JPS6338592A - Electrolytic electrode and its production - Google Patents
Electrolytic electrode and its productionInfo
- Publication number
- JPS6338592A JPS6338592A JP61182616A JP18261686A JPS6338592A JP S6338592 A JPS6338592 A JP S6338592A JP 61182616 A JP61182616 A JP 61182616A JP 18261686 A JP18261686 A JP 18261686A JP S6338592 A JPS6338592 A JP S6338592A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- electrode
- mol
- chlorine
- coating
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000010936 titanium Chemical class 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 5
- 229910052718 tin Chemical class 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 abstract description 22
- 239000000460 chlorine Substances 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000003014 ion exchange membrane Substances 0.000 abstract description 7
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 239000012267 brine Substances 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 2
- 239000007787 solid Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電解用電極に関し、特にイオン交換膜性食塩
水電解用の陽極に適した電解用電極及びその製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrode for electrolysis, and particularly to an electrode for electrolysis suitable as an anode for ion-exchange membrane saline electrolysis, and a method for manufacturing the same.
従来から、チタン（Ｔｉ）に代表される皮膜形成性金属
等を基体とし、ルテニウム（Ｒｕ）等の白金族金属の酸
化物を主体とした電極触媒活性被覆を設けた電解用電極
は、基本発明である特公昭４８−３９５４号として知ら
れて以来、画期的な不溶性金属電極として種々の電気化
学分野で応用され、特に食塩電解工業における陽極とし
て、それまでの黒鉛電極にとって代わり広く実用化され
ている。そして、該電極は電解技術の発展や用途に応し
て種々の応用或いは改良がなされてきている。Conventionally, electrolytic electrodes are based on film-forming metals such as titanium (Ti) and provided with an electrocatalytically active coating mainly composed of oxides of platinum group metals such as ruthenium (Ru). Since it was known as Japanese Patent Publication No. 48-3954, it has been applied in various electrochemical fields as a revolutionary insoluble metal electrode, and has been widely put into practical use, especially as an anode in the salt electrolysis industry, replacing the conventional graphite electrode. ing. Various applications and improvements have been made to these electrodes in accordance with the development of electrolytic technology and applications.
特公昭４６−２１８８４号の電極は、白金族金属酸化物
等とＴｉ、 Ｔａ、 Ｎｂ等の皮膜形成性金属酸化物と
の固溶体被覆を設けたもので、特に水銀法食塩電屑用陽
極として耐久性に優れ、例えばＲｕ０ｚ−Ｔ’＋０□を
被覆したものが広く実用化されているが、隔膜法又はイ
オン交換膜法食塩電解に使用した場合、塩素発生用には
好ましくない副反応による酸素発生量が比較的多い欠点
がある。The electrode disclosed in Japanese Patent Publication No. 46-21884 is coated with a solid solution of a platinum group metal oxide and a film-forming metal oxide such as Ti, Ta, Nb, etc., and is particularly durable as an anode for mercury-method saline electrode scraps. For example, those coated with Ru0z-T'+0□ have been widely put into practical use. However, when used in the diaphragm method or ion exchange membrane method for salt electrolysis, oxygen generation occurs due to side reactions that are undesirable for chlorine generation. The drawback is that the amount is relatively large.
ＲｕＯ□−ＴｉＯ□では、ＲｕＯ□の割合を少なくする
ことによって酸素発生量をある程度低くおさえることが
できるが十分ではなく、又ＲｕＯ□の割合が少ない場合
、塩素発生過電圧の上昇が避けられない。In RuO□-TiO□, the amount of oxygen generated can be suppressed to some extent by reducing the proportion of RuO□, but this is not sufficient, and if the proportion of RuO□ is small, an increase in chlorine generation overvoltage is unavoidable.
特公昭５０−１）３３０号の電極は、上記の電極の皮膜
形成性金属酸化物の代わりにスズ（Ｓｎ）酸化物等を組
成させた混合酸化′＋ｙＪ被覆を設けたもので、使用条
件によっては耐久性は比較的良いが、ＲｕとＳｎの組合
せでは塩素過電圧を低くし、同時−こ酸素発生量を少な
くすることは困工「である。 ＲｕＯ□の割合を少な（
することにより、酸素発生量をある程度低くおさえるこ
とができるが十分ではない。 又、長期の使用ではＲｕ
０□の選択的消耗が見られ、徐々に塩素過電圧が上昇す
るという欠点を持っている。The electrode of Japanese Patent Publication No. 50-1) No. 330 has a mixed oxide '+yJ coating composed of tin (Sn) oxide, etc. instead of the film-forming metal oxide of the above electrode, and depending on the usage conditions. has relatively good durability, but with the combination of Ru and Sn, it is difficult to lower the chlorine overvoltage and simultaneously reduce the amount of oxygen generated.
By doing so, the amount of oxygen generated can be suppressed to a certain degree, but it is not sufficient. Also, for long-term use, Ru
It has the disadvantage that selective consumption of 0□ is observed and the chlorine overvoltage gradually increases.
特公昭５３−３５５５０号では、主にＲｕ０ｚ−ＴｉＯ
ｚ−５ｎＯ□からなる電極が記載されているが、上記Ｒ
ｕ０ｚ−ＴｉＯｚ 、Ｒｕ０ｚ−３ｎＯｚと同様の欠点
を持っている。 さらにＲｕＯ□を主体とする電極は水
銀法、隔膜法では十分の寿命を有するものの、近年主流
となりつつあるイオン交換膜法では十分の耐久性を持た
ない。 最近では米国特許第４５１３１０２号に記載さ
れているように、ＲｕＯ２−１ｒＯ□−５ｎＯｚを主成
分とする電極が提案されている。 ＩｒＯ□はイオン交
換膜性食塩電解用陽極に必要とされるアルカリ耐性を持
つ。In Special Publication No. 53-35550, mainly Ru0z-TiO
Although an electrode made of z-5nO□ is described, the above R
It has the same drawbacks as u0z-TiOz and Ru0z-3nOz. Further, although electrodes mainly composed of RuO□ have a sufficient lifespan in the mercury method and the diaphragm method, they do not have sufficient durability in the ion exchange membrane method, which has become mainstream in recent years. Recently, as described in US Pat. No. 4,513,102, an electrode mainly composed of RuO2-1rO□-5nOz has been proposed. IrO□ has the alkali resistance required for an ion-exchange membrane anode for salt electrolysis.
従って、Ｒｕ０ｚ−１ｒＯ□−５ｎＯ□は塩素過電圧が
低く、電解による消耗も小さいが、酸素発生量はまだ十
分に低くない。 米国特許第４５６４４３４号では、Ｒ
ｕ０ｚ−１ｒＯｚ−ＴｉＯｚが提案され、酸素発生量は
低くおさえられ、電解による消耗も小さいが、塩素過電
圧が十分低いとは言えない。Therefore, although Ru0z-1rO□-5nO□ has a low chlorine overvoltage and low consumption due to electrolysis, the amount of oxygen generated is still not low enough. In U.S. Pat. No. 4,564,434, R
u0z-1rOz-TiOz has been proposed, and although the amount of oxygen generated is kept low and the consumption due to electrolysis is small, it cannot be said that the chlorine overvoltage is sufficiently low.
近年イオン交換膜性食塩電解技術の発展と省エネルギー
の要請から、より過電圧が低く、塩素中の酸素濃度が低
く、且つ耐久性のある電極が望まれている。 これら従
来の電極は、これらすべての要求を満たすものとは言え
ない。In recent years, due to the development of ion-exchange membrane salt electrolysis technology and the demand for energy conservation, electrodes with lower overvoltage, lower oxygen concentration in chlorine, and durability are desired. These conventional electrodes cannot be said to meet all these requirements.
本発明は、塩素過電圧が低く、塩素中の酸素濃度が低く
、且つ耐久性に優れた、特にイオン交換膜注量塩電解用
に適した電極及びその製造方法を提供することを目的と
するものである。An object of the present invention is to provide an electrode that has a low chlorine overvoltage, a low oxygen concentration in chlorine, and excellent durability, and is particularly suitable for ion exchange membrane injection salt electrolysis, and a method for manufacturing the same. It is.
Ｃ問題点を解決するための手段〕 本発明の目的は、下記の本発明によって達成される。Means to solve problem C] The objects of the invention are achieved by the invention described below.
即ち第一の発明は、
皮膜形成性金属又はその合金基体上に電極触媒活性を存
する被覆を設けた電解用電極において、二亥被覆力く、
２０〜３５モル％のルテニウム酸化吻及びイリジウム酸
化物と、４５〜７０モル％のチタン酸化物と、５〜３０
モル％のスズ酸化物からなる複合酸化物であることを特
徴とする電解用電極である。That is, the first invention provides an electrolytic electrode in which a coating having electrocatalytic activity is provided on a film-forming metal or alloy substrate thereof, wherein
20-35 mol% ruthenium oxide and iridium oxide, 45-70 mol% titanium oxide, 5-30 mol%
This is an electrode for electrolysis characterized by being a composite oxide consisting of tin oxide of mol%.
第二の発明は、
皮膜形成性金属又はその合金基体上に、ルテニウム、イ
リジウム、チタニウム及びスズの熱分解可能な塩を含む
溶液を塗布し、酸化性雰囲気中で加熱して、該基体上に
２０〜３５モル％のルテニウム酸化物及びイリジウム酸
化物と、４５〜７０モル％のチタン酸化物と、５〜３０
モル％のスズ酸化物からなる複合酸化物被覆を形成する
ことを特徴とする電解用電極の製造方法である。The second invention is to apply a solution containing thermally decomposable salts of ruthenium, iridium, titanium, and tin onto a film-forming metal or alloy substrate, heat it in an oxidizing atmosphere, and apply it onto the substrate. 20-35 mol% ruthenium oxide and iridium oxide, 45-70 mol% titanium oxide, 5-30 mol%
This is a method for producing an electrode for electrolysis, characterized by forming a composite oxide coating consisting of tin oxide in a molar percentage.
以下、本発明をより詳細に説明する。The present invention will be explained in more detail below.
本発明における皮膜形成性金属基体は、Ｔｉ（チタン）
、Ｔａ （タンタル） 、Ｎｂ （ニオブ）、Ｚｒ
（ジルコニウム）等の耐食性のある４電性金属又はこれ
らの基合金が用いられ、従来から用いられている金属Ｔ
ｉ、又はＴｉ−Ｔａ−Ｎｂ５Ｔｉ−Ｐｄ等のＴｉ基合金
が好適である。 その形状は板、有孔板、棒状体、網状
体等所望のものとすることが出来る。The film-forming metal substrate in the present invention is Ti (titanium)
, Ta (tantalum), Nb (niobium), Zr
Corrosion-resistant tetraelectric metals such as (zirconium) or their base alloys are used, and conventionally used metal T
or Ti-based alloys such as Ti-Ta-Nb5Ti-Pd are preferred. Its shape can be any desired, such as a plate, a perforated plate, a rod-like body, or a net-like body.
該皮膜形成性金属基体は、適宜、表面清浄化処理等を行
い、本発明の電極触媒活性を有する被覆が設けられる。The film-forming metal substrate is appropriately subjected to a surface cleaning treatment, etc., and is provided with a coating having electrocatalytic activity of the present invention.
該被覆は、２０〜３５モル％のＲｕＯ□及び）ｒｏｚ
と、４５〜７０モル％のＴｉ１ｔと、５〜３０モル％の
ＳｎＯ□とからなる複合酸化物であり、混合体、固溶体
又は両者の混合体のいずれでも良い。The coating contains 20-35 mol% RuO□ and )roz
, 45 to 70 mol % of Tilt, and 5 to 30 mol % of SnO□, and may be a mixture, a solid solution, or a mixture of both.
基体に該複合酸化物を被覆する方法としては、前記特公
昭４８−３９５４号に記載の如き種々の手段が適用でき
るが、とりわけ、各被覆成分金属の熱分解可能な無機又
は存機の塩を含む溶液を基体上に塗布し、酸化性雰囲気
中で加熱する、いわゆる熱分解酸化法が好適である。
加熱温度は、ｉｌ！ｉ常空気中空気中０〜６５０°Ｃが
適当である。As a method for coating the composite oxide on the substrate, various methods such as those described in the above-mentioned Japanese Patent Publication No. 48-3954 can be applied, but in particular, thermally decomposable inorganic or existing salts of the respective coating component metals can be applied. A so-called thermal decomposition oxidation method, in which a solution containing the oxidation agent is applied onto a substrate and heated in an oxidizing atmosphere, is suitable.
The heating temperature is il! i In normal air 0 to 650°C is suitable.
本発明における電極被覆を構成する個々の成分の作用及
び組成範囲について、以下に説明する。The effects and composition ranges of the individual components constituting the electrode coating in the present invention will be explained below.
（１）Ｒｕ０ｚ及びＩｒ０ｚ
ＲｕＯ□及びＩｒＯ□は、主に塩素発生用Ｔ、極触媒と
して優れた機能を有し、特に前者は低い塩素過電圧をも
たらし、後者は耐久性を向上させる。そのため、本発明
においては被覆中にＲｕＯ□及びＩｒ０ｚの形で合計し
て２０〜３５モル％含有することが好ましい。 ２０モ
ル％未満では塩素過電圧が上昇し、又３５モル％を越え
ると酸素発生量が増え、耐久性も悪（なる。 ＲｕとＩ
ｒの割合は適宜選定できるが、原子比で１０＝９０〜９
０ ： １０の範囲であることが望ましい。(1) Ru0z and Ir0z RuO□ and IrO□ mainly have excellent functions as T and polar catalysts for chlorine generation, and in particular, the former brings about a low chlorine overvoltage, and the latter improves durability. Therefore, in the present invention, it is preferable that the coating contains 20 to 35 mol% of RuO□ and IrOz in total. If it is less than 20 mol%, the chlorine overvoltage will increase, and if it exceeds 35 mol%, the amount of oxygen generated will increase and the durability will be poor.Ru and I
The ratio of r can be selected as appropriate, but the atomic ratio is 10 = 90 to 9.
A range of 0:10 is desirable.
（２１７ｉ Ｏｚ
ＴｉＯ□は物理的、化学的安定を増す効果を持ち、耐久
性を向上させる。 又、適当量の存在により、酸素発生
量を低くおさえる効果がある。 そのため４５〜７０モ
ル％含有することが実用上好ましり、４５モル％未満で
は該効果を期待できず、７０モル％を越えると塩素過電
圧が高くなる。(217i Oz TiO□ has the effect of increasing physical and chemical stability and improves durability. Also, the presence of an appropriate amount has the effect of keeping the amount of oxygen generated low. Therefore, it contains 45 to 70 mol%. Practically speaking, this is preferred; if it is less than 45 mol%, the effect cannot be expected, and if it exceeds 70 mol%, the chlorine overvoltage will increase.
＋３１５ｎＯ□
ＳｎＱ□は酸素発生量を低くおさえる作用は弱いが、塩
素過電圧を低く維持する効果を持つ。 ５〜３０モル％
の適量存在させることにより、酸素発生量を増やさず、
塩素過電圧を低くおさえることができる。 ５モル％未
満では、塩素過電圧を低くする効果は小さく、３０モル
％を越えると発生塩素中の酸素発生量が増大する。+315nO□ SnQ□ has a weak effect of suppressing the amount of oxygen generated, but has the effect of keeping the chlorine overvoltage low. 5-30 mol%
By having an appropriate amount of , it does not increase the amount of oxygen generated,
Chlorine overvoltage can be kept low. If it is less than 5 mol %, the effect of lowering the chlorine overvoltage is small, and if it exceeds 30 mol %, the amount of oxygen generated in the generated chlorine increases.
以下、本発明の実施例を記載するが、これらの実施例は
本発明を限定するものではない。Examples of the present invention will be described below, but these examples do not limit the present invention.
去施■
塩化第二スズをｎ−アミルアルコールで加熱還流して得
られたアルコキシスズと塩化ルテニウム、塩化イリジウ
ム、ブチルチタネートを所定の割合に、イソプロピルア
ルコールに加温溶解し、塗布液を得た。Application ■ Alkoxytin obtained by heating refluxing stannic chloride with n-amyl alcohol, ruthenium chloride, iridium chloride, and butyl titanate in a predetermined ratio were dissolved in isopropyl alcohol under heating to obtain a coating solution. .
この塗布液を、予め脱脂し、沸膝塩酸中でエツチング処
理した純チタンよりなる開口率５０％の有孔板にブラシ
で塗布し、６０℃で１５分間乾燥した後、空気を循環し
たマンフル炉中４７５℃で１５分間加熱した。 上記塗
布、加熱の工程を８回操り返して第１表に示す組成の複
合酸化物被覆を有する試料電極を作製した。This coating solution was applied with a brush to a perforated plate made of pure titanium with an aperture ratio of 50% that had been degreased in advance and etched in boiling hydrochloric acid, dried at 60°C for 15 minutes, and then dried in a manflu oven with air circulation. The mixture was heated at 475° C. for 15 minutes. The above coating and heating steps were repeated eight times to produce sample electrodes having composite oxide coatings having the compositions shown in Table 1.
これらの試料で３ＯＡ／ｄｍ” 、９０℃、２００ｇ／
ｌＮａＣｌ溶液中における塩素過電圧の測定、ｐ１）３
での食塩水電解における塩素ガス中酸素濃度の測定、並
びに通常の条件でイオン交換脱法食塩水電解による被覆
層消耗量の測定を行った。3OA/dm”, 90℃, 200g/dm for these samples.
Measurement of chlorine overpotential in lNaCl solution, p1)3
We measured the oxygen concentration in chlorine gas during saline solution electrolysis, and measured the amount of coating layer consumption during ion-exchange removal saline electrolysis under normal conditions.
比較用として従来の、及び本発明の範囲外の被覆電極試
料を作製し、同様の測定を行った。For comparison, conventional coated electrode samples and coated electrode samples outside the scope of the present invention were prepared, and similar measurements were performed.
第１表の結果から、本発明の電極は、本発明で限定した
範囲外の電極（比較１）及び従来のＲｕ０２−ＴｒＯｚ
−５ｎＯｚ電極（比較２ ） １． ＲｕＯ□−ＩｒＯ
ｚ−ＴｉＯｚ電極（比較３ 、 ４ ） 、Ｒｕ（ｌｚ
−ＴｉＯｚ−５ｎＯｚ電極（比較５ ） 、Ｒｕ０ｚ−
ＴｉＯｚ電極（比較６）及びＲｕ０ｚ−５ｎＯｚ電極（
比較７）に比べて、塩素過電圧、酸素濃度、被覆層消耗
量がいずれも十分低い値を示し、優れた電解用電極であ
ることがねある。 これに対して、比較の電極はいずれ
も上記特性の少なくとも一つの特性で高い値を示してい
る。From the results in Table 1, the electrode of the present invention is superior to the electrode outside the range limited by the present invention (Comparison 1) and the conventional Ru02-TrOz
-5nOz electrode (comparison 2) 1. RuO□-IrO
z-TiOz electrode (Comparison 3, 4), Ru(lz
-TiOz-5nOz electrode (comparison 5), Ru0z-
TiOz electrode (comparison 6) and Ru0z-5nOz electrode (
Compared to Comparison 7), the chlorine overvoltage, oxygen concentration, and amount of coating layer consumption all showed sufficiently low values, and it may be an excellent electrode for electrolysis. On the other hand, all comparative electrodes exhibit high values for at least one of the above characteristics.
本発明は、皮膜形成性金属又は合金基体上に、Ｒｕ０ｚ
−１ｒＯｚ−ＴｉＯｚ−３ｎｏ□の特定組成の複合酸化
物被覆を設けたので、極めて塩素過電圧が低く、同時に
塩素ガス中の酸素濃度も低く、且つ耐久性に優れた電解
用電極が得られる。The present invention provides Ru0z on a film-forming metal or alloy substrate.
Since a complex oxide coating with a specific composition of -1rOz-TiOz-3no□ is provided, an electrode for electrolysis with extremely low chlorine overvoltage, low oxygen concentration in chlorine gas, and excellent durability can be obtained.
そのため、特に本発明の電極はイオン交換脱法食塩電解
の陽極に適し、長期間安定して低電圧、低酸素操業が可
能である。Therefore, the electrode of the present invention is particularly suitable as an anode for ion-exchange decomposition salt electrolysis, and is capable of stable, low-voltage, low-oxygen operation for a long period of time.
Claims (2)
活性を有する被覆を設けた電解用電極において、該被覆
が２０〜３５モル％のルテニウム酸化物及びイリジウム
酸化物と、４５〜７０モル％のチタン酸化物と、５〜３
０モル％のスズ酸化物からなる複合酸化物であることを
特徴とする電解用電極。(1) In an electrolytic electrode in which a coating having electrocatalytic activity is provided on a film-forming metal or alloy substrate thereof, the coating contains 20 to 35 mol% of ruthenium oxide and iridium oxide and 45 to 70 mol% of the ruthenium oxide and iridium oxide. % titanium oxide and 5-3
An electrode for electrolysis, characterized in that it is a composite oxide consisting of 0 mol% tin oxide.
ム、イリジウム、チタン及びスズの熱分解可能な塩を含
む溶液を塗布し、酸化性雰囲気中で加熱して、該基体上
に２０〜３５モル％のルテニウム酸化物及びイリジウム
酸化物と、４５〜７０モル％のチタン酸化物と、５〜３
０モル％のスズ酸化物からなる被合酸化物を形成するこ
とを特徴とする電解用電極の製造方法。(2) A solution containing thermally decomposable salts of ruthenium, iridium, titanium, and tin is applied onto a film-forming metal or its alloy substrate, and heated in an oxidizing atmosphere to form a 20 to 30% mol% of ruthenium oxide and iridium oxide, 45-70 mol% of titanium oxide, 5-3
1. A method for producing an electrode for electrolysis, which comprises forming an oxide to be mixed consisting of 0 mol % of tin oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61182616A JPS6338592A (en) | 1986-08-05 | 1986-08-05 | Electrolytic electrode and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61182616A JPS6338592A (en) | 1986-08-05 | 1986-08-05 | Electrolytic electrode and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6338592A true JPS6338592A (en) | 1988-02-19 |
| JPH0248634B2 JPH0248634B2 (en) | 1990-10-25 |
Family
ID=16121402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61182616A Granted JPS6338592A (en) | 1986-08-05 | 1986-08-05 | Electrolytic electrode and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6338592A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100349247B1 (en) * | 1999-09-18 | 2002-08-19 | 이호인 | Elextrolysis electrode for treating wastewater and method of making the same |
| KR100406142B1 (en) * | 1998-11-09 | 2003-11-15 | 김희정 | Dimensionally stable electrode for treating hard-resoluble waster water |
| CN110129822A (en) * | 2019-06-24 | 2019-08-16 | 蓝星(北京)化工机械有限公司 | Electrode and preparation method thereof is precipitated in chlorine |
| IT201800006544A1 (en) * | 2018-06-21 | 2019-12-21 | ANODE FOR ELECTROLYTIC EVOLUTION OF CHLORINE | |
| CN112725831A (en) * | 2020-12-18 | 2021-04-30 | 西安泰金工业电化学技术有限公司 | Improve Ti/RuO2-TiO2Sintering process for anode electrocatalytic activity and stability |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59190381A (en) * | 1983-03-11 | 1984-10-29 | ベ−・ベ−・ツエ−・アクチエンゲゼルシヤフト・ブラウン・ボヴエリ・ウント・コンパニイ | Catalyst for coating anode and manufacture |
| JPS60162787A (en) * | 1984-01-31 | 1985-08-24 | Tdk Corp | Electrode for electrolysis |
| JPS6171049A (en) * | 1984-09-13 | 1986-04-11 | 日本遠赤外線株式会社 | Sauna apparatus with water recirculation type shower apparatus |
| JPS6171050A (en) * | 1984-09-14 | 1986-04-11 | 日本遠赤外線株式会社 | Sauna apparatus with water recirculation sterilizing type shower device |
-
1986
- 1986-08-05 JP JP61182616A patent/JPS6338592A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59190381A (en) * | 1983-03-11 | 1984-10-29 | ベ−・ベ−・ツエ−・アクチエンゲゼルシヤフト・ブラウン・ボヴエリ・ウント・コンパニイ | Catalyst for coating anode and manufacture |
| JPS60162787A (en) * | 1984-01-31 | 1985-08-24 | Tdk Corp | Electrode for electrolysis |
| JPS6171049A (en) * | 1984-09-13 | 1986-04-11 | 日本遠赤外線株式会社 | Sauna apparatus with water recirculation type shower apparatus |
| JPS6171050A (en) * | 1984-09-14 | 1986-04-11 | 日本遠赤外線株式会社 | Sauna apparatus with water recirculation sterilizing type shower device |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100406142B1 (en) * | 1998-11-09 | 2003-11-15 | 김희정 | Dimensionally stable electrode for treating hard-resoluble waster water |
| KR100349247B1 (en) * | 1999-09-18 | 2002-08-19 | 이호인 | Elextrolysis electrode for treating wastewater and method of making the same |
| IT201800006544A1 (en) * | 2018-06-21 | 2019-12-21 | ANODE FOR ELECTROLYTIC EVOLUTION OF CHLORINE | |
| WO2019243163A1 (en) * | 2018-06-21 | 2019-12-26 | Industrie De Nora S.P.A. | Anode for electrolytic evolution of chlorine |
| CN112313368A (en) * | 2018-06-21 | 2021-02-02 | 德诺拉工业有限公司 | Anode for the electrolytic evolution of chlorine |
| US20210238757A1 (en) * | 2018-06-21 | 2021-08-05 | Industrie De Nora S.P.A. | Anode for electrolytic evolution of chlorine |
| JP2021529251A (en) * | 2018-06-21 | 2021-10-28 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | Anode for electrolysis generation of chlorine |
| TWI821317B (en) * | 2018-06-21 | 2023-11-11 | 義商第諾拉工業公司 | Anode for electrolytic evolution of chlorine |
| CN110129822A (en) * | 2019-06-24 | 2019-08-16 | 蓝星(北京)化工机械有限公司 | Electrode and preparation method thereof is precipitated in chlorine |
| CN112725831A (en) * | 2020-12-18 | 2021-04-30 | 西安泰金工业电化学技术有限公司 | Improve Ti/RuO2-TiO2Sintering process for anode electrocatalytic activity and stability |
| CN112725831B (en) * | 2020-12-18 | 2022-10-18 | 西安泰金工业电化学技术有限公司 | Improve Ti/RuO 2 -TiO 2 Sintering process for anode electrocatalytic activity and stability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0248634B2 (en) | 1990-10-25 |
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