JPH10287991A - Oxygen generating electrode and its production - Google Patents
Oxygen generating electrode and its productionInfo
- Publication number
- JPH10287991A JPH10287991A JP9033513A JP3351397A JPH10287991A JP H10287991 A JPH10287991 A JP H10287991A JP 9033513 A JP9033513 A JP 9033513A JP 3351397 A JP3351397 A JP 3351397A JP H10287991 A JPH10287991 A JP H10287991A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- electrode
- salt
- oxygen
- substrate
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001301 oxygen Substances 0.000 title claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000004020 conductor Substances 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 13
- 239000013535 sea water Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XZKPQDKQWRJMOG-UHFFFAOYSA-K C(CCC)O.[Ir](Cl)(Cl)Cl Chemical compound C(CCC)O.[Ir](Cl)(Cl)Cl XZKPQDKQWRJMOG-UHFFFAOYSA-K 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003902 seawater pollution Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、海水をはじめとす
る塩素イオン含有水溶液の電解にカソードとして使用
し、塩素の発生を抑えて酸素を発生するための電極に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode which is used as a cathode for electrolysis of an aqueous solution containing chlorine ions such as seawater and suppresses the generation of chlorine to generate oxygen.
【０００２】[0002]
【従来の技術】海水を電解すると、通常はアノードで水
素と水酸化ナトリウムとが発生し、アノードで塩素が発
生して、この水酸化ナトリウムと塩素とから次亜塩素酸
ナトリウムが生成する。 この場合のアノードは、耐食
金属であるチタンの表面を白金族金属の酸化物で被覆し
た電極が、高性能の電極として使用されている。2. Description of the Related Art When seawater is electrolyzed, hydrogen and sodium hydroxide are usually generated at the anode, chlorine is generated at the anode, and sodium hypochlorite is generated from the sodium hydroxide and chlorine. As the anode in this case, an electrode obtained by coating the surface of titanium, which is a corrosion-resistant metal, with an oxide of a platinum group metal is used as a high-performance electrode.
【０００３】次亜塩素酸は、海水中の生物が水中構造物
に付着して生育することを防ぐ効果があるので、このよ
うな海水電解を意図的に行なうこともあったが、近年は
塩素による海水汚染は避けるべきものとして、あまり行
なわれない。Hypochlorous acid has the effect of preventing organisms in the seawater from growing on the underwater structures, so that such electrolysis of seawater has been performed intentionally. Seawater pollution due to storms is rarely done.
【０００４】一方、通常の水電解と同様に、海水から水
素と酸素とを分離して得る電解が試みられている。 こ
の場合は、カソードで水素を発生し、アノードでは酸素
のみを発生させなければならないから、それを可能にす
る電極が必要になる。[0004] On the other hand, similar to ordinary water electrolysis, electrolysis obtained by separating hydrogen and oxygen from seawater has been attempted. In this case, since hydrogen must be generated at the cathode and only oxygen must be generated at the anode, an electrode that enables this is required.
【０００５】海水中では、酸素発生の平衡電位は塩素発
生の平衡電位より約０．６Ｖ低く、熱力学的には、酸素
が容易に発生するはずである。 ところが、塩素の発生
が単純な電極反応２Ｃｌ→Ｃｌ2 ＋２ｅであって、電解
電位も平衡電位に近いのに対し、酸素の発生は何段階も
の素反応からなる複雑な反応を経て起るため、電解電位
は容易に塩素発生の平衡電位を超えてしまう。 従っ
て、酸素の発生をみるときには多量の塩素も発生してし
まい、所望の結果が得られない。In seawater, the equilibrium potential for oxygen generation is about 0.6 V lower than the equilibrium potential for chlorine generation, and thermodynamically oxygen should be easily generated. However, since the generation of chlorine is a simple electrode reaction 2Cl → Cl 2 + 2e, and the electrolytic potential is close to the equilibrium potential, the generation of oxygen occurs through a complicated reaction consisting of a number of elementary reactions. The electrolytic potential easily exceeds the equilibrium potential for chlorine generation. Therefore, when observing the generation of oxygen, a large amount of chlorine is also generated, and a desired result cannot be obtained.
【０００６】本発明者らは、この問題を克服し、塩素発
生には不活性であるが酸素発生には高度に活性であるよ
うなアノードを提供することを意図して研究し、耐食金
属であるＴｉを導電性材料として使用し、その表面をＭ
ｎの酸化物で被覆した電極が、酸素発生効率約７０％を
実現することを知った。 ここで、「酸素発生効率」の
語は、通電電流に対する酸素発生に利用された電流の割
合として定義される。The present inventors have studied with the aim of overcoming this problem and providing an anode which is inert for chlorine generation but highly active for oxygen generation, and has been developed for corrosion resistant metals. A certain Ti is used as a conductive material, and its surface is
It has been found that an electrode coated with n oxide achieves an oxygen generation efficiency of about 70%. Here, the term “oxygen generation efficiency” is defined as the ratio of the current used for oxygen generation to the supplied current.
【０００７】その後の研究の結果、Ｗの酸化物およびＭ
ｏの酸化物の一方または両方を（両方の場合は合計量
で）０．２〜２０モル％含有し、残部を実質上Ｍｎの酸
化物が占める導電性被覆を、導電性材料の基体表面に形
成してなる電極が、いっそう高い酸素発生効率を示すこ
とを見出して、すでに提案した（特願平８−６４５３９
号）。As a result of subsequent studies, it was found that oxides of W and M
a conductive coating containing 0.2 to 20 mol% of one or both of the oxides of o (in the total amount of both) and substantially the remainder of the oxide of Mn, on the surface of the substrate of the conductive material. The inventors have found that the formed electrode shows higher oxygen generation efficiency and have already proposed it (Japanese Patent Application No. 8-64539).
issue).
【０００８】上記の海水電解のための酸素発生用電極の
製造方法は、基本的には、Ｍｎの塩に加えて、Ｗの塩お
よびＭｏの塩の一方または両方を溶解または分散させた
液を導電性材料の基体上に塗布し、乾燥の後、加熱して
塩を分解することにより、導電性基体上にＷの酸化物お
よびＭｏの酸化物の一方または両方を０．２〜２０モル
％含有し、残部を実質上Ｍｎの酸化物が占める導電性被
覆を形成することからなる。 ここで、「Ｍｎ（Ｗ，Ｍ
ｏ）の塩」とは、これら金属がカチオンとして存在する
ものに限らず、アニオンを形成しているものであっても
よく、要するにＭｎ（Ｗ，Ｍｏ）を含有する水溶性の塩
を指す。The above-described method for producing an electrode for generating oxygen for seawater electrolysis basically includes a method in which one or both of a salt of W and a salt of Mo are dissolved or dispersed in addition to a salt of Mn. After coating on a substrate of a conductive material, drying and heating to decompose the salt, one or both of the oxide of W and the oxide of Mo are added to the conductive substrate in an amount of 0.2 to 20 mol%. To form a conductive coating containing substantially the remainder of Mn oxide. Here, “Mn (W, M
The “salt of o)” is not limited to those in which these metals exist as cations, but may be those in which an anion is formed. In short, it refers to a water-soluble salt containing Mn (W, Mo).
【０００９】上記の塩の熱分解は、大気中で４００〜５
００℃の温度に数分間〜数時間加熱することにより実施
でき、この操作自体は簡単であるが、１回に形成できる
層の厚さが薄く、多数回繰り返して行なわなければなら
ず、労力を要するのが難点である。The thermal decomposition of the above salt is carried out in the atmosphere at 400 to 5
This operation can be carried out by heating to a temperature of 00 ° C. for several minutes to several hours. This operation itself is simple, but the thickness of a layer that can be formed at one time is thin and must be repeated many times. The difficulty is that it costs.
【００１０】そこでさらに研究を重ね、上記の電極活物
質を構成する金属酸化物が陽極析出法により効果的に導
電性基体表面に形成できることを見出した。Therefore, the present inventors have further studied and found that the metal oxide constituting the above-mentioned electrode active material can be effectively formed on the surface of the conductive substrate by an anodic deposition method.
【００１１】[0011]
【発明が解決しようとする課題】本発明の目的は、上記
の新しい知見を利用し、海水を代表とする塩素イオンを
含有する水溶液の電解に使用したときに、塩素の発生を
抑えて酸素を発生させることのできる電極、すなわち酸
素発生効率の高い電極を提供すること、およびそのよう
な電極の製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to utilize the above-mentioned new knowledge and to suppress the generation of chlorine and to reduce oxygen when used for electrolysis of an aqueous solution containing chloride ions such as seawater. An object of the present invention is to provide an electrode that can be generated, that is, an electrode having high oxygen generation efficiency, and to provide a method for manufacturing such an electrode.
【００１２】[0012]
【課題を解決するための手段】本発明の酸素発生用電極
は、Ｗの酸化物およびＭｏの酸化物の一方または両方を
（両方の場合は合計量で）０．２〜２０モル％含有し、
残部を実質上Ｍｎの酸化物が占める混合酸化物の導電性
被覆を、導電性材料の基体表面に陽極析出法により形成
してなる、塩素イオン含有水溶液を電解するための酸素
発生用電極である。The oxygen generating electrode of the present invention contains 0.2 to 20 mol% of one or both of the oxide of W and the oxide of Mo (in both cases, in total). ,
An electrode for oxygen generation for electrolyzing a chlorine ion-containing aqueous solution, which is obtained by forming a conductive coating of a mixed oxide occupied substantially by an oxide of Mn on the substrate surface of a conductive material by an anodic deposition method. .
【００１３】この酸素発生用電極を与える本発明の製造
方法は、Ｍｎの塩に加えて、Ｗの塩およびＭｏの塩の一
方または両方を溶解した液中で導電性材料の基体を陽極
として電解を行なうことにより、導電性基体上にＷの酸
化物およびＭｏの酸化物の一方または両方を０．２〜２
０モル％含有し残部を実質上Ｍｎの酸化物が占める導電
性被覆を形成することからなる。According to the production method of the present invention for providing the oxygen generating electrode, the electrolysis is performed using a conductive material substrate as an anode in a solution in which one or both of a salt of W and a salt of Mo are dissolved in addition to the salt of Mn. By performing one or both of the oxide of W and the oxide of Mo on the conductive substrate by 0.2 to 2
Forming a conductive coating containing 0 mol% and the remainder substantially composed of an oxide of Mn.
【００１４】[0014]
【作用】さきの発明に関して述べたように、Ｗの酸化物
もＭｏの酸化物も、それ自体ではアノード材料として高
い酸素発生活性を示すものではないが、Ｍｎの酸化物に
適量配合することにより、高い酸素発生効率が得られ
る。 この効果は、Ｍｎの酸化物中へのＷの酸化物また
はＭｏの酸化物の固溶によるものか、または酸化物間の
化合物を形成するためと考えられる。As described in connection with the above invention, neither the oxide of W nor the oxide of Mo shows a high oxygen generating activity as an anode material by itself. And high oxygen generation efficiency can be obtained. This effect is considered to be due to the solid solution of the oxide of W or the oxide of Mo in the oxide of Mn, or to the formation of a compound between the oxides.
【００１５】配合の効果は０．２モル％程度から認めら
れ、１０〜１５モル％で最も高いレベルに達し、１５％
を超える領域では飽和する。 経済性も考え合わせる
と、２０モル％を超える配合は不利となる。The effect of the composition is recognized from about 0.2 mol%, and reaches the highest level at 10 to 15 mol%,
Saturation occurs in the region exceeding. In consideration of economic efficiency, a composition exceeding 20 mol% is disadvantageous.
【００１６】導電性基体は、本発明においてもＴｉまた
はその合金が適切である。 Ｔｉ合金の具体例として
は、ＴｉとＺｒ，Ｎｂ，Ｔａなどの合金、またＴｉ−Ｐ
ｄ合金が挙げられる。 これを使用するときは、電極形
成作業に伴うＴｉ表面の不働態化（ＴｉＯ2 被膜の形
成）で絶縁性被膜の形成を避けるため、あらかじめＴｉ
基体の表面を酸化イリジウムで被覆する処理を施してお
くことが好ましい。 この処理は、塩化イリジウム酸の
有機溶媒溶液を塗布し、乾燥後、焼成する熱分解法によ
り、容易に実施できる。 酸化物被覆形成後の熱処理
は、被覆を基体金属に密着させるための処理であって、
大気中で４００〜５００℃の温度に数分間〜数時間加熱
することによって実施すればよい。In the present invention, Ti or an alloy thereof is suitable for the conductive substrate. Specific examples of the Ti alloy include Ti and alloys such as Zr, Nb, and Ta, and Ti-P
d alloy. When this is used, in order to avoid the formation of an insulating film due to passivation of the Ti surface (formation of a TiO 2 film) during the electrode formation operation,
It is preferable that the surface of the substrate is treated with iridium oxide. This treatment can be easily performed by a thermal decomposition method in which an organic solvent solution of iridic acid chloride is applied, dried, and fired. The heat treatment after forming the oxide coating is a process for bringing the coating into close contact with the base metal,
It may be carried out by heating in air at a temperature of 400 to 500 ° C. for several minutes to several hours.
【００１７】陽極析出は、Ｍｎの可溶性塩、代表的には
ＭｎＳＯ4 に加えて、Ｗの可溶性塩、代表的にはＮａ2
ＷＯ4とＭｏの可溶性塩、代表的にはＮａ2ＭｏＯ4の一
方または両方を溶解含有する水溶液のpHを、硫酸などの
添加によって酸性にし（pHにして０．５〜１．５付近が
好適）、温めた（温度６０〜９０℃が適切）ものを電解
液として使用し、上記導電性材料の基体を陽極として電
解を行なうことにより実施する。 通常、電流密度３〜
２０Ａ／dm2 程度で２．５〜１２分間の電解を行なえ
ば、十分な厚さの陽極活物質が析出し、Ｍｎ−Ｗ混合酸
化物電極、Ｍｎ−Ｍｏ混合酸化物電極、Ｍｎ−Ｗ−Ｍｏ
混合酸化物電極が得られる。The anodic deposition involves the addition of a soluble salt of W, typically Na 2 , in addition to a soluble salt of Mn, typically MnSO 4.
WO 4 and soluble salts of Mo, the pH of the aqueous solution typically containing dissolved either or both of Na 2 MoO 4, preferably around 0.5 to 1.5 in the acidified (pH by the addition of such acid ), Using a warmed one (appropriately at a temperature of 60 to 90 ° C.) as an electrolytic solution and performing electrolysis using the conductive material substrate as an anode. Usually, current density 3 ~
When electrolysis is performed at about 20 A / dm 2 for 2.5 to 12 minutes, a sufficiently thick anode active material is deposited, and a Mn—W mixed oxide electrode, a Mn—Mo mixed oxide electrode, and a Mn—W— Mo
A mixed oxide electrode is obtained.
【００１８】[0018]
【実施例】Ｔｉの基材上に塩化イリジウム−ブタノール
溶液をハケ塗りして乾燥させたのち、大気中で４５０℃
に加熱して塩化イリジウムを酸化イリジウムに変える作
業を数回繰り返し、最後に４５０℃で１時間焼成して、
ＩｒＯ2 被覆したＴｉ電極下地材を用意した。EXAMPLE An iridium chloride-butanol solution was brush-coated on a Ti substrate and dried.
The operation of changing iridium chloride to iridium oxide by heating to iridium oxide is repeated several times, and finally baked at 450 ° C. for 1 hour,
A Ti electrode base material coated with IrO 2 was prepared.
【００１９】［実施例１］ＭｎＳＯ4 を０．２Ｍ、Ｎａ
2 ＷＯ4 を０．０２Ｍの割合で含有する溶液に硫酸を加
えてpHを１に調整し、９０℃に温めた。 この溶液中
で、上記の導電性下地材を陽極として電流密度３Ａ／dm
2 で１０分間の電解を行ない、Ｍｎ−Ｗ混合酸化物電極
を得た。 この電極の電極活物質中のＷの濃度は、ＥＰ
ＭＡ分析によれば８モル％であった。Example 1 MnSO 4 was 0.2 M, Na
The 2 WO 4 by adding sulfuric acid to a solution containing a ratio of 0.02M pH was adjusted to 1, was warmed to 90 ° C.. In this solution, a current density of 3 A / dm was obtained using the above-mentioned conductive base material as an anode.
Electrolysis was performed for 10 minutes at 2 to obtain a Mn-W mixed oxide electrode. The concentration of W in the electrode active material of this electrode is EP
According to MA analysis, it was 8 mol%.
【００２０】上記の電極を陽極として、pHを８に調整し
た０．５Ｍ−ＮａＣｌ水溶液１リットル中、３０℃にお
いて、電流密度２Ａ／dm2 で電解を行なった。 通電量
１０００クーロンの電解ののち、液中に溶存している次
亜塩素酸の量をヨウ素滴定法により定量し、塩素発生に
消費された電気量を算出することにより酸素発生効率を
算出したところ、９８．２％という高い値を得た。Using the above electrode as an anode, electrolysis was performed at a current density of 2 A / dm 2 at 30 ° C. in 1 liter of a 0.5 M NaCl aqueous solution adjusted to pH 8. After electrolysis with a current flow of 1000 coulombs, the amount of hypochlorous acid dissolved in the liquid was quantified by iodometric titration, and the oxygen generation efficiency was calculated by calculating the amount of electricity consumed for chlorine generation. , 98.2%.
【００２１】［実施例２］ＭｎＳＯ4 とＮａ2 ＷＯ4 と
を種々の割合で含む水溶液を酸性にして９０℃に温め、
実施例１と同様に、ＩｒＯ2 で被覆した導電性下地材を
陽極として、電流密度３０mA／dm2 で１０分間の電解を
行なって、ＭｎとＷとを種々の割合で含有するＭｎ−Ｗ
混合酸化物電極を得た。Example 2 An aqueous solution containing MnSO 4 and Na 2 WO 4 at various ratios was acidified and heated to 90 ° C.
In the same manner as in Example 1, Mn-W containing Mn and W at various ratios was obtained by performing electrolysis at a current density of 30 mA / dm 2 for 10 minutes using a conductive base material coated with IrO 2 as an anode.
A mixed oxide electrode was obtained.
【００２２】これらの電極を陽極として使用し、pHを８
に調整した０．５Ｍ−ＮａＣｌ水溶液１リットル中、３
０℃において、電流密度２Ａ／dm2 で電解を行なった。These electrodes were used as anodes and the pH was adjusted to 8
In 1 liter of a 0.5M NaCl aqueous solution adjusted to 3
Electrolysis was performed at 0 ° C. at a current density of 2 A / dm 2 .
【００２３】通電密度１０００クーロンの電解ののち、
実施例１と同様、ヨウ素滴定による次亜塩素酸の定量に
もとづいて酸素発生効率を算出した。 その結果を、電
極活物質中のＷ含有量とともに、下に示す。After electrolysis with a current density of 1000 coulombs,
Similarly to Example 1, the oxygen generation efficiency was calculated based on the determination of hypochlorous acid by iodine titration. The results are shown below together with the W content in the electrode active material.
【００２４】 Ｗ含量（モル％） 酸素発生効率（％） ０．２ ８２．０ ０．８ ８９．０ １．４ ９３．１ ２．０ ９５．０ ３．２ ９６．７ ４．８ ９７．６ ６．４ ９７．９ ８．０ ９８．２ ９．６ ９８．４ １１．８ ９８．８ １４．０ ９９．０ １５．６ ９９．２ １８．２ ９９．２ １９．９ ９９．２ ０（比較例） ８０ 最下段は、比較のため使用したＭｎ酸化物電極で得た値。 W content (mol%) Oxygen generation efficiency (%) 0.2 82.0 0.8 89.0 1.4 93.1 2.0 95.0 3.2 96.7 4.8 97. 6 6.4 97.9 8.0 98.2 9.6 98.4 11.8 98.8 14.0 99.0 15.6 99.2 18.2 99.2 19.9 99.2 0 (Comparative Example) 80 The bottom row shows values obtained with the Mn oxide electrode used for comparison.
【００２５】［実施例３］実施例２のＮａ2 ＷＯ4 に代
えてＮａ2 ＭｏＯ4 を使用し、実施例２と同じ操作を繰
り返した。 ただし、陽極を形成するための電解に当っ
て、陽極室と陰極室とを分離するガラスフィルターを使
用した。Example 3 The same operation as in Example 2 was repeated, except that Na 2 MoO 4 was used instead of Na 2 WO 4 of Example 2. However, in the electrolysis for forming the anode, a glass filter for separating the anode chamber and the cathode chamber was used.
【００２６】得られた電極の電極活物質中のＭｏの含有
量と、その電極を用いたときの酸素発生効率とを、下に
示す。The content of Mo in the electrode active material of the obtained electrode and the oxygen generation efficiency when the electrode is used are shown below.
【００２７】 Ｍｏ含量（モル％） 酸素発生効率（％） ０．２ ８２．１ ０．７ ８７．５ １．５ ９３．５ ２．１ ９５．２ ３．６ ９６．９ ５．２ ９７．７ ７．２ ９８．１ ８．８ ９８．３ １０．０ ９８．５ １２．１ ９８．７ １３．８ ９８．９ １５．８ ９９．２ １８．０ ９９．２ ２０．０ ９９．２ ０ ８０ 最下段は比較例。 Mo content (mol%) Oxygen generation efficiency (%) 0.2 82.1 0.7 87.5 1.5 93.5 2.1 95.2 3.6 96.9 5.2 97. 7 7.2 98.1 8.8 98.3 10.0 98.5 12.1 98.7 13.8 98.9 15.8 99.2 18.0 99.2 20.0 99.2 0 80 The bottom row is a comparative example.
【００２８】［実施例４］ＭｎＳＯ4 に加えてＮａ2 Ｍ
ｏＯ4 とＮａ2 ＷＯ4 との両方を使用し、実施例３を繰
り返した。 得られた電極の電極活物質中のＭｏおよび
Ｗの含有量と、その電極を用いたときの酸素発生効率と
を、下の表に示す。Example 4 In addition to MnSO 4 , Na 2 M
Example 3 was repeated using both oO 4 and Na 2 WO 4 . The content of Mo and W in the electrode active material of the obtained electrode and the oxygen generation efficiency when the electrode is used are shown in the table below.
【００２９】 Ｍｏ含量（モル％） Ｗ含量（モル％） 酸素発生効率（％） ０．１ ０．１ ８２．１ ０．２ ０．４ ８６．３ １．０ ０．６ ９３．９ ２．１ １．０ ９６．７ ２．５ １．３ ９７．１ ２．１ ３．５ ９７．７ ３．０ ４．５ ９８．２ ３．１ ５．８ ９８．４ ６．０ ５．１ ９８．５ ６．２ ５．９ ９８．７ ６．２ ８．０ ９９．０ ６．５ ８．８ ９９．１ ６．５ １１．０ ９９．２ ７．８ １２．１ ９９．２ Mo content (mol%) W content (mol%) Oxygen generation efficiency (%) 0.1 0.1 82.1 0.2 0.4 86.3 1.0 0.6 93.9 2. 1 1.0 96.7 2.5 1.3 97.1 2.1 3.5 3.5 97.7 3.0 4.5 98.2 3.1 5.8 98.4 6.0 5.1 98 5.5 6.2 5.9 98.7 6.2 8.0 99.0 6.5 8.8 99.1 6.5 11.0 99.2 7.8 12.1 99.2
【００３０】[0030]
【発明の効果】本発明に従って、陽極析出法により金属
酸化物を生成させ、導電性基体の表面を被覆するＭｎ酸
化物中にＷの酸化物およびＭｏの酸化物の一方または両
方を適量存在させた電極は、海水を電解して塩素の発生
を避けつつ発生させるための電極として、高い効率を示
す。 陽極析出法は、多大の労力および時間を要するこ
となく必要量の電極活物質を形成することができ、有利
である。 電極下地材としてＴｉまたはその合金を使用
し、陽極活物質である上記金属酸化物の析出に先立って
表面にＩｒＯ2 被膜を施した好ましい態様においては、
ＴｉＯ2 の生成による絶縁層が形成されることなく、電
極の寿命が長い。According to the present invention, a metal oxide is formed by an anodic deposition method, and an appropriate amount of one or both of the W oxide and the Mo oxide is present in the Mn oxide covering the surface of the conductive substrate. The electrode has high efficiency as an electrode for electrolyzing seawater to generate chlorine while avoiding generation of chlorine. The anodic deposition method is advantageous because a required amount of an electrode active material can be formed without requiring much labor and time. In a preferred embodiment in which Ti or an alloy thereof is used as an electrode base material and an IrO 2 coating is applied to the surface prior to the deposition of the metal oxide as an anode active material,
The electrode has a long service life without forming an insulating layer due to the formation of TiO 2 .
【００３１】本発明は、海水の電解に止まらず、その他
の塩素イオンを含有する水溶液、具体的には、塩化ナト
リウム水溶液、塩化カリウム水溶液、地下カン水、ゴミ
焼却場廃塩水、塩酸洗淨中和廃液など、各種の産業廃水
の電解処理に適用して、その効果を発揮することができ
る。The present invention is not limited to the electrolysis of seawater, but also includes an aqueous solution containing other chloride ions, specifically, an aqueous solution of sodium chloride, an aqueous solution of potassium chloride, underground water, waste salt water of a garbage incineration plant, and washing with hydrochloric acid. It can be applied to the electrolytic treatment of various types of industrial wastewater such as Japanese wastewater to exhibit its effect.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 秋山 英二 宮城県仙台市太白区向山２−13−５ ハイ ツルーベンス210 (72)発明者 幅崎 浩樹 宮城県仙台市太白区長町８−２−31−206 (72)発明者 川嶋 朝日 宮城県仙台市太白区ひより台37−17 (72)発明者 浅見 勝彦 宮城県仙台市太白区太白２−５−３ ──────────────────────────────────────────────────続 き Continuing on the front page (72) Eiji Akiyama, 2-13-5 Mukaiyama, Taihaku-ku, Sendai, Miyagi Prefecture 210 (72) Inventor Hiroki Hirosaki 8-2-231 Nagamachi, Taihaku-ku, Sendai, Miyagi −206 (72) Inventor Kawashima Asahi 37-17 Hiyoridai, Taihaku-ku, Sendai City, Miyagi Prefecture (72) Inventor Katsuhiko Asami 2-5-3, Taihaku, Taihaku-ku, Sendai City, Miyagi Prefecture
Claims (5)
たは両方を（両方の場合は合計量で）０．２〜２０モル
％含有し、残部を実質上Ｍｎの酸化物が占める混合酸化
物の導電性被覆を、導電性材料の基体表面に陽極析出法
により形成してなる、塩素イオン含有水溶液を電解する
ための酸素発生用電極。1. A mixed oxide containing 0.2 to 20 mol% (in both cases in total) of one or both of an oxide of W and an oxide of Mo, with the remainder substantially being an oxide of Mn. An electrode for oxygen generation for electrolyzing a chlorine ion-containing aqueous solution, wherein an electroconductive coating of a substance is formed on a substrate surface of an electroconductive material by an anodic deposition method.
からなるものである請求項１の酸素発生用電極。2. The oxygen generating electrode according to claim 1, wherein the base of the conductive material is made of Ti or an alloy thereof.
からなり、その表面であって前記混合酸化物の導電性被
覆の下に酸化イリジウムの層を有する請求項１の酸素発
生用電極。3. The oxygen-generating electrode according to claim 1, wherein the base of the conductive material is made of Ti or an alloy thereof, and has a layer of iridium oxide on the surface thereof and under the conductive coating of the mixed oxide.
塩の一方または両方を溶解した液中で導電性材料の基体
を陽極として電解を行なうことにより、導電性基体上に
Ｗの酸化物およびＭｏの酸化物の一方または両方を０．
２〜２０モル％含有し残部を実質上Ｍｎの酸化物が占め
る導電性被覆を形成することからなる、塩素イオン含有
水溶液を電解するための酸素発生用電極の製造方法。4. An electrolysis is performed in a solution in which one or both of a salt of W and a salt of Mo in addition to a salt of Mn is dissolved using a substrate of a conductive material as an anode. One or both of the oxide and the oxide of Mo may be added to 0.1.
A method for producing an electrode for oxygen generation for electrolyzing a chlorine ion-containing aqueous solution, comprising forming a conductive coating containing 2 to 20 mol% and the remainder substantially composed of an oxide of Mn.
使用し、その表面に酸化イリジウム被覆を施したのち導
電性酸化物被膜の形成を行なう請求項４の製造方法。5. The method according to claim 4, wherein Ti or an alloy thereof is used as the conductive substrate, and the surface thereof is coated with iridium oxide, and then the conductive oxide film is formed.
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|---|---|---|---|
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| JP3180697 | 1997-02-17 | ||
| JP9-31806 | 1997-02-17 | ||
| JP03351397A JP3724096B2 (en) | 1997-02-17 | 1997-02-18 | Oxygen generating electrode and manufacturing method thereof |
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| Publication Number | Publication Date |
|---|---|
| JPH10287991A true JPH10287991A (en) | 1998-10-27 |
| JP3724096B2 JP3724096B2 (en) | 2005-12-07 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077319A (en) * | 2004-09-13 | 2006-03-23 | Koji Hashimoto | Oxygen generation type electrode and its production method |
| JP2006233302A (en) * | 2005-02-25 | 2006-09-07 | Daiki Engineering Kk | Oxygen generating electrode and manufacturing method thereof |
| JP2007138254A (en) * | 2005-11-18 | 2007-06-07 | Koji Hashimoto | Oxygen generating electrode and manufacturing method thereof |
| JP2007302927A (en) * | 2006-05-09 | 2007-11-22 | Daiki Ataka Engineering Co Ltd | Oxygen generating electrode |
| JP2010059523A (en) * | 2008-09-05 | 2010-03-18 | Daiki Ataka Engineering Co Ltd | Electrode for producing oxygen |
| JP2012511099A (en) * | 2008-10-30 | 2012-05-17 | マクダーミッド インコーポレーテッド | Chromium plating method from trivalent chromium plating bath |
-
1997
- 1997-02-18 JP JP03351397A patent/JP3724096B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077319A (en) * | 2004-09-13 | 2006-03-23 | Koji Hashimoto | Oxygen generation type electrode and its production method |
| JP2006233302A (en) * | 2005-02-25 | 2006-09-07 | Daiki Engineering Kk | Oxygen generating electrode and manufacturing method thereof |
| JP2007138254A (en) * | 2005-11-18 | 2007-06-07 | Koji Hashimoto | Oxygen generating electrode and manufacturing method thereof |
| JP2007302927A (en) * | 2006-05-09 | 2007-11-22 | Daiki Ataka Engineering Co Ltd | Oxygen generating electrode |
| JP2010059523A (en) * | 2008-09-05 | 2010-03-18 | Daiki Ataka Engineering Co Ltd | Electrode for producing oxygen |
| JP2012511099A (en) * | 2008-10-30 | 2012-05-17 | マクダーミッド インコーポレーテッド | Chromium plating method from trivalent chromium plating bath |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3724096B2 (en) | 2005-12-07 |
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