JPS62258741A - Treatment of ion in solution by conductive organic polymer electrode - Google Patents
Treatment of ion in solution by conductive organic polymer electrodeInfo
- Publication number
- JPS62258741A JPS62258741A JP10237986A JP10237986A JPS62258741A JP S62258741 A JPS62258741 A JP S62258741A JP 10237986 A JP10237986 A JP 10237986A JP 10237986 A JP10237986 A JP 10237986A JP S62258741 A JPS62258741 A JP S62258741A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- organic polymer
- conductive organic
- solution
- anion
- 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
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 84
- 150000002500 ions Chemical class 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000001450 anions Chemical class 0.000 claims abstract description 32
- 238000005341 cation exchange Methods 0.000 claims abstract description 19
- 150000001768 cations Chemical class 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims 2
- 238000003672 processing method Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002242 deionisation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 8
- 229920000447 polyanionic polymer Polymers 0.000 description 8
- 229920000557 Nafion® Polymers 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 5
- 229920000767 polyaniline Polymers 0.000 description 5
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000827 poly(xylylviologen) polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Description
【発明の詳細な説明】
崖又上■剋里圀団
本発明は、導電性有機重合体電極による溶液中のイオン
の処理方法に関し、詳しくは、イオンを含む溶液中にお
いて、それぞれ導電性有機重合体からなる一対の電極間
に電圧を印加して、これら電極に溶液中のイオンを可逆
的に捕捉させ、或いは放出させて、溶液中のイオンを電
気化学的に処理する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating ions in a solution using a conductive organic polymer electrode. The present invention relates to a method of electrochemically treating ions in a solution by applying a voltage between a pair of electrodes made of a combination, causing these electrodes to reversibly capture or release ions in the solution.
従来の技術
イオン交換が可能である正又は負の解離基を有するイオ
ン交換樹脂によって、溶液中に存在する種々のイオンを
捕捉除去するイオンの処理方法はよく知られている。し
かし、この方法においては、イオン交換樹脂の再生に多
量の酸若しくはアルカリ、又は多量の塩を必要とするの
で、再生処理が煩瑣であるうえに、イオン交換樹脂の有
する上記解1iiI基が溶液中のイオンを強固に吸着し
た場合は、再生が困難である。BACKGROUND OF THE INVENTION Ion treatment methods are well known in which various ions present in a solution are captured and removed by ion exchange resins having positive or negative dissociative groups capable of ion exchange. However, in this method, a large amount of acid or alkali, or a large amount of salt is required to regenerate the ion exchange resin, so the regeneration process is cumbersome, and the above-mentioned 1iiiI group of the ion exchange resin is removed from the solution. If ions are strongly adsorbed, regeneration is difficult.
そこで、酸化還元機能を有する重合体、所謂レドックス
ポリマーを用いて、溶液中のイオンの除去やイオン交換
樹脂の再生を電気化学的に行なうことが既に提案されて
いる(A、 Factor et al、。Therefore, it has already been proposed to electrochemically remove ions from solutions and regenerate ion exchange resins using polymers with redox functions, so-called redox polymers (A, Factor et al.).
J、E1ectrochen+1cal Soc、、
127.1313 (1980))。J, E1ectrochen+1cal Soc,,
127.1313 (1980)).
この方法によれば、イオンを含む溶液中において、第1
の電極上の架橋ポリメシチルビオロゲンを酸化して、こ
の電極にアニオンを捕捉させると共に、第2の電極上の
ポリキシリルビオロゲンとポリスチレンスルホン酸とか
らなる複合重合体を還元して、溶液中のカチオンをこの
電極に捕捉させ、このようにして、溶液を脱イオンする
ことができる。According to this method, the first
The cross-linked polymesityl viologen on the second electrode is oxidized to trap anions on this electrode, and the composite polymer consisting of polyxylyl viologen and polystyrene sulfonic acid on the second electrode is reduced to form a solution. cations can be trapped on this electrode and in this way the solution can be deionized.
しかし、この方法によれば、用いる重合体が本来電気的
に絶縁性であるので、有効に脱イオンを行なうためには
、電極上のその厚みが制約され、従って、イオン交換量
も自ずから制限される。更に、重合体が電気絶縁性であ
ることから、電極の製造に際しては、予め重合体を製造
した後、これを電極上に製膜することを要するので、電
極の製造に手間と費用を要する。However, according to this method, since the polymer used is electrically insulating in nature, its thickness on the electrode is limited in order to effectively deionize, and therefore the amount of ion exchange is naturally limited. Ru. Furthermore, since the polymer is electrically insulating, it is necessary to manufacture the polymer in advance and then form a film on the electrode, which requires time and cost to manufacture the electrode.
他方、従来より種々の導電性有機重合体が知られている
。これらの殆どはp型半導体であって、過塩素酸イオン
、塩素イオン、四フフ化ホウ素イオン等の低分子量アニ
オンがドーピングされている自体はカチオン性の重合体
である。かがる導電性を機雷合体も、電気化学的に可逆
的に酸化ぶ元される。換言すれば、酸化還元機能を有し
て、レドックスポリマーとして機能する。より詳細には
、このような導電性有機重合体は、溶液中にて還元され
ることによってアニオンを放出し、自体は中性となり、
再酸化によって、再びアニオンをドーパントとして捕捉
する。即ち、低分子量アニオンがドニピングされている
p型導電性有機重合体は、アニオン捕捉能を有する。On the other hand, various conductive organic polymers have been known. Most of these are p-type semiconductors, and are themselves cationic polymers doped with low molecular weight anions such as perchlorate ions, chloride ions, and boron tetrafluoride ions. The coalescence of the electrically conductive mine is also electrochemically reversibly oxidized. In other words, it has a redox function and functions as a redox polymer. More specifically, when such a conductive organic polymer is reduced in a solution, it releases anions and becomes neutral.
By reoxidation, the anion is again captured as a dopant. That is, the p-type conductive organic polymer doped with low molecular weight anions has an anion-trapping ability.
しかし、本発明者らは、既に、上記低分子量アニオンに
代えて、分子内に多数のアニオン性基を有する高分子量
重合体(以下、ポリアニオンという。)がドーピングさ
れたp型導電性有機重合体は、前記低分子量アニオンが
ドーピングされたp型導電性有機重合体とは対照的に、
導電性有機重合体において上記ポリアニオンが高分子量
を有するために拡散し難く、従って、導電性有機重合体
を溶液中にて還元することによって、溶液中のカチオン
を分子内にtIl提し、次いで、導電性有機重合体を再
酸化することによって、上記捕捉したカチオンを放出す
ることを見出している(大谷ら、第34同高分子学会講
演予稿集第2829頁(1985))。即ち、ポリアニ
オンがドーピングされたp型導電性有機重合体は、その
還元によって、ポリアニオンが本来有しているカチオン
交換能を有する。However, the present inventors have already developed a p-type conductive organic polymer doped with a high molecular weight polymer having a large number of anionic groups in the molecule (hereinafter referred to as polyanion) in place of the low molecular weight anion. In contrast to the low molecular weight anion-doped p-type conductive organic polymer,
Since the polyanion has a high molecular weight in the conductive organic polymer, it is difficult to diffuse. Therefore, by reducing the conductive organic polymer in a solution, the cation in the solution is incorporated into the molecule, and then, It has been discovered that the captured cations can be released by reoxidizing the conductive organic polymer (Otani et al., Proceedings of the 34th Society of Polymer Science, p. 2829 (1985)). That is, the p-type conductive organic polymer doped with a polyanion has the cation exchange ability originally possessed by the polyanion due to its reduction.
発明が解決しようとする問題点
そこで、本発明者らは、溶液中のイオン処理及びこのイ
オン処理に用いる電極の製造における上記した問題を解
決するために鋭意研究した結果、第1及び第2の電極と
して、それぞれp型半導体としての導電性有機重合体に
低分子量及び高分子量のドーパントをドーピングさせて
なる重合体を用い、かかる電極間に電圧を印加すること
によって、溶液中のイオンを電極に可逆的に捕捉放出さ
せ得ると共に、電極を電気化学的に再生することができ
ることを見出して、本発明に至ったものである。Problems to be Solved by the Invention Therefore, the present inventors conducted extensive research to solve the above-mentioned problems in ion treatment in a solution and in manufacturing electrodes used for this ion treatment, and as a result, the first and second problems were solved. The electrodes are made by doping conductive organic polymers with low-molecular weight and high-molecular weight dopants, respectively, as p-type semiconductors, and by applying a voltage between the electrodes, ions in the solution are transferred to the electrodes. The present invention was achieved by discovering that it is possible to capture and release reversibly and to regenerate the electrode electrochemically.
従って、本発明は、導電性有機重合体からなる一対の電
極間に電圧を印加して、溶液中のイオンを可逆的に電極
に捕捉させ、或いは放出させて、溶液中のイオンを処理
し、また、他の側面として、上記電極を電気化学的に再
生する方法を提供することを目的とする。Therefore, the present invention treats ions in a solution by applying a voltage between a pair of electrodes made of a conductive organic polymer to reversibly capture or release ions in the solution, Another aspect of the present invention is to provide a method for electrochemically regenerating the electrode.
問題点を解ンするための平戸
本発明による導電性有機重合体電極による溶液中のイオ
ンの処理方法の第1は、イオンを含む溶液中において、
第1の電極としてのアニオン捕捉能をもつp型厚電性有
機重合体を電気化学的に酸化すると共に、第2の電極と
してのカチオン交換能をもつp型導電性有機重合体を電
気化学的に還元することによって、溶液中のアニオンを
第1の電極にて捕捉させ、カチオンを第2の電極にて捕
捉させることを特徴とする。Hirato To solve the problem, the first method of treating ions in a solution using a conductive organic polymer electrode according to the present invention is to treat ions in a solution containing ions.
A p-type thick conductive organic polymer with anion-trapping ability is electrochemically oxidized as the first electrode, and a p-type conductive organic polymer with cation exchange ability is electrochemically oxidized as the second electrode. The method is characterized in that anions in the solution are captured by the first electrode and cations are captured by the second electrode.
本発明による導電性有機重合体電極による溶液中のイオ
ンの処理方法の第2は、イオンを含む溶液中において、
第1の電極としてのアニオン捕捉能をもつp型導電性有
機重合体を電気化学的に酸化すると共に、第2の電極と
してのカチオン交換能をもつp型導電性有機重合体を電
気化学的に還元することによって、溶液中のアニオンを
第1の電極にて捕捉させ、カチオンを第2の電極にて捕
捉させ、次いで、上記第1の電極を電気化学的に還元す
ると共に、第2の電極を電気化学的に酸化することによ
って、上記第1の電極から上記アニオンを放出させ、上
記第2の電極から上記カチオンを放出させ、同時に、上
記第1及び第2の電極を電気化学的に再生することを特
徴とする。The second method for treating ions in a solution using a conductive organic polymer electrode according to the present invention is to
A p-type conductive organic polymer with anion-trapping ability is electrochemically oxidized as the first electrode, and a p-type conductive organic polymer with cation exchange ability is electrochemically oxidized as the second electrode. By reducing, anions in the solution are captured by the first electrode, cations are captured by the second electrode, and then the first electrode is electrochemically reduced, and the second electrode The anions are released from the first electrode, the cations are released from the second electrode, and at the same time, the first and second electrodes are electrochemically regenerated. It is characterized by
以下に本発明の方法を詳細に説明する。The method of the present invention will be explained in detail below.
本発明において用いる導電性有機重合体は、その調製時
にアニオンがドーピングされている自体はカチオン性を
有するp型半導体である。かかる導電性有機重合体の具
体例として、ピロール、その窒素、3位及び/又は4位
に置換基を有する誘導体、チオフェン、その、3位及び
/又は4位に置換基を存する誘導体、フラン、その3位
及び/又は4位に置換基を有する誘導体等の複素環式化
合物単量体や、アニリン、フェノール、チオフェノール
、これらの誘導体等の芳香族化合物単量体の電解酸化重
合又は化学酸化重合による重合体等を挙げることができ
る。The conductive organic polymer used in the present invention is doped with an anion during its preparation and is itself a p-type semiconductor having cationic properties. Specific examples of such conductive organic polymers include pyrrole, derivatives having substituents at the nitrogen, 3rd and/or 4th positions, thiophene, derivatives having substituents at the 3rd and/or 4th positions, furan, Electrolytic oxidative polymerization or chemical oxidation of heterocyclic compound monomers such as derivatives having a substituent at the 3- and/or 4-position, and aromatic compound monomers such as aniline, phenol, thiophenol, and their derivatives. Examples include polymers obtained by polymerization.
本発明において用いるアニオン捕捉能をもつp整導電性
有機重合体とは、この導電性有機重合体中を容易に拡散
し得る低分子量のアニオンがドーピングされた導電性有
機重合体を意味し、かかる低分子量アニオンの具体例と
して、例えば、前述した塩素イオン、四フッ化ホウ素イ
オン、エチル硫酸イオン等の無機及び有機アニオンを挙
げることができる。The p-aligned conductive organic polymer having anion-trapping ability used in the present invention means a conductive organic polymer doped with a low molecular weight anion that can easily diffuse through the conductive organic polymer. Specific examples of low molecular weight anions include inorganic and organic anions such as the aforementioned chlorine ion, boron tetrafluoride ion, and ethyl sulfate ion.
他方、カチオン交換能を有するp整導電性有機重合体と
は、この導電性有機重合体中を容易には拡散し得ない前
記ポリアニオンがドーピングされている導電性有機重合
体を意味する。かかるポリアニオンの具体例として、「
ナフィオン」 (米国デュポン社製)として市販されて
いるフッ素系重合体を挙げることができる。この重合体
は、分子側鎖に多数のスルホン酸基を有する。しかし、
本発明において、ポリアニオンはこれに限定されるもの
ではなく、例えば、ポリビニル硫酸、ポリスチレンスル
ホン酸等も好ましく用いられる。On the other hand, a p-aligned conductive organic polymer having cation exchange ability means a conductive organic polymer doped with the polyanion that cannot easily diffuse into the conductive organic polymer. A specific example of such a polyanion is “
A fluoropolymer commercially available as "Nafion" (manufactured by DuPont, USA) can be mentioned. This polymer has a large number of sulfonic acid groups in the side chains of the molecule. but,
In the present invention, the polyanion is not limited to these, and for example, polyvinyl sulfuric acid, polystyrene sulfonic acid, etc. are also preferably used.
このように、p整導電性有機重合体とドーパントとして
のアニオンとの複合物からなる導電性有機重合体は、既
に知られているように(例えば、J、 Chem、 S
oc、、 Chew、 Commun、+ 1979.
635や、特開昭59−98615号公報)、前記した
導電性有機重合体を形成し得る単量体の溶液中に前記し
た低分子量アニオン又はポリアニオンを溶解させ、この
溶液中にて前記単量体を酸化重合させることによって得
ることができる。上記酸化重合の方法は、特に制限され
るものではないが、重合の制御が容易であることから、
電解酸化重合が有利である。In this way, conductive organic polymers consisting of a composite of a p-aligned conductive organic polymer and an anion as a dopant are known (e.g., J. Chem. S.
oc, Chew, Commun, + 1979.
635, JP-A No. 59-98615), the above-mentioned low molecular weight anion or polyanion is dissolved in a solution of the monomer capable of forming the above-mentioned conductive organic polymer, and the above-mentioned monomer is dissolved in this solution. It can be obtained by subjecting the body to oxidative polymerization. The above oxidative polymerization method is not particularly limited, but since the polymerization can be easily controlled,
Electrolytic oxidative polymerization is preferred.
本発明においては、アニオン捕捉能をもつp整導電性有
機重合体は、溶液中のアニオンを多量に捕捉し得るよう
に、導電性有機重合体は予め部分的に還元されて、重合
体に静電的に結合している低分子量アニオンが一部脱ド
ーピングされているものであることが好ましい。一般に
、導電性有機重合体は、脱ドーピングによって導電性か
ら絶縁性に移行するので、本発明においては、上記部分
脱ドーピング量は、用いる導電性有機重合体や溶液中の
対象とするイオンの種類等によって適宜に選ばれるが、
通常、導電性有機重合体が10−’S/ cm以上の導
電性を有する程度に留めることが好ましい。この脱ドー
ピングのための4電性有機重合体の還元の方法は、何ら
制限されるものではなく、電解還元又は化学還元のいず
れによることもできるが、脱ドーピング量を容易に制御
し得る電解還元によるのが好ましい。In the present invention, the p-balanced conductive organic polymer having anion-capturing ability is partially reduced in advance so as to be able to trap a large amount of anions in the solution. It is preferable that the electrically bonded low molecular weight anions are partially dedoped. In general, conductive organic polymers change from conductive to insulating through dedoping. It is selected appropriately according to
Generally, it is preferable that the conductive organic polymer has a conductivity of 10-'S/cm or more. The method of reducing the tetraelectric organic polymer for this dedoping is not limited in any way and may be either electrolytic reduction or chemical reduction, but electrolytic reduction can easily control the amount of dedoping. Preferably.
本発明の方法においては、第1の電極として、上記した
ようなアニオン捕捉能をもつp整導電性有機重合体、好
ましくは、上記のように、一部脱ドーピングしたp整導
電性有機重合体を用い、第2の電極としてカチオン交換
能をもつp整導電性有機重合体を用い、これら電極を電
位負荷装置を介してイオンを含む溶液中において電気的
に接続し、これら電極間に電圧を印加して、溶液中のイ
オンを電極に可逆的に捕捉放出させ、このようにして、
イオンを処理し、また、電極を電気化学的に再生するも
のである。In the method of the present invention, the first electrode is a p-aligned conductive organic polymer having an anion-trapping ability as described above, preferably a p-aligned conductive organic polymer partially dedoped as described above. A p-aligned conductive organic polymer with cation exchange ability is used as the second electrode, these electrodes are electrically connected in a solution containing ions through a potential loading device, and a voltage is applied between these electrodes. the ions in the solution are reversibly captured and released by the electrode, thus
It processes ions and electrochemically regenerates electrodes.
より詳細に説−明すれば、本発明の方法によれば、イオ
ンを含む溶液中において、上記アニオン捕捉能をもつp
整導電性有機重合体からなる電極(以下、アニオン捕捉
性電極という。)を陽極とし、カチオン交換能をもつp
整導電性有機重合体を有する電極(以下、カチオン交換
性電極という。)を陰極とする電圧を印加して、上記ア
ニオン捕捉能をもつp整導電性有機重合体を酸化すると
共に、カチオン交換能をもつp整導電性有機重合体を還
元することによって、溶液中のアニオンは上記アニオン
捕捉性電極に捕捉され、他方、溶液中のカチオンは上記
カチオン交換性電極に11n捉される。To explain in more detail, according to the method of the present invention, in a solution containing ions, p
An electrode made of a conductive organic polymer (hereinafter referred to as an anion-trapping electrode) is used as an anode, and a p
A voltage is applied using an electrode having a conductive organic polymer (hereinafter referred to as a cation exchange electrode) as a cathode to oxidize the p conductive organic polymer having an anion trapping ability, and at the same time improve the cation exchange ability. By reducing the p-aligned conductive organic polymer with 11n, anions in the solution are captured by the anion-trapping electrode, while cations in the solution are captured by the cation-exchanging electrode.
電極間に印加する負荷電圧は、電極上のそれぞれのp整
導電性有機重合体の酸化還元電位によって適宜に選ばれ
るが、通常は、数■である。The load voltage applied between the electrodes is appropriately selected depending on the redox potential of each p-aligned conductive organic polymer on the electrodes, but is usually several square meters.
次いで、本発明の方法に従って、印加電圧の極性を逆転
させて、前記アニオン捕捉性電極を陰極とし、前記カチ
オン交換性電極を陽極とし°ζ、アニオン捕捉能をもつ
p整導電性有機重合体を還元すると共に、カチオン交換
能をもつp型埋電性有機重合体を酸化することによって
、それぞれの電極が捕捉していたアニオン及びカチオン
がそれぞれ溶液中に放出されると共に、このようにして
、それぞれの電極が電気化学的に再生される。尚、この
それぞれの電極からのアニオン及びカチオンの放出或い
は電極の再生に際しては、必要に応じて、又は目的に応
じて、電極を異なる電解質を含む溶液に浸漬してもよい
。Then, in accordance with the method of the present invention, the polarity of the applied voltage is reversed, the anion-trapping electrode is used as the cathode, and the cation-exchangeable electrode is used as the anode, thereby producing a p-aligned conductive organic polymer having anion-trapping ability. By reducing and oxidizing the p-type charged organic polymer with cation exchange ability, the anions and cations captured by each electrode are released into the solution, and in this way, each electrodes are electrochemically regenerated. In addition, when releasing anions and cations from each electrode or regenerating the electrode, the electrode may be immersed in a solution containing a different electrolyte as necessary or according to the purpose.
本発明において用いるイオンを含む溶液は、その媒体が
水であっても、有機化合物であっても、また、これらの
混合物であってもよく、媒体において何ら制限されるも
のではない。The medium of the solution containing ions used in the present invention may be water, an organic compound, or a mixture thereof, and the medium is not limited in any way.
本発明の方法によれば、更に、上記したように、第1及
び第2の電極をイオンを含む溶液中に同時に浸漬せずに
、例えば、白金からなる通常の電極と共に前記第1の電
極をイオンを含む溶液中に浸漬し、これら電極間に電圧
を印加し、第1の電極を酸化して、所要のアニオンを第
1の電極に捕捉させ、次いで、この第1の電極を前記第
2の電極と置き換え、第2の電極を還元することによっ
て、溶液中のカチオンをこの第2の電極に捕捉させるこ
ともできる。勿論、この順序を逆転させることもできる
。更に、前述したように、この後、第1及び第2の電極
に印加する電圧の極性を逆転させて、それぞれの電極か
ら同時に、又は個別的にそれぞれアニオン及びカチオン
を放出させて、電極を再生することができる。According to the method of the present invention, as described above, the first electrode and the second electrode are not simultaneously immersed in a solution containing ions, but the first electrode is immersed together with a conventional electrode made of platinum, for example. immersed in a solution containing ions and applying a voltage between these electrodes to oxidize the first electrode to trap the desired anions in the first electrode; By replacing the electrode with the second electrode and reducing the second electrode, cations in the solution can be captured by the second electrode. Of course, this order can also be reversed. Furthermore, as described above, after this, the polarity of the voltage applied to the first and second electrodes is reversed to release anions and cations from each electrode simultaneously or individually, thereby regenerating the electrodes. can do.
又里□□□四米
以上のように、本発明の方法においては、それぞれの電
極がアニオン捕捉能及びカチオン交換能を有するように
形成されているので、イオンを含む溶液中において、こ
れらイオンを電気化学的に電極に捕捉して、例えば、水
の脱イオンを電気化的に行なうことができ、また、電極
から可逆的に放出させて、電極を電気化学的に再生する
ことができるのみならず、特に、それぞれの電極がドー
ピングされているp型埋電性有機重合体から形成されて
いるために、電極上の導電性有機重合体の層の厚みを大
きくして、イオン交換量を太き(することができる。Matasato □□□As mentioned above, in the method of the present invention, each electrode is formed to have anion trapping ability and cation exchange ability, so that these ions can be removed in a solution containing ions. Only if it can be electrochemically captured at the electrode to effect electrolytic deionization of water, for example, and can be reversibly released from the electrode to electrochemically regenerate the electrode. In particular, since each electrode is formed from a doped p-type buried organic polymer, it is possible to increase the thickness of the conductive organic polymer layer on the electrode to increase the amount of ion exchange. (can do)
更に、本発明の方法において用いる電極は、例えば、導
電性有機重合体を電気化学的に電極上に製膜することに
よって直ちに製造することができるので、電極の製造が
容易であり、且つ、この製造の過程において、導電性有
機重合体の厚みを任意に制御することもできる。Further, the electrode used in the method of the present invention can be easily manufactured, for example, by electrochemically forming a film of a conductive organic polymer on the electrode, and therefore, the electrode can be easily manufactured. During the manufacturing process, the thickness of the conductive organic polymer can also be arbitrarily controlled.
本発明の方法は、その具体的な適用において何ら限定さ
れるものではないが、例えば、前記した脱イオン水の製
造のほか、水の軟水化や有機溶液中の徽盪のイオン性を
機物質、有価金属イオンの回収分離等に好適に用いるこ
とができる。Although the method of the present invention is not limited in any way to its specific application, for example, in addition to the production of deionized water described above, the method of the present invention can be used to soften water or to improve the ionicity of agitation in an organic solution. , can be suitably used for recovery and separation of valuable metal ions, etc.
大施開
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例1
白金板(5cal)を作用極とし、白金線を対極とし、
飽和カロメル電極(S CE)を参照電極として、ビロ
ール(0,1mol/l)及び塩化カリウム(0,01
mol/I)を含む水溶液について、7.5mAの定電
流電解を2時間行なって、塩素イオンがドーピングされ
たポリピロールを電極上に調製した0次いで、このポリ
ピロールを塩化カリウム(0,1mol/I)水溶液中
で電流量が4クーロンに達するまで定N流還元(SCE
に対して−1,OV)し、ポリピロールを部分的に脱ド
ーピングして、アニオン捕捉性電極とした。Example 1 A platinum plate (5 cal) was used as a working electrode, a platinum wire was used as a counter electrode,
Using a saturated calomel electrode (S CE) as a reference electrode, virol (0.1 mol/l) and potassium chloride (0.01
Polypyrrole doped with chlorine ions was prepared on the electrode by electrolyzing at a constant current of 7.5 mA for 2 hours on an aqueous solution containing potassium chloride (0.1 mol/I). Constant N flow reduction (SCE) in an aqueous solution until the current reaches 4 coulombs.
-1, OV), and polypyrrole was partially dedoped to form an anion-trapping electrode.
別に、白金板(5−)を作用極とし、白金線を対極とし
、SCEを参照電極として、ビロール(0,1mol/
I)及びポリビニル硫酸カリウム(0゜01 mol/
1)を含む水溶液について、7.5 m Aの定電流電
解を2時間行なって、電極上にポリビニル硫酸がドーピ
ングされたポリピロールを調製した。これをカチオン交
換性電極とした。Separately, a platinum plate (5-) was used as a working electrode, a platinum wire was used as a counter electrode, and SCE was used as a reference electrode.
I) and polyvinyl potassium sulfate (0°01 mol/
An aqueous solution containing 1) was subjected to constant current electrolysis at 7.5 mA for 2 hours to prepare polypyrrole with polyvinyl sulfate doped on the electrode. This was used as a cation exchange electrode.
以上のようにして得られた電極について、アニオン捕捉
性電極を陽極、カチオン交換性電極を陰極として、第1
表に示す種々の電解質溶液中において、0.5 m A
の定電流電解を1時間行ない、イオン除去を行なった後
、電解質溶液中の各イオンの濃度を測定した。結果を第
1表に示す。Regarding the electrode obtained as described above, the anion-trapping electrode was used as an anode and the cation-exchanging electrode was used as a cathode.
0.5 mA in various electrolyte solutions shown in the table
After performing constant current electrolysis for 1 hour to remove ions, the concentration of each ion in the electrolyte solution was measured. The results are shown in Table 1.
次いで、電極への印加電圧を逆転させ、アニオン捕捉性
電極を陰極、カチオン交換性電極を陽極として、0.5
m Aの定電流電解を1時間行ない、電極からイオン
を放出させる電極の再生を行なった後、電解質溶液中の
各イオンの濃度を測定した。Next, the voltage applied to the electrodes was reversed, and the anion-trapping electrode was used as the cathode and the cation-exchanging electrode was used as the anode.
After performing constant current electrolysis at mA for 1 hour and regenerating the electrode to release ions from the electrode, the concentration of each ion in the electrolyte solution was measured.
結果を第1表に示す。The results are shown in Table 1.
最初の操作によって溶液中のイオンが効果的に除去され
、その後の操作によって、電極が再生されていることが
理解される。It will be appreciated that the first operation effectively removes the ions in the solution and the subsequent operation regenerates the electrode.
実施例2
白金板(5cffl)を作用極とし、白金線を対極とし
、SCEを参照電極として、アニリン塩酸塩(10重量
%)を含む水溶液について、10mAの定電流電解を2
時間行なって、電極上に塩素イオンがドーピングされた
ポリアニリンを調製した。Example 2 Using a platinum plate (5 cffl) as a working electrode, a platinum wire as a counter electrode, and an SCE as a reference electrode, an aqueous solution containing aniline hydrochloride (10% by weight) was subjected to constant current electrolysis at 10 mA for 2 seconds.
Polyaniline doped with chloride ions on the electrode was prepared over a period of time.
次いで、電流量が5クーロンに達するまで、上記ポリア
ニリンを塩酸(0,1mol/I)中で定電位還元(S
CEに対して−0,8V)して、アニオン捕捉性電極と
した。Next, the polyaniline was subjected to potentiostatic reduction (S) in hydrochloric acid (0.1 mol/I) until the amount of current reached 5 coulombs.
-0.8 V vs. CE) to form an anion-trapping electrode.
別に、ナフィオンの酸型(5重量%)の水−低級アルコ
ール混合溶)夜(水10重量%)とアニリン(0,02
mol/l)を混合してなる溶液中において、白金板(
5col)を作用極とし、白金線を対極とし、SCEを
参照電極として、2mAの定電流電解を10時間行なっ
て、電極上にナフィオンがドーピングされたポリアニリ
ンを調製して、これをカチオン交換性電極とした。Separately, the acid form of Nafion (5% by weight) in water-lower alcohol mixed solution) (10% by weight in water) and aniline (0.02% by weight)
A platinum plate (
5 col) was used as a working electrode, a platinum wire was used as a counter electrode, and SCE was used as a reference electrode, constant current electrolysis at 2 mA was performed for 10 hours to prepare polyaniline doped with Nafion on the electrode, and this was used as a cation exchange electrode. And so.
これら電極を用いて、実施例1と同様にして、塩化カリ
ウム水溶液の脱塩を行なった。結果を第2表に示す。Using these electrodes, an aqueous potassium chloride solution was desalted in the same manner as in Example 1. The results are shown in Table 2.
実施例3
チオフェン(0,1mol/I)及びテトラ−n−ブチ
ルアンモニウム四フッ化ホウ素(0,01mol/I)
を含むアセトニトリル溶液中にて、白金板(5cal)
を作用極とし、白金線を対極とし、これら電極間にIO
Vの電圧を印加し、60クーロンの電流を通電して、電
極上に四フッ化ホウ素イオンがドーピングされたポリチ
オフェンを製膜した。次に、このポリチオフェンをテト
ラ−n−ブチルアンモニウム四フッ化ホウ素(0,1m
ol/I)を含むアセトニトリル溶液中において、電流
量が5クーロンに達するまで定電流5元(SCEに対し
て−0,5V)して、アニオン捕捉性電極とした。Example 3 Thiophene (0.1 mol/I) and tetra-n-butylammonium boron tetrafluoride (0.01 mol/I)
Platinum plate (5 cal) in an acetonitrile solution containing
is used as a working electrode, a platinum wire is used as a counter electrode, and IO is connected between these electrodes.
A voltage of V was applied and a current of 60 coulombs was passed to form a film of polythiophene doped with boron tetrafluoride ions on the electrode. Next, this polythiophene was mixed with tetra-n-butylammonium boron tetrafluoride (0.1 m
In an acetonitrile solution containing ol/I), a constant current of 5 yuan (-0.5 V versus SCE) was applied until the current amount reached 5 coulombs to obtain an anion-trapping electrode.
別に、ナフィオンの酸型(5重量%)の水−低級アルコ
ール混合溶液(水10重世%)とチオフェン(0,05
mol/I)を混合してなる溶液中において、チオフェ
ン(0,05mol/l)及びナフィオンの酸型(5重
量%)の水−低級アルコール溶液(10重量%)を混合
し、これを白金板(5cal)を作用極とし、白金線を
対極とし、SCEを参照電極として、10mAの定電流
電解を1.5時間行なって、電極上にナフィオンがドー
ピングされたポリチオフェンを調製して、これをカチオ
ン交換性電極とした。Separately, a water-lower alcohol mixed solution (water 10% by weight) of the acid form of Nafion (5% by weight) and thiophene (0.05% by weight) were prepared.
A water-lower alcohol solution (10% by weight) of thiophene (0.05 mol/l) and the acid form of Nafion (5% by weight) was mixed in a solution obtained by mixing thiophene (0.05 mol/l) and the acid form of Nafion (10% by weight), and this was mixed with a platinum plate. (5 cal) was used as a working electrode, a platinum wire was used as a counter electrode, and SCE was used as a reference electrode. Constant current electrolysis at 10 mA was performed for 1.5 hours to prepare a polythiophene doped with Nafion on the electrode, which was then cationized. It was used as an exchangeable electrode.
これら電極を用いて、実施例1と同様にして、塩化カリ
ウム水溶液の脱塩を行なった。結果を第2表に示す。Using these electrodes, an aqueous potassium chloride solution was desalted in the same manner as in Example 1. The results are shown in Table 2.
実施例4
実施例3と同様にして、電極上に四フッ化ホウ素イオン
がドーピングされたポリチオフェンを調製した後、実施
例3と同様にして定電流電解を行なって、アニオン捕捉
性電極とした。Example 4 Polythiophene having an electrode doped with boron tetrafluoride ions was prepared in the same manner as in Example 3, and then constant current electrolysis was performed in the same manner as in Example 3 to obtain an anion-trapping electrode.
他方、実施例1において、ポリビニル硫酸カリウムに代
えてポリスチレンスルホン酸ナトリウムを用いた以外は
、実施例1と同様にして、電極上にポリスチレンスルホ
ン酸がドーピングされたポリピロールを得、これをカチ
オン交換性電極とした。On the other hand, polypyrrole doped with polystyrene sulfonic acid on the electrode was obtained in the same manner as in Example 1 except that sodium polystyrene sulfonate was used in place of potassium polyvinyl sulfate, and this was It was used as an electrode.
これら電極を用いて、実施例1と同様にして、塩化カリ
ウム水溶液の脱塩を行なった。結果を第2表に示す。Using these electrodes, an aqueous potassium chloride solution was desalted in the same manner as in Example 1. The results are shown in Table 2.
実施例5
実施例2と同様にして、塩素イオンがドーピングされた
ポリアニリンを電極上に製膜した後、実施例2と同様に
して定電流電解を行なって、アニオン捕捉性電極とした
。Example 5 A film of polyaniline doped with chlorine ions was formed on an electrode in the same manner as in Example 2, and then constant current electrolysis was performed in the same manner as in Example 2 to obtain an anion-trapping electrode.
また、アニリン(0,02mol/l)及びポリスチレ
ンスルホン酸の酸型(0,02mol/l)の水溶液を
混合し、白金板(5col)を作用極とし、白金線〈ロ
イロ
を対極とし、SCEを参照電極として、2mAの定電流
電解を10時間行なって、ポリスチレンスルホン酸がド
ーピングされたポリアニリンを電極上に製膜して、これ
をカチオン交換性電極とした。In addition, an aqueous solution of aniline (0.02 mol/l) and acid form of polystyrene sulfonic acid (0.02 mol/l) was mixed, a platinum plate (5 col) was used as a working electrode, a platinum wire was used as a counter electrode, and SCE Using this as a reference electrode, constant current electrolysis at 2 mA was performed for 10 hours to form a film of polyaniline doped with polystyrene sulfonic acid on the electrode, which was used as a cation exchange electrode.
前記アニオン捕捉性電極をSCEに対して+1゜5■、
対極を上記カチオン交換性電極として、塩化カリウム水
溶液(1mmole/I)中にて定電位電解を60分間
行なったところ、カリウムイオンの濃度は0.81 m
mole/lに、また、塩素イオンの濃度は0.77
mmole/Iにそれぞれ減少した。The anion-trapping electrode is set at +1°5■ with respect to SCE,
When constant potential electrolysis was performed for 60 minutes in a potassium chloride aqueous solution (1 mmole/I) using the above cation exchange electrode as the counter electrode, the concentration of potassium ions was 0.81 m
mole/l, and the concentration of chloride ions is 0.77
mmole/I, respectively.
次いで、アニオン捕捉性電極をSCEに対して−i、
o vとして、定電位電解を60分間行なった結果、カ
リウムイオンの濃度は0.95 mmole/1に、ま
た、塩素イオンの濃度は0.93 ++a+ole/1
にそれぞれ増加した。The anion-trapping electrode is then applied to the SCE-i,
As a result of constant potential electrolysis for 60 minutes, the concentration of potassium ions was 0.95 mmole/1, and the concentration of chlorine ions was 0.93 ++a+ole/1.
each increased.
Claims (10)
のアニオン捕捉能をもつp型導電性有機重合体を電気化
学的に酸化すると共に、第2の電極としてのカチオン交
換能をもつp型導電性有機重合体を電気化学的に還元す
ることによって、溶液中のアニオンを第1の電極にて捕
捉させ、カチオンを第2の電極にて捕捉させることを特
徴とする導電性有機重合体電極による溶液中のイオンの
処理方法。(1) In a solution containing ions, electrochemically oxidize a p-type conductive organic polymer with anion-trapping ability as the first electrode, and a p-type conductive polymer with cation-exchange ability as the second electrode. A conductive organic polymer electrode characterized in that anions in a solution are captured by a first electrode and cations are captured by a second electrode by electrochemically reducing the conductive organic polymer. method of processing ions in solution.
予め一部脱ドーピングされていることを特徴とする特許
請求の範囲第1項記載の導電性有機重合体電極による溶
液中のイオンの処理方法。(2) A p-type conductive organic polymer with anion-trapping ability is
A method for treating ions in a solution using a conductive organic polymer electrode according to claim 1, wherein the conductive organic polymer electrode is partially dedoped in advance.
重合体であることを特徴とする特許請求の範囲第1項又
は第2項記載の導電性有機重合体電極による溶液中のイ
オンの処理方法。(3) The conductive organic polymer electrode according to claim 1 or 2, characterized in that the conductive organic polymer is an oxidized polymer of a heterocyclic compound monomer, is used in a solution. How to process ions.
合体であることを特徴とする特許請求の範囲第1項又は
第2項記載の導電性有機重合体電極による溶液中のイオ
ンの処理方法。(4) Ions in a solution produced by the conductive organic polymer electrode according to claim 1 or 2, wherein the conductive organic polymer is an oxidized polymer of an aromatic compound monomer. processing method.
この導電性有機重合体にアニオン捕捉能を有せしめる程
度の低分子量アニオンをドーパントとして有し、カチオ
ン交換能をもつ導電性有機重合体が、この導電性有機重
合体にカチオン交換能を有せしめる程度に高分子であっ
て、且つ、分子内に多数のアニオン性基を有する重合体
をドーパントとして有することを特徴とする特許請求の
範囲第1項乃至第4項いずれかに記載の導電性有機重合
体電極による溶液中のイオンの処理方法。(5) A p-type conductive organic polymer with anion-trapping ability is
The conductive organic polymer has a low molecular weight anion as a dopant to the extent that this conductive organic polymer has anion-trapping ability, and the conductive organic polymer has cation exchange ability to the extent that this conductive organic polymer has cation exchange ability. The conductive organic polymer according to any one of claims 1 to 4, characterized in that the conductive organic polymer has a polymer having a large number of anionic groups in the molecule as a dopant. A method for processing ions in solution using a coalescing electrode.
のアニオン捕捉能をもつp型導電性有機重合体を電気化
学的に酸化すると共に、第2の電極としてのカチオン交
換能をもつp型導電性有機重合体を電気化学的に還元す
ることによって、溶液中のアニオンを第1の電極にて捕
捉させ、カチオンを第2の電極にて捕捉させ、次いで、
上記第1の電極を電気化学的に還元すると共に、第2の
電極を電気化学的に酸化することによって、上記第1の
電極から上記アニオンを放出させ、上記第2の電極から
上記カチオンを放出させ、同時に、上記第1及び第2の
電極を電気化学的に再生することを特徴とする導電性有
機重合体電極による溶液中のイオンの処理方法。(6) In a solution containing ions, electrochemically oxidize a p-type conductive organic polymer with anion-trapping ability as the first electrode, and a p-type conductive polymer with cation-exchange ability as the second electrode. By electrochemically reducing the conductive organic polymer, anions in the solution are captured at the first electrode, cations are captured at the second electrode, and then,
By electrochemically reducing the first electrode and electrochemically oxidizing the second electrode, the anion is released from the first electrode and the cation is released from the second electrode. A method for treating ions in a solution using a conductive organic polymer electrode, characterized in that the first and second electrodes are electrochemically regenerated at the same time.
予め一部脱ドーピングされていることを特徴とする特許
請求の範囲第6項記載の導電性有機重合体電極による溶
液中のイオンの処理方法。(7) A p-type conductive organic polymer with anion-trapping ability is
7. A method for treating ions in a solution using a conductive organic polymer electrode according to claim 6, wherein the conductive organic polymer electrode is partially undoped in advance.
重合体であることを特徴とする特許請求の範囲第6項又
は第7項記載の導電性有機重合体電極による溶液中のイ
オンの処理方法。(8) In a solution using the conductive organic polymer electrode according to claim 6 or 7, the conductive organic polymer is an oxidized polymer of a heterocyclic compound monomer. How to process ions.
合体であることを特徴とする特許請求の範囲第6項又は
第7項記載の導電性有機重合体電極による溶液中のイオ
ンの処理方法。(9) Ions in a solution produced by the conductive organic polymer electrode according to claim 6 or 7, wherein the conductive organic polymer is an oxidized polymer of an aromatic compound monomer. processing method.
、この導電性有機重合体にアニオン捕捉能を有せしめる
程度の低分子量アニオンをドーパントとして有し、カチ
オン交換能をもつ導電性有機重合体が、この導電性有機
重合体にカチオン交換能を有せしめる程度に高分子量で
あって、且つ、分子内に多数のアニオン性基を有する重
合体をドーパントとして有することを特徴とする特許請
求の範囲第6項乃至第9項いずれかに記載の導電性有機
重合体電極による溶液中のイオンの処理方法。(10) A p-type conductive organic polymer having an anion-trapping ability has a low molecular weight anion as a dopant that gives the conductive organic polymer an anion-trapping ability, and a conductive organic polymer having a cation-exchanging ability A patent claim characterized in that the conductive organic polymer has a polymer having a high molecular weight to the extent that it has a cation exchange ability and has a large number of anionic groups in the molecule as a dopant. A method for treating ions in a solution using the conductive organic polymer electrode according to any one of items 6 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10237986A JPH0724760B2 (en) | 1986-05-02 | 1986-05-02 | Method for treating ions in solution with conductive organic polymer electrodes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10237986A JPH0724760B2 (en) | 1986-05-02 | 1986-05-02 | Method for treating ions in solution with conductive organic polymer electrodes |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62258741A true JPS62258741A (en) | 1987-11-11 |
JPH0724760B2 JPH0724760B2 (en) | 1995-03-22 |
Family
ID=14325821
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10237986A Expired - Lifetime JPH0724760B2 (en) | 1986-05-02 | 1986-05-02 | Method for treating ions in solution with conductive organic polymer electrodes |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0724760B2 (en) |
-
1986
- 1986-05-02 JP JP10237986A patent/JPH0724760B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0724760B2 (en) | 1995-03-22 |
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