
- 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.)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気透析による水スプ
リット法において特に有用なバイポーラ膜に関するもの
である。FIELD OF THE INVENTION The present invention relates to a bipolar membrane which is particularly useful in the water splitting method by electrodialysis.
【０００２】[0002]
【従来の技術】バイポーラ膜の陰イオン交換膜側を陽極
側に、陽イオン交換膜側を陰極側に向けて電極間に配置
して電流を印加せしめると、水が分裂（split ）して水
素イオンと水酸イオンに解離することは、Friletteが１
９５６年に報告しており、広く知られている。2. Description of the Related Art When an anion exchange membrane side of a bipolar membrane is placed on the anode side and a cation exchange membrane side is placed on the cathode side, and an electric current is applied between the electrodes, water splits and hydrogen is generated. Dissociation into ions and hydroxide ions is
It was reported in 956 and is widely known.
【０００３】バイポーラ膜はこの能力を有するために有
用であり、陰イオン交換膜及び／又は陽イオン交換膜を
適宜併用することにより、芒硝などの中性塩を原料とし
て硫酸と苛性ソーダなどの酸とアルカリを製造できるこ
とが知られている。酸やアルカリの製造コストの面から
考えると、膜による電圧降下が小さく、また同時に水の
解離効率が高いバイポーラ膜がなければならず、これら
の性能が長期にわたって発現されなければならない。A bipolar membrane is useful because it has this ability, and by using an anion exchange membrane and / or a cation exchange membrane in appropriate combination, a neutral salt such as Glauber's salt is used as a raw material to produce sulfuric acid and an acid such as caustic soda. It is known that alkali can be produced. Considering the production costs of acids and alkalis, it is necessary to have a bipolar membrane that has a small voltage drop across the membrane and at the same time has high water dissociation efficiency, and these performances must be exhibited for a long period of time.
【０００４】バイポーラ膜及びその製造方法は、すでに
いくつかのものが報告されている。例えば、スチレン−
ジビニルベンゼン共重合体をベースとするフィルムの片
面にスルホン化等の処理により陽イオン交換基を導入
し、もう一方の片面に４級アンモニウム基の陰イオン交
換基を導入してなるバイポーラ膜が特公昭６０−３１８
６０号及び特開昭６３−９５２３５号に開示されてい
る。また、予め製造された陰イオン交換膜と陽イオン交
換膜とを熱と圧力で融着させることによって製造する方
法が米国特許第３，３７２，１０１号に、ポリビニルア
ミンを接着剤として用いて接合する方法が特開昭６１−
２０７４４４号に開示されている。Several bipolar films and their manufacturing methods have already been reported. For example, styrene-
A bipolar membrane in which a cation exchange group is introduced on one side of a film based on a divinylbenzene copolymer by a treatment such as sulfonation and an anion exchange group of a quaternary ammonium group is introduced on the other side Kosho 60-318
No. 60 and JP-A-63-95235. In addition, a method of producing by previously fusing an anion exchange membrane and a cation exchange membrane by heat and pressure is disclosed in US Pat. No. 3,372,101, which uses polyvinylamine as an adhesive agent. The method to do this is JP-A-61-1
No. 207444.
【０００５】しかし、これらのバイポーラ膜は同一膜中
に陽イオン交換基と陰イオン交換基を有するため、これ
らの反対の電荷を持つ基が相互に侵入してイオン的に結
合し、中性の層を形成し、大きな電圧降下を生じる欠点
を有している。However, since these bipolar membranes have a cation exchange group and an anion exchange group in the same membrane, these groups having opposite charges invade each other and ionically bind to each other, resulting in a neutral It has the disadvantage of forming layers and causing a large voltage drop.
【０００６】これを回避するために、米国特許４，２５
３，９００号、特公昭６０−３５９３６号には、高い架
橋構造を有する有機イオン交換樹脂を陽イオン交換膜と
陰イオン交換膜の間に導入させ、反対の電荷を有する基
の相互侵入を防ぐバイポーラ膜が開示されている。ま
た、陽イオン交換膜又は陰イオン交換膜の界面に水溶性
無機化合物を含浸させるか又は含浸させた後にアルカリ
処理した後にプレスすることによって製造されたバイポ
ーラ膜が特開昭５９−４７２３５号及び特表平３−５０
５８９４号に開示されている。In order to avoid this, US Pat. No. 4,25
No. 3,900 and Japanese Patent Publication No. 60-35936, an organic ion exchange resin having a high cross-linking structure is introduced between a cation exchange membrane and an anion exchange membrane to prevent mutual intrusion of groups having opposite charges. Bipolar membranes are disclosed. Further, a bipolar membrane manufactured by impregnating the interface of a cation exchange membrane or an anion exchange membrane with a water-soluble inorganic compound, or impregnating it with an alkali and then pressing it is disclosed in JP-A-59-47235. Front flat 3-50
No. 5894.
【０００７】しかし、従来のバイポーラ膜は次のごとき
欠点を有している。即ち、高架橋イオン交換樹脂を界面
に存在させた場合、高い架橋構造を有するといえども有
機物ではイオン交換基の相互侵入を防ぎ得ず、経時的な
電圧降下の増加を生ずる。また、界面に無機化合物を介
在させる場合も、それらの物質が次第に膜外に溶出し、
やはり経時的な電圧降下の上昇を生じてしまう。However, the conventional bipolar film has the following drawbacks. That is, when a highly cross-linked ion exchange resin is present at the interface, even if it has a high cross-linking structure, the organic substance cannot prevent mutual intrusion of ion exchange groups, resulting in an increase in voltage drop over time. Also, when interposing an inorganic compound at the interface, those substances are gradually eluted out of the film,
After all, the voltage drop increases with time.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記の如き従
来のバイポーラ膜における欠点を解決し、電圧降下が小
さく、水の解離効率が高く、しかも長期間にわたって安
定な性能を有するバイポーラ膜を提供するものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of conventional bipolar membranes and provides a bipolar membrane having a small voltage drop, high water dissociation efficiency, and stable performance for a long period of time. To do.
【０００９】[0009]
【課題を解決するための手段】上記目的は、陽イオン交
換膜と陰イオン交換膜との界面に酸性塩型無機イオン交
換体層を存在せしめたことを特徴とするバイポーラ膜に
よって達成される。The above object can be achieved by a bipolar membrane characterized in that an acidic salt type inorganic ion exchanger layer is present at the interface between a cation exchange membrane and an anion exchange membrane.
【００１０】本発明で使用される酸性塩型無機イオン交
換体としては、種々のものが使用される。例えば、酸性
塩型無機イオン交換体の金属イオンとしてはＺｒ、Ｔ
ｉ、Ｓｎ、Ｇｅ、Ｈｆ、Ｔａ、Ｎｂ、Ｆｅ、Ａｌ、Ｇ
ａ、Ｉｎ、Ｔｈなどが使用され、また、酸としてはリン
酸のほか、Ｖ、Ａｓ、Ｎｂ、Ｓｂ、Ｔａ、Ｍｏ、Ｔｅ、
Ｗ、Ｓｅ、Ｓｉ、Ｃｒなどの酸素酸が使用される。なか
でも金属イオンが３価以上のカチオンからなる酸性塩型
無機イオン交換体が好ましい。本発明で使用される酸性
塩型無機イオン交換体の代表例としては、リン酸ジルコ
ニウム、リン酸チタン、リン酸スズ、モリブデン酸ジル
コニウム、タングステン酸スズ、アンチモン酸チタン、
ヒドロキシアパタイトなどが挙げられる。Various types of acidic salt type inorganic ion exchangers are used in the present invention. For example, as the metal ions of the acidic salt type inorganic ion exchanger, Zr, T
i, Sn, Ge, Hf, Ta, Nb, Fe, Al, G
a, In, Th, etc. are used, and as the acid, in addition to phosphoric acid, V, As, Nb, Sb, Ta, Mo, Te,
Oxygen acids such as W, Se, Si and Cr are used. Among them, an acidic salt type inorganic ion exchanger in which the metal ion is a cation having a valence of 3 or more is preferable. Representative examples of the acidic salt type inorganic ion exchanger used in the present invention include zirconium phosphate, titanium phosphate, tin phosphate, zirconium molybdate, tin tungstate, titanium antimonate,
Examples thereof include hydroxyapatite.
【００１１】酸性塩型無機イオン交換体層の厚みは、
０．０１〜１００μｍ、特には０．１〜１０μｍが好ま
しい。酸性塩型無機イオン交換体層がこれよりも薄いと
経時的に膜外に溶出し、バイポーラ膜の電圧降下が次第
に増加し、またこれよりも厚いと陰イオン交換膜と陽イ
オン交換膜の接合強度が低下し好ましくない。The thickness of the acidic salt type inorganic ion exchanger layer is
The thickness is preferably 0.01 to 100 μm, particularly preferably 0.1 to 10 μm. If the acid salt type inorganic ion exchanger layer is thinner than this, it elutes out of the membrane over time, and the voltage drop of the bipolar membrane gradually increases, and if it is thicker than this, the anion exchange membrane and the cation exchange membrane are joined. It is not preferable because the strength is lowered.
【００１２】酸性塩型無機イオン交換体の粒径は１μｍ
以下であることが好ましく、粒径がこれより大きいと、
陰イオン交換膜と陽イオン交換膜の接合強度が低下した
り、接合時に接合界面に気泡が入り好ましくない。なか
でも粒径０．０１〜０．５μｍが特に好ましい。The particle size of the acidic salt type inorganic ion exchanger is 1 μm.
The following is preferable, and if the particle size is larger than this,
It is not preferable because the bonding strength between the anion exchange membrane and the cation exchange membrane is lowered, or bubbles are introduced into the bonding interface during bonding. Among them, the particle diameter of 0.01 to 0.5 μm is particularly preferable.
【００１３】酸性塩型無機イオン交換体層を陰イオン交
換膜と陽イオン交換膜の間に導入する方法としては、種
々の手段が採用されるが、好ましくは次の手段が採用さ
れる。酸性塩型無機イオン交換体を溶媒中に分散させた
液又はペーストを陽イオン交換膜又は陰イオン交換膜の
表面に、塗布、キャスト、スプレー、スクリーン印刷、
熱転写などを用いて付着させ、しかる後、付着層を有す
るイオン交換膜と反対の電荷を有するイオン交換膜をキ
ャスト、熱圧着などにより接合する方法を用いることが
できる。As a method for introducing the acidic salt type inorganic ion exchanger layer between the anion exchange membrane and the cation exchange membrane, various means are adopted, but the following means is preferably adopted. A liquid or paste prepared by dispersing an acidic salt type inorganic ion exchanger in a solvent is applied on the surface of a cation exchange membrane or an anion exchange membrane, and cast, spray, screen print,
A method may be used in which the particles are attached by thermal transfer or the like, and thereafter, the ion exchange membrane having the adhesion layer and the ion exchange membrane having the opposite electric charge are joined by casting, thermocompression bonding or the like.
【００１４】酸性塩型無機イオン交換層は、電圧降下を
小さくさせるためには、陽イオン交換膜と陰イオン交換
膜の全界面にわたって設けることが望ましいが、陽イオ
ン交換膜と陰イオン交換膜の接合強度を大きくするた
め、２５〜９５％の面積に設けることが好ましい。酸性
塩型無機イオン交換体層が導入された面積がこれより大
きいと接合強度が低下し、これより小さいと電圧降下が
大きくなり好ましくない。さらに電解透析面にのみ設け
た場合には、接合強度が大きく、電圧降下を小さく保つ
ことができ最も望ましい。The acid salt type inorganic ion exchange layer is preferably provided over the entire interface between the cation exchange membrane and the anion exchange membrane in order to reduce the voltage drop. In order to increase the bonding strength, it is preferable to provide it in an area of 25 to 95%. If the area into which the acidic salt type inorganic ion exchanger layer is introduced is larger than this, the bonding strength decreases, and if it is smaller than this, the voltage drop becomes large, which is not preferable. Further, when it is provided only on the electrodialysis surface, the bonding strength is large and the voltage drop can be kept small, which is the most desirable.
【００１５】本発明のバイポーラ膜を構成する陽イオン
交換膜としては、バイポーラ膜内で生成する水素イオン
の透過性が大きく、陰イオンを透過させがたい陽イオン
交換膜が使用でき、好ましくはスルホン酸基を有する強
酸性陽イオン交換膜が例示される。かかる強酸性陽イオ
ン交換膜としては、スチレン−ジビニルベンゼン系重合
体フィルム、スチレン−ブタジエン系重合体フィルム等
の芳香環を有する重合体フィルムにスルホン酸基を導入
した膜、又はスチレン等のモノマーを、オレフィン系や
含フッ素系の重合体、織布、不織布などにグラフト重合
したものにスルホン酸基を導入した膜などが例示され
る。As the cation exchange membrane which constitutes the bipolar membrane of the present invention, a cation exchange membrane which has a large permeability for hydrogen ions generated in the bipolar membrane and which is difficult for anions to permeate can be used, and preferably a sulfone. A strongly acidic cation exchange membrane having an acid group is exemplified. As such a strongly acidic cation exchange membrane, a styrene-divinylbenzene polymer film, a membrane in which a sulfonic acid group is introduced into a polymer film having an aromatic ring such as a styrene-butadiene polymer film, or a monomer such as styrene is used. Examples thereof include a film obtained by introducing a sulfonic acid group into what is obtained by graft-polymerizing an olefin-based or fluorine-containing polymer, a woven fabric or a non-woven fabric.
【００１６】さらに、化２で表される繰り返し単位から
なるパーフルオロカーボン重合体によって形成される陽
イオン交換膜が電流効率の発現性に加えて、塩酸、硫
酸、硝酸、フッ酸などに対する耐酸性や耐熱性に優れて
いるので特に好ましい。かかる陽イオン交換膜はイオン
交換基がクラスター構造を形成するため高いアニオン排
除性を有し、バイポーラ膜で高い水の解離効率を発現す
ることができる。Further, the cation exchange membrane formed of the perfluorocarbon polymer composed of the repeating unit represented by the chemical formula 2 has a current efficiency, and in addition to acid resistance to hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and the like. It is particularly preferable because it has excellent heat resistance. Such a cation exchange membrane has a high anion exclusion property because the ion exchange groups form a cluster structure, and can exhibit high water dissociation efficiency in a bipolar membrane.
【００１７】[0017]
【化２】 なお、化２においてｍは０又は１、ｎは１〜５、ｘ／ｙ
は２〜１６、ＸはＳＯ 3 Ｍ又はＣＯＯＭを表し、Ｍは水
素、アルカリ金属、アルカリ土類金属又はアンモニウム
を表す。[Chemical 2]In Chemical formula 2, m is 0 or 1, n is 1 to 5, x / y
Is 2 to 16, X is SO 3 Represents M or COOM, where M is water
Elemental, alkali metal, alkaline earth metal or ammonium
Represents
【００１８】バイポーラ膜を構成する陽イオン交換膜の
厚さは、５μｍ〜３００μｍの範囲で通常使用される
が、膜抵抗及び強度の点から、好ましくは２０μｍ〜１
５０μｍの範囲のものが使用される。イオン交換容量に
ついては、膜抵抗と輸率の面から、０．５〜２．０ｍｅ
ｑ／ｇ乾燥樹脂、特には０．８〜１．５ｍｅｑ／ｇ乾燥
樹脂であることが望ましい。The thickness of the cation exchange membrane constituting the bipolar membrane is usually in the range of 5 μm to 300 μm, but preferably 20 μm to 1 from the viewpoint of membrane resistance and strength.
Those in the range of 50 μm are used. Regarding the ion exchange capacity, from the viewpoint of membrane resistance and transport number, 0.5 to 2.0 me
A q / g dry resin, particularly 0.8 to 1.5 meq / g dry resin is desirable.
【００１９】本発明のバイポーラ膜を構成する陰イオン
交換膜としては、バイポーラ膜内で生成される水酸イオ
ンの透過性が大きく、陽イオンの透過が可及的に小さい
陰イオン交換膜が使用される。その例としては、ポリオ
レフィンの基材に担持されたスチレン重合体又はスチレ
ンとジビニルベンゼンとの共重合体からなり、陰イオン
交換基として４級アンモニウム基を有する膜などが使用
できる。As the anion exchange membrane constituting the bipolar membrane of the present invention, an anion exchange membrane having a high permeability of hydroxide ions generated in the bipolar membrane and a minimum permeability of cations is used. To be done. As an example thereof, a film made of a styrene polymer supported on a polyolefin substrate or a copolymer of styrene and divinylbenzene and having a quaternary ammonium group as an anion exchange group can be used.
【００２０】なかでも耐アルカリ性及び耐薬品性に優れ
ていることから、好ましくはポリプロピレン、ポリエチ
レンなどのポリオレフィンの基材を使用し、その織布に
スチレンとジビニルベンゼンとの共重合体、又は、さら
にこれにビニルベンジルクロリドを加えた共重合体の一
部が放射線などの高エネルギーによって上記ポリオレフ
ィンにグラフト重合した４級アンモニウム基を有する陰
イオン交換膜が好ましい。Among them, since it is excellent in alkali resistance and chemical resistance, it is preferable to use a polyolefin base material such as polypropylene or polyethylene, and the woven cloth thereof is a copolymer of styrene and divinylbenzene, or An anion exchange membrane having a quaternary ammonium group in which a part of the copolymer obtained by adding vinylbenzyl chloride thereto is graft-polymerized with the above-mentioned polyolefin by high energy such as radiation is preferable.
【００２１】バイポーラ膜を構成する陰イオン交換膜の
厚さは、５μｍ〜３００μｍの範囲で通常使用される
が、膜抵抗及び強度の点から、好ましくは２０μｍ〜１
５０μｍの範囲のものが使用される。イオン交換容量に
ついては、０．５〜４．０ｍｅｑ／ｇ乾燥樹脂、特には
０．８〜３．０ｍｅｑ／ｇ乾燥樹脂が好ましい。The thickness of the anion exchange membrane constituting the bipolar membrane is usually in the range of 5 μm to 300 μm, but preferably 20 μm to 1 from the viewpoint of membrane resistance and strength.
Those in the range of 50 μm are used. With respect to the ion exchange capacity, 0.5 to 4.0 meq / g dry resin, particularly 0.8 to 3.0 meq / g dry resin is preferable.
【００２２】[0022]
【作用】本発明のバイポーラ膜は、上記のように長期間
にわたって小さい電圧降下が保持されるが、そのメカニ
ズムは下記のように推測される。即ち、本発明のバイポ
ーラ膜の界面に存在する酸性塩型無機イオン交換体は堅
固な構造を持つために、酸性塩型無機イオン交換体層と
接触する各イオン交換膜のイオン交換基は、無機イオン
交換体層に侵入することができず、イオン的な結合を生
じて中性層を形成することが困難である。また、酸性塩
型無機イオン交換体は有機イオン交換樹脂に比べ、体積
あたりのイオン交換容量が大きく、しかも多くの水を保
有できる構造のために無機イオン交換体層の電気抵抗が
小さく、バイポーラ膜の電圧降下を小さくすることがで
きる。また、酸性塩型無機イオン交換体は他の無機イオ
ン交換体に比べ、耐酸性、耐アルカリ性に優れるため、
長期間にわたり、安定した性能を発現できるものと思わ
れる。The bipolar film of the present invention retains a small voltage drop for a long period of time as described above, and the mechanism is presumed as follows. That is, since the acidic salt type inorganic ion exchanger present at the interface of the bipolar membrane of the present invention has a solid structure, the ion exchange group of each ion exchange membrane in contact with the acidic salt type inorganic ion exchanger layer is an inorganic substance. It cannot penetrate into the ion exchanger layer, and it is difficult to form an ionic bond to form a neutral layer. In addition, the acidic salt type inorganic ion exchanger has a larger ion exchange capacity per volume than the organic ion exchange resin, and because of its structure capable of retaining a large amount of water, the electric resistance of the inorganic ion exchanger layer is small and the bipolar membrane The voltage drop can be reduced. Further, since the acid salt type inorganic ion exchanger is superior in acid resistance and alkali resistance as compared with other inorganic ion exchangers,
It seems that stable performance can be achieved over a long period of time.
【００２３】[0023]
【実施例】以下実施例により本発明を説明するが、かか
る実施例により本発明が制限されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to the examples.
【００２４】［実施例１］スチレン−ジビニルベンゼン
共重合体よりなり、ポリプロピレン織布にて補強した４
級アンモニウム基を有する陰イオン交換膜（イオン交換
容量３．０ｍｅｑ／ｇ乾燥樹脂、膜厚１２０μｍ）上に
リン酸ジルコニウムの分散液を塗布して乾燥し、厚さ５
μｍのリン酸ジルコニウム層を形成させた。しかる後に
ＣＦ2 ＝ＣＦ2 とＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ（ＣＦ3 ）
ＯＣＦ2 ＣＦ2 ＳＯ3 Ｈとの共重合体からなる陽イオン
交換膜（イオン交換容量１．１ｍｅｑ／ｇ乾燥樹脂、膜
厚８０μｍ）を１９０℃、７０ｋｇ／ｃｍでロールプレ
スし、バイポーラ膜を製造した。バイポーラ膜は０．５
Ｎの塩化ナトリウム水溶液中に保管後、図１に示す電気
透析槽のバイポーラ膜１としてその性能を評価した。[Example 1] 4 made of a styrene-divinylbenzene copolymer and reinforced with a polypropylene woven cloth 4
A dispersion of zirconium phosphate was applied onto an anion exchange membrane having a primary ammonium group (ion exchange capacity 3.0 meq / g dry resin, film thickness 120 μm) and dried to give a thickness of 5
A μm zirconium phosphate layer was formed. After that, CF 2 = CF 2 and CF 2 = CFOCF 2 CF (CF 3 )
A cation exchange membrane (ion exchange capacity 1.1 meq / g dry resin, film thickness 80 μm) consisting of a copolymer with OCF 2 CF 2 SO 3 H is roll pressed at 190 ° C. and 70 kg / cm to produce a bipolar membrane. did. Bipolar film is 0.5
After being stored in a sodium chloride aqueous solution of N, its performance was evaluated as the bipolar membrane 1 of the electrodialysis tank shown in FIG.
【００２５】図１の電気透析槽において、陽極室１３、
陰極室１４及び中性塩室９、１０に１５重量％の硫酸ナ
トリウム水溶液を供給し、アルカリ生成室５は生成され
る水酸化ナトリウムの濃度が２０重量％となるようにイ
オン交換水を調節して供給するとともに、酸生成室６は
生成される硫酸水溶液の濃度が１０重量％となるように
イオン交換水の量を調節した。In the electrodialysis tank of FIG. 1, the anode chamber 13,
A 15 wt% sodium sulfate aqueous solution is supplied to the cathode chamber 14 and the neutral salt chambers 9 and 10, and the alkali generation chamber 5 adjusts ion-exchanged water so that the concentration of sodium hydroxide produced is 20 wt%. The amount of ion-exchanged water was adjusted so that the concentration of the aqueous sulfuric acid solution produced was 10% by weight.
【００２６】陽イオン交換膜７、１１、１２にはスチレ
ン−ジビニルベンゼン共重合体系スルホン酸膜（イオン
交換容量３．３ｍｅｑ／ｇ乾燥樹脂、膜厚１４０μｍ）
を用い、陰イオン交換膜８にはスチレン−ジビニルベン
ゼン共重合体系弱塩基性陰イオン交換膜（イオン交換容
量２．０ｍｅｑ／ｇ乾燥樹脂、膜厚１２０μｍ）を用い
た。６０℃にて電流密度１０Ａ／ｄｍ2 の電気透析を行
ったところ、バイポーラ膜による電圧降下は１．０Ｖ、
水の解離効率は９５％以上であった。この性能は３ケ月
を経過しても変わらなかった。Styrene-divinylbenzene copolymer type sulfonic acid membranes (ion exchange capacity 3.3 meq / g dry resin, film thickness 140 μm) are used for the cation exchange membranes 7, 11 and 12.
As the anion exchange membrane 8, a styrene-divinylbenzene copolymer system weakly basic anion exchange membrane (ion exchange capacity 2.0 meq / g dry resin, film thickness 120 μm) was used. When electrodialysis at a current density of 10 A / dm 2 was performed at 60 ° C., the voltage drop due to the bipolar membrane was 1.0 V,
The dissociation efficiency of water was 95% or more. This performance did not change after three months.
【００２７】［実施例２］実施例１で用いたバイポーラ
膜用陰イオン交換膜上にスクリーン印刷を用いて厚さ１
μｍのリン酸チタン層を形成し、実施例１で用いたバイ
ポーラ膜用陽イオン交換膜を１９０℃、７０ｋｇ／ｃｍ
でロールプレスし、バイポーラ膜を製造した。実施例１
と同様にして、このバイポーラ膜の性能を評価したとこ
ろ、電圧降下１．０Ｖ、水の解離効率は９５％以上であ
った。この性能は３ケ月を経過しても変わらなかった。[Example 2] A thickness of 1 was obtained by screen printing on the anion-exchange membrane for bipolar membrane used in Example 1.
A titanium phosphate layer of μm was formed, and the cation exchange membrane for a bipolar membrane used in Example 1 was used at 190 ° C. and 70 kg / cm.
Roll-pressed to produce a bipolar film. Example 1
When the performance of this bipolar film was evaluated in the same manner as above, the voltage drop was 1.0 V and the water dissociation efficiency was 95% or more. This performance did not change after three months.
【００２８】［実施例３］実施例１で用いたバイポーラ
膜用陰イオン交換膜上にスクリーン印刷を用いて厚さ１
μｍのモリブデン酸ジルコニウム層を形成させた。しか
る後に、ＣＦ2 ＝ＣＦ2 とＣＦ2 ＝ＣＦＯＣＦ2 ＣＦ
（ＣＦ3 ）ＯＣＦ2 ＣＦ2 ＳＯ3 Ｈとの共重合体からな
る陽イオン交換体（イオン交換容量０．９１ｍｅｑ／ｇ
乾燥樹脂）のエタノール溶液を流延し、１５０℃で１５
分乾燥し、厚さ３０μｍの陽イオン交換膜を形成し、バ
イポーラ膜を得た。実施例１と同様にして、このバイポ
ーラ膜の性能を評価したところ、電圧降下１．０Ｖ、水
の解離効率は９５％以上であった。この性能は３ケ月を
経過しても変わらなかった。[Example 3] A thickness of 1 was obtained by screen printing on the anion-exchange membrane for bipolar membrane used in Example 1.
A μm zirconium molybdate layer was formed. After that, CF 2 = CF 2 and CF 2 = CFOCF 2 CF
A cation exchanger (ion exchange capacity of 0.91 meq / g) composed of a copolymer with (CF 3 ) OCF 2 CF 2 SO 3 H
An ethanol solution of dry resin) is cast, and the solution is dried at 150 ° C. for 15
After minute drying, a cation exchange membrane having a thickness of 30 μm was formed to obtain a bipolar membrane. When the performance of this bipolar film was evaluated in the same manner as in Example 1, the voltage drop was 1.0 V and the water dissociation efficiency was 95% or more. This performance did not change after three months.
【００２９】［実施例４］実施例１で用いたバイポーラ
膜用陰イオン交換膜上にスクリーン印刷を用いて厚さ１
０μｍのタングステン酸スズ層を形成し、実施例１で用
いたバイポーラ膜用陽イオン交換膜を１９０℃、７０ｋ
ｇ／ｃｍでロールプレスし、バイポーラ膜を製造した。
実施例１と同様にして、このバイポーラ膜の性能を評価
したところ、電圧降下１．１Ｖ、水の解離効率は９５％
以上であった。この性能は３ケ月を経過しても変わらな
かった。[Example 4] A thickness of 1 was obtained by screen printing on the anion-exchange membrane for bipolar membrane used in Example 1.
A tin tungstate layer having a thickness of 0 μm was formed, and the cation exchange membrane for a bipolar membrane used in Example 1 was used at 190 ° C. and 70 k.
Roll pressing was performed at g / cm to manufacture a bipolar film.
When the performance of this bipolar film was evaluated in the same manner as in Example 1, the voltage drop was 1.1 V and the dissociation efficiency of water was 95%.
That was all. This performance did not change after three months.
【００３０】［実施例５］実施例１で用いたバイポーラ
膜用陰イオン交換膜上にスプレー法を用いて厚さ０．１
μｍのアンチモン酸チタン層を形成し、実施例１で用い
たバイポーラ膜用陽イオン交換膜を１９０℃、７０ｋｇ
／ｃｍでロールプレスし、バイポーラ膜を製造した。実
施例１と同様にして、このバイポーラ膜の性能を評価し
たところ、電圧降下１．０Ｖ、水の解離効率は９５％以
上であった。この性能は３ケ月を経過しても変わらなか
った。[Embodiment 5] A thickness of 0.1 is formed on the anion-exchange membrane for a bipolar membrane used in Embodiment 1 by a spray method.
A titanium antimonate layer of μm was formed, and the cation exchange membrane for a bipolar membrane used in Example 1 was heated at 190 ° C. and 70 kg.
Roll-pressing was performed at a pressure of 1 cm / cm to produce a bipolar film. When the performance of this bipolar film was evaluated in the same manner as in Example 1, the voltage drop was 1.0 V and the water dissociation efficiency was 95% or more. This performance did not change after three months.
【００３１】[0031]
【発明の効果】本発明におけるバイポーラ膜は、従来法
に比して電圧降下が小さく、また水解離効率が高く、し
かも長期間にわたり安定な性能を示す。The bipolar membrane of the present invention has a smaller voltage drop than the conventional method, a high water dissociation efficiency, and stable performance for a long period of time.
【図１】バイポーラ膜を評価する電気透析装置の模式図FIG. 1 is a schematic diagram of an electrodialysis device for evaluating a bipolar membrane.
１：バイポーラ膜 ２：陽イオン交換膜 ３：酸性塩型無機イオン交換体層 ４：陰イオン交換膜 ５：アルカリ生成室 ６：酸生成室 ７、１１、１２：陽イオン交換膜 ８：陰イオン交換膜 ９、１０：中性塩室 １３：陽極室 １４：陰極室 １５：陽極 １６：陰極 1: Bipolar membrane 2: Cation exchange membrane 3: Acid salt type inorganic ion exchanger layer 4: Anion exchange membrane 5: Alkali generation chamber 6: Acid generation chamber 7, 11, 12: Cation exchange membrane 8: Anion Exchange membrane 9, 10: Neutral salt chamber 13: Anode chamber 14: Cathode chamber 15: Anode 16: Cathode
Claims (4)
に酸性塩型無機イオン交換体層を存在せしめたことを特
徴とするバイポーラ膜。1. A bipolar membrane having an acidic salt type inorganic ion exchanger layer at the interface between a cation exchange membrane and an anion exchange membrane.
３価以上のカチオンである請求項１のバイポーラ膜。2. The bipolar membrane according to claim 1, wherein the metal ion of the acidic salt type inorganic ion exchanger is a cation having a valence of 3 or more.
単位を有する共重合体からなる請求項１のバイポーラ
膜。 【化１】 なお、化１においてｍは０又は１、ｎは１〜５、ｘ／ｙ
は２〜１６、ＸはＳＯ3 Ｍ又はＣＯＯＭを表し、Ｍは水
素、アルカリ金属、アルカリ土類金属又はアンモニウム
基を表す。3. The bipolar membrane according to claim 1, wherein the cation exchange membrane comprises a copolymer having a repeating unit represented by Chemical formula 1. [Chemical 1] In Chemical formula 1, m is 0 or 1, n is 1 to 5, x / y
2 to 16 and X represents SO 3 M or COOM, and M represents hydrogen, an alkali metal, an alkaline earth metal or an ammonium group.
に担持されたスチレン重合体又はスチレンとジビニルベ
ンゼンとの共重合体からなり、陰イオン交換基として４
級アンモニウム基を有する請求項１のバイポーラ膜。4. An anion exchange membrane is composed of a styrene polymer or a copolymer of styrene and divinylbenzene supported on a polyolefin substrate, and has 4 as an anion exchange group.
The bipolar film according to claim 1, which has a quaternary ammonium group.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4350988A JPH06172557A (en) | 1992-12-04 | 1992-12-04 | New bipolar film |
| EP93119371A EP0600470A3 (en) | 1992-12-04 | 1993-12-01 | Bipolar membrane. |
| US08/161,262 US5401408A (en) | 1992-12-04 | 1993-12-03 | Bipolar membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4350988A JPH06172557A (en) | 1992-12-04 | 1992-12-04 | New bipolar film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06172557A true JPH06172557A (en) | 1994-06-21 |
Family
ID=18414275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4350988A Withdrawn JPH06172557A (en) | 1992-12-04 | 1992-12-04 | New bipolar film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06172557A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018517236A (en) * | 2015-04-14 | 2018-06-28 | ロッキード マーティン エナジー, エルエルシーLockheed Martin Energy, Llc | Balancing cell for flow battery with bipolar membrane and method of use thereof |
-
1992
- 1992-12-04 JP JP4350988A patent/JPH06172557A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018517236A (en) * | 2015-04-14 | 2018-06-28 | ロッキード マーティン エナジー, エルエルシーLockheed Martin Energy, Llc | Balancing cell for flow battery with bipolar membrane and method of use thereof |
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