JPS6045710B2 - electrolytic cell - Google Patents

electrolytic cell

Info

Publication number
JPS6045710B2
JPS6045710B2 JP56107104A JP10710481A JPS6045710B2 JP S6045710 B2 JPS6045710 B2 JP S6045710B2 JP 56107104 A JP56107104 A JP 56107104A JP 10710481 A JP10710481 A JP 10710481A JP S6045710 B2 JPS6045710 B2 JP S6045710B2
Authority
JP
Japan
Prior art keywords
nickel plating
iron
cathode
nickel
cathode chamber
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.)
Expired
Application number
JP56107104A
Other languages
Japanese (ja)
Other versions
JPS589988A (en
Inventor
正敏 杉森
和孝 崎山
淳治 小柴
隆 毛利
節夫 吉田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Toyo Soda Manufacturing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Soda Manufacturing Co Ltd filed Critical Toyo Soda Manufacturing Co Ltd
Priority to JP56107104A priority Critical patent/JPS6045710B2/en
Publication of JPS589988A publication Critical patent/JPS589988A/en
Publication of JPS6045710B2 publication Critical patent/JPS6045710B2/en
Expired legal-status Critical Current

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Description

【発明の詳細な説明】 本発明は、隔膜を用いた塩化アルカリ水溶液の電解にお
いて、鉄の溶出が全くなく、長期間安定して、かつ少な
い消費電力にて苛性アルカリを製造するに適した新規な
電解槽に関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel method suitable for producing caustic alkali stably over a long period of time and with low power consumption, with no iron elution at all in the electrolysis of aqueous alkali chloride solutions using a diaphragm. This relates to electrolytic cells.

例えは、陽イオン交換膜を隔膜として食塩水溶液の電解
を行ない、塩素および苛性ソーダを製造する方法は公知
である。
For example, a method for producing chlorine and caustic soda by electrolyzing a saline solution using a cation exchange membrane as a diaphragm is known.

この陽イオン交換膜を用いる電解方法は、陰極て生成す
る苛性ソーダ中に混入する食塩の量が極めて少なく、又
、水銀法やアスベスト法などに比較して公害問題もなく
、近年になつて特に注目されてきた。陰極室で得られる
苛性ソーダの濃度及び電流効率を高めるべく陽イオン交
換膜の開発、改良がなされ、最近では20wt%以上の
苛性ソーダが90%以上の高い電流効率で得ることがで
きる。
This electrolysis method using a cation exchange membrane has attracted particular attention in recent years because the amount of salt mixed into the caustic soda produced at the cathode is extremely small, and there is no pollution problem compared to the mercury method or asbestos method. It has been. Cation exchange membranes have been developed and improved in order to increase the concentration and current efficiency of caustic soda obtained in the cathode chamber, and recently, caustic soda of 20 wt % or more can be obtained with a high current efficiency of 90% or more.

バーフルオロカーボン重合体を基材とした陽イオン交換
膜が開発され、一部では商業化なされようとしている。
一方、近年エネルギー節約の重要性が世界的に認識され
つつあり、この見地からこの分野においては電解電力を
極力少なくすること、即ち電摺電圧を極力低下させるこ
とが強く望まれている。これまで電摺電圧を低下させる
目的で、発生するガスを電極の背後に抜け易くするため
に、エキスパンドメタル、パンチメタル、金網状などの
多孔性電極の使用、これらの電極自体の組成や極間距離
をコントロールしたり、あるいは陽イオン交換膜の組成
、交換基の種類を特定化する等の種々の手段が提案され
ている。この内、特に隔膜を用いた水素発生反応を陰極
主反応とする塩化アルカリ水溶液の電解においては、主
に前述の形状の鉄陰極がコスト的に安価であり、かつ、
かなり低い水素過電圧を示すという理由で使用されてい
る。
Cation exchange membranes based on barfluorocarbon polymers have been developed, and some are on the verge of commercialization.
On the other hand, in recent years, the importance of energy saving has been recognized worldwide, and from this point of view, it is strongly desired in this field to reduce the electrolytic power as much as possible, that is, to reduce the electric voltage as much as possible. Until now, for the purpose of reducing the electric sliding voltage, porous electrodes such as expanded metal, punch metal, and wire mesh have been used, and the composition of these electrodes themselves and the gap between the electrodes have been changed in order to make it easier for the generated gas to escape behind the electrode. Various methods have been proposed, such as controlling the distance, or specifying the composition of the cation exchange membrane and the type of exchange group. Among these, especially in the electrolysis of an aqueous alkali chloride solution in which the main cathode reaction is hydrogen generation reaction using a diaphragm, the iron cathode of the above-mentioned shape is mainly used at low cost, and
It is used because it exhibits a fairly low hydrogen overvoltage.

しかし、前述したようにJ特に陽イオン交換膜法食塩電
解技術の発展と共に省エネルギーの面から電力消費の一
層の低下が望まれ、特開昭55−92295号、特開昭
56−62148号等に見られるように鉄よりも低い水
素過電圧を有する陰極の開発が種々なされている。これ
らの低水ク素過電圧を有する金属被覆を施してなる陰極
自体それなりに当初の目的は達成しうるものの新たに下
記の重大な問題点を含でいることが明らかになつた。即
ち、これまでの鉄陰極に代えて、鉄または鉄系金属から
なる基材表面に低水素過電圧を有する金属被覆を施して
なる陰極を、内面が鉄または鉄系金属からなる陰極室に
取付けて用いた場合は、鉄の溶出量が短期間に極端に増
加する現象が認められるのである。
However, as mentioned above, with the development of cation exchange membrane salt electrolysis technology, further reduction in power consumption is desired from the viewpoint of energy saving, and Japanese Patent Application Laid-open Nos. 55-92295 and 1982-62148 etc. As can be seen, various efforts have been made to develop cathodes having hydrogen overpotentials lower than those of iron. Although these cathodes formed with metal coatings having a low hydrogen overvoltage can achieve their original purpose to a certain extent, it has become clear that they include the following serious problems. That is, instead of the conventional iron cathode, a cathode made of a base material made of iron or iron-based metal and coated with a metal having a low hydrogen overvoltage is installed in a cathode chamber whose inner surface is made of iron or iron-based metal. When used, a phenomenon is observed in which the amount of iron eluted increases dramatically in a short period of time.

この現象は更に高温、高アルカリ濃度指向というきびし
い電解条件下においては一層顕著に現われるという傾向
を示す。この鉄の溶出は、取得苛性アルカリの品質悪化
、陽イオン交換膜等の隔膜の性能劣化を来たすばかりて
なく、鉄または鉄系金属で構成された陰極室内面の腐食
が進行して電解槽自体の寿命の短縮という深刻な問題に
発展する。
This phenomenon tends to become more pronounced under severe electrolytic conditions such as high temperature and high alkali concentration. This elution of iron not only deteriorates the quality of the obtained caustic alkali and deteriorates the performance of diaphragms such as cation exchange membranes, but also causes corrosion of the inside of the cathode chamber, which is made of iron or iron-based metals, to progress to the electrolytic cell itself. This develops into a serious problem of shortening the lifespan of people.

この鉄の溶出を防止する手段として、対アルカリ耐食性
を有するニッケル等の金属にて陰極室を構成することが
考えられる。しかながら、陰極室の構成金属のすべてに
、対アルカリ耐食性金属を用いることは高価となり、実
用的ではない。更に、この場合は陰極基材も対アルカリ
耐食性の金属を用なければならないのである。なぜなら
ば、鉄または鉄系金属の基体にニッケル等の低い水素過
電圧を有する被覆をメッキ法等により施した陰極を用い
た場合は、該陰極を陰極室に溶接等の方法により取付け
る−際、いかに注意深く行なつても被膜に損傷を来たし
て鉄の素地が露出し、この露出部からの鉄の溶出が進行
するからてある。従つて、鉄または鉄系金属からなる陰
極室内面および陰極にそれぞれ対アルカリ耐食性有する
被覆をメッキ法等により施、し、しかる後に溶接等の方
法によつて両者を一体化する方法も同様の理由により問
題がある。他の手段として、プラスチック製の電解槽を
採用することが考えられる。しかしこれは加工および強
度の点で問題があると共に、仮に採用できた,としても
、鉄の溶出防止の抜本的な手段となり得ないのである。
本発明者らは、これらの問題点を挙に解決すべく種々検
討の結果、低水素過電圧を有する金属被覆を施してなる
陰極を使用しても、これまで使用・していた鉄または鉄
系金属て構成された鉄陰極、陰極室枠がそのまま使用可
能で、いかなる複雑な電解槽構造であつても、鉄の溶出
を防ぎ、しかも長期間安定して、かつ少ない消費電力に
て苛性アルカリを製造しうる電解槽を完成したのである
As a means to prevent this elution of iron, it is conceivable to construct the cathode chamber with a metal such as nickel that has corrosion resistance against alkali. However, using metals resistant to alkali corrosion for all of the constituent metals of the cathode chamber would be expensive and impractical. Furthermore, in this case, the cathode base material must also be made of a metal that is resistant to alkali corrosion. This is because when using a cathode in which a substrate made of iron or iron-based metal is coated with a coating such as nickel that has a low hydrogen overvoltage by plating, etc., the cathode is attached to the cathode chamber by a method such as welding. Even if this is done carefully, the coating will be damaged and the iron matrix will be exposed, and iron will continue to dissolve from this exposed area. Therefore, the same reason applies to a method in which a coating having resistance to alkali corrosion is applied to the inner surface of the cathode chamber and the cathode made of iron or iron-based metal by a plating method, etc., and then the two are integrated by a method such as welding. There is a problem with this. Another possibility is to use a plastic electrolytic cell. However, this has problems in terms of processing and strength, and even if it could be adopted, it would not be a fundamental means of preventing iron elution.
As a result of various studies to solve these problems, the present inventors found that even if a cathode coated with a metal having a low hydrogen overvoltage is used, iron or iron-based The iron cathode and cathode chamber frame made of metal can be used as is, and no matter how complex the electrolytic cell structure is, it prevents iron from leaching, and it can be used stably over a long period of time and with low power consumption. They completed a manufacturable electrolytic cell.

即ち、本発明は隔膜を用い陽極室と陰極室とを区割し、
陽極室に塩化アルカリ水溶液を供給して陽極室より塩素
、陰極室より水素並びに苛性アルカリを製造するに用い
る電解槽において鉄もしくは鉄系金属から成る陰極室内
面、陰極およびその他の陰極室内部材表面の全てにニッ
ケル塩を含むニッケルメッキ浴からニッケルメッキを施
した後、ニッケル塩と含硫黄化合物を含む活性ニツケフ
ルメツキ浴を用いて、活性ニッケルメッキを施して成る
電解槽にある。ここでいうその他の陰極室内部材とは、
導電棒、集電体、溶接部など陰極室内に存在する部材を
意味する。これまて鉄または鉄系金属から成る陰極基材
に・含硫黄化合物、例えば、ロダンニツケルを溶解した
ニッケルメッキ浴を用いてニッケルメッキを行なうと、
得られた被膜は低水素過電圧を示すことは古くから知ら
れている。
That is, the present invention uses a diaphragm to separate an anode chamber and a cathode chamber,
In an electrolytic cell used to supply an aqueous alkali chloride solution to the anode chamber and produce chlorine from the anode chamber and hydrogen and caustic alkali from the cathode chamber, the inner surface of the cathode chamber, the cathode, and the surfaces of other cathode chamber members made of iron or iron-based metals are Everything is in an electrolytic cell in which nickel plating is applied from a nickel plating bath containing nickel salts, and then active nickel plating is applied using an activated nickel plating bath containing nickel salts and sulfur-containing compounds. The other cathode chamber members mentioned here are:
Refers to members present inside the cathode chamber, such as conductive rods, current collectors, and welded parts. When nickel plating is performed on a cathode base material made of iron or iron-based metal using a nickel plating bath in which a sulfur-containing compound, such as rodanium nickel, is dissolved,
It has long been known that the resulting coatings exhibit low hydrogen overpotentials.

しかしながら、このようにして得られた被膜は、顕微鏡
等て表面を注意・深く観察すると、多数の亀裂が入つて
いることが認められ、かつまた被膜自体、鉄素地との密
着性に欠ける。したがつて、鉄素地上に直接このような
活性被覆を施した場合、被覆の剥離、脱落等の現象が起
きりやすく、また仮に素地に密着していたとしても、ク
ラックから鉄の溶出が進行して素地を被膜の間に空隙を
生じ、被被膜の脱落を来たす。その結果、素地の鉄が露
出し、この部分から鉄の溶出が進むため、活性被膜の剥
離、脱落は促進されることになる。鉄または鉄系金属か
らなる基体と、例えは口タンニッケル等を含む活性ニッ
ケルメッキ浴から施した活性ニッケルメッキとの密着性
を改良する目的で、鉄または鉄系素地上に銅の被覆を施
し、しかる後に活性ニッケルメッキを行なう方法が提案
されている。
However, when the surface of the coating thus obtained is carefully and deeply observed using a microscope, it is found that there are many cracks, and the coating itself lacks adhesion to the iron base. Therefore, if such an active coating is applied directly to the iron substrate, phenomena such as peeling or falling off of the coating are likely to occur, and even if it is in close contact with the substrate, the iron will continue to leach out through cracks. This creates a gap between the substrate and the coating, causing the coating to fall off. As a result, the iron base is exposed, and iron elution progresses from this portion, which accelerates the peeling and falling off of the active coating. For the purpose of improving the adhesion between a substrate made of iron or iron-based metal and activated nickel plating applied from an activated nickel plating bath containing tanned nickel, etc., a copper coating is applied to the iron or iron-based base material. A method has been proposed in which active nickel plating is then performed.

しかしながら、本発明者らのこれまでの経験では、銅自
体アルカリに対する耐食性が優れているとはいい難く、
したがつて活性ニッケルメッキを施して密着性そのもの
は改善されたにしても、クラックから銅の腐食が進行し
、やがて活性被膜の脱落を来たすことは、鉄素地に直接
活性ニッケルを施した場合と同様であることが確認され
た。本発明者らは、これらの問題点を改善すべく探求の
結果、ニッケル塩を含むニッケルメッキ浴から施したニ
ッケルメッキとニッケル塩及び含硫黄化合物を含む活性
ニッケルメッキ浴から施した活性ニッケルメッキとが優
れた密着性を有するものてあることの知見を得た。
However, in the experience of the present inventors, it is difficult to say that copper itself has excellent corrosion resistance against alkalis.
Therefore, even if the adhesion itself is improved by applying activated nickel plating, corrosion of the copper progresses through cracks, and eventually the active film will fall off, compared to when activated nickel is applied directly to the iron base. It was confirmed that they are the same. As a result of our search to improve these problems, the present inventors discovered that nickel plating was performed from a nickel plating bath containing nickel salts, and active nickel plating was performed from an activated nickel plating bath containing nickel salts and sulfur-containing compounds. It has been found that there are some materials that have excellent adhesion.

本発明はこの知見に基づいて完成したものである。即ち
、鉄または鉄系金属素地上に、含硫黄化合物を含まずニ
ッケル塩を含むニッケルメッキ浴を用いてニッケルメッ
キを行なつた後、ニッケル塩および含硫黄化合物を含む
活性ニッケルメッキ浴を用いて更に活性ニッケルメッキ
を行なうことにより、全体として陰極室、陰極等の鉄素
地との密着性の極めて優れた活性被覆を得ることがてき
るのである。
The present invention was completed based on this knowledge. That is, after nickel plating is performed on an iron or iron-based metal substrate using a nickel plating bath that does not contain sulfur-containing compounds and contains nickel salts, it is then plated using an activated nickel plating bath that contains nickel salts and sulfur-containing compounds. Furthermore, by performing active nickel plating, it is possible to obtain an active coating that has extremely excellent adhesion to the iron substrate of the cathode chamber, cathode, etc. as a whole.

ニッケルメッキ浴の組成は以下のようなものである。The composition of the nickel plating bath is as follows.

ニッケル塩は可溶性の塩であればよく、通常、硫酸ニッ
ケル、塩化ニッケル、硫酸ニッケルアンモニウム、スル
ファミン酸ニッケル等任意の水溶性ニッケル塩の一種以
上が用いられる。
The nickel salt may be any soluble salt, and usually one or more of any water-soluble nickel salts such as nickel sulfate, nickel chloride, ammonium nickel sulfate, and nickel sulfamate are used.

ニッケル塩の濃度は特に制限を受けないが、通常、0.
1モル濃度から2.0モル濃度の範囲で用いられる。こ
の場合、ニッケルメッキ浴に用いられたニッケル塩と同
種の塩を活性ニッケルメッキ浴にも用いた活性ニッケル
メッキを施せば、ニッケルメッキと活性ニッケルメッキ
との密着性は更に優れたものになる。そして、ニッケル
メッキに用いられたニッケル塩のみならず、その他の成
分及びそれらの濃度まで同一にした活性ニッケルメッキ
浴を用いた場合が最もその密着性において有効である。
本発明において、陰極室、陰極等の鉄素地にニッケル塩
を含むニッケルメッキ浴を用いてニッケルメッキを施す
方法としては、電気メッキ法、無電解メッキ法いずれも
行なうことができるが、このうち無電解メッキ法が好ま
しい。そして特に密着性の極めて優れ、強固て、かつ長
期間にわたつて安定して低い水素過電圧を示す被覆を有
する陰極および陰極室を得る最良の方法としては、陰極
室内面、陰極およびその他の陰極室内部材表面すべてに
無電解ニッケルメッキを施し、更に電気ニッケルメッキ
を行ない、最後に活性ニッケルメッキを行なう方法であ
る。従つて、鉄または鉄系金属の陰極室、陰極およびそ
の他の陰極室内部材表面をあらかじめ無電解ニッケルメ
ッキして組立てられた電解槽に本発明の手段を適用する
ことも有効な方法である。本発明の優れた特徴の一つは
、陰極を陰極室に取付けた後に、陰極室面、陰極および
その他の陰極室内部材表面すへてにわたつて被覆を施す
ことができるので、鉄素地の露出は皆無であるというこ
とである。
The concentration of nickel salt is not particularly limited, but is usually 0.
It is used in a concentration range of 1 molar to 2.0 molar. In this case, if active nickel plating is performed in which the same type of nickel salt as the nickel salt used in the nickel plating bath is also used in the active nickel plating bath, the adhesion between the nickel plating and the active nickel plating will be even better. It is most effective in terms of adhesion when an active nickel plating bath is used in which not only the nickel salt used in nickel plating but also other components and their concentrations are made the same.
In the present invention, as a method for applying nickel plating to the iron substrate of the cathode chamber, cathode, etc. using a nickel plating bath containing nickel salt, both electroplating method and electroless plating method can be performed. Electrolytic plating is preferred. In particular, the best way to obtain a cathode and cathode chamber with a coating that is extremely adhesive, strong, and exhibits a stable and low hydrogen overvoltage over a long period of time is to This method involves applying electroless nickel plating to all parts surfaces, then electrolytic nickel plating, and finally active nickel plating. Therefore, it is also an effective method to apply the means of the present invention to an electrolytic cell assembled by electroless nickel plating of the cathode chamber, cathode, and other cathode chamber interior surfaces made of iron or iron-based metal in advance. One of the excellent features of the present invention is that after the cathode is installed in the cathode chamber, the entire surface of the cathode chamber, the cathode, and other cathode chamber components can be coated, so that no iron substrate is exposed. This means that there are no such cases.

仮りに陰極室および陰極それぞれに被覆を施し、これを
溶接等の方法によつて一体化せしめようとすると、被覆
の損傷を来たし、活性の劣化および鉄素地の露出を免れ
ることができないことは前述の通りである。本発明の更
に優れた特徴の一つは、陰極のみならず、陰極室内面ま
で活性ニッケルメッキが施されるので、電摺電圧は更に
低下するということである。
As mentioned above, if the cathode chamber and the cathode are coated, and an attempt is made to integrate them by welding or other methods, the coating will be damaged, and the deterioration of activity and exposure of the iron base cannot be avoided. It is as follows. One of the more excellent features of the present invention is that active nickel plating is applied not only to the cathode but also to the inner surface of the cathode chamber, so that the electric voltage is further reduced.

即ち、陰極のみに活性被覆を施した場合に比べ、活性被
覆を施した面積が大きくなるので、実質的に電流密度が
低下したと同じ効果をもたらし、電摺電圧が低下するの
である。このことは特に複極式電解槽を用いる場合に顕
著である。勿論、複雑な形状をした陰極室、陰極および
その他の陰極室内部材に均一に活性被覆を施すことは一
般的には困難てあるが、本発明においては、このことは
いささかも障害となるものではない。なぜなら最も電流
が流れやすいところは、陰極の対陽極面てあるから、こ
の部分に最も厚く活性被覆が施される。そして食塩水の
電解を行なう場合も最も多く電流が流れるところは陰極
の対陽極面であるから、この部分に最も厚く活性被覆が
施されているということは、むしろ効率的であるといえ
る。鉄素地にニッケルメッキを施す場合、その厚さは4
〜100pが適当てある。
That is, compared to the case where the active coating is applied only to the cathode, the area covered with the active coating is larger, so the effect is substantially the same as that of a reduction in current density, and the electric voltage is reduced. This is particularly noticeable when using a bipolar electrolytic cell. Of course, it is generally difficult to apply an active coating uniformly to cathode chambers, cathodes, and other cathode chamber components having complex shapes, but this is not a hindrance in the slightest in the present invention. do not have. This is because the area where current most easily flows is on the opposite anode side of the cathode, so the thickest active coating is applied to this area. When electrolyzing saline water, the area where the most current flows is the opposite anode surface of the cathode, so it can be said that it is more efficient to have the thickest active coating applied to this area. When applying nickel plating to an iron base, the thickness is 4
~100p is a good guess.

陰極、陰極室およびその他の陰極室内部材表面全面が均
一な厚さにメッキされる必要はなく、この範囲の中に入
つていればよい。鉄素地に無電解ニッケルメッキを施し
てからニッケルメッキを行なう場合、無電解ニッケルメ
ッキの厚さは2〜50μが適当である。
It is not necessary that the entire surface of the cathode, cathode chamber, and other cathode chamber members be plated to a uniform thickness, but it is sufficient that the thickness falls within this range. When electroless nickel plating is applied to an iron substrate and then nickel plating is performed, the appropriate thickness of the electroless nickel plating is 2 to 50 μm.

これより薄いと鉄の溶出を防止する効果が小さく、また
これより厚いと不経済である。無電解ニッケルメッキの
フ上に施すニッケルメッキの厚さは2〜50μが適当で
ある。2μ以下では活性ニッケルメッキとの密着力が弱
く、また50μ以上の厚さにメッキすることは不経済で
ある。
If it is thinner than this, the effect of preventing iron elution is small, and if it is thicker than this, it is uneconomical. The appropriate thickness of the nickel plating applied on the electroless nickel plate is 2 to 50 microns. If the thickness is less than 2μ, the adhesion to the active nickel plating is weak, and plating to a thickness of 50μ or more is uneconomical.

ニッケルメッキの上になれる活性ニツケルメツキの厚さ
は、5μ以上100μ以下が好ましい。5μ以下の厚さ
では水素過電圧低下の効果が小さく、また100μ以上
の厚さにメッキすることはコスト高になる。
The thickness of the activated nickel plating on the nickel plating is preferably 5 μm or more and 100 μm or less. If the thickness is less than 5 μm, the effect of reducing the hydrogen overvoltage will be small, and plating to a thickness of 100 μm or more will increase the cost.

活性ニッケルメッキに用いられる含硫黄化合物は、チオ
シアン酸塩、チオ尿素、硫化アンモニウム等の硫化物、
更には亜硫酸塩、重亜硫酸塩、亜ニチオン酸塩等の化合
物であり、チオシアン酸塩および/もしくはチオ尿素が
殊に効果的である。
Sulfur-containing compounds used in activated nickel plating include sulfides such as thiocyanate, thiourea, ammonium sulfide,
Furthermore, there are compounds such as sulfites, bisulfites, dithionites, and thiocyanates and/or thioureas are particularly effective.

そしてメッキ浴中に加えられるこれらの含硫黄化合物の
濃度は、0.01モル濃度以上、1.5モル濃度以下、
好ましくは0.05モル濃度以上、0.5モル濃度以下
に制限される。その理由は0.01モル以下の濃度では
水素過電圧低下の効果が不充分であり、1.5モル以上
の濃度になると、活性ニッケルメッキのニッケルメッキ
に対する密着性が低下するためである。なお、ニッケル
塩を含むニッケルメッキ浴ならびにニッケル塩および含
硫黄化合物を含む活性ニッケルメッキ浴は、あらかじめ
別途に調整したものを採用することも可能であるが、陰
極室、陰極等の鉄素材に始めにニッケル塩を含むニッケ
ルメッキ浴にてニッケルメッキを施した後、使用済みの
該ニッケルメッキ浴に含硫黄化合物を溶解調整した活性
ニッケルメッキ浴を用いることができ,る。
The concentration of these sulfur-containing compounds added to the plating bath is 0.01 molar or more and 1.5 molar or less,
Preferably, the concentration is limited to 0.05 molar or more and 0.5 molar or less. The reason for this is that at a concentration of 0.01 mol or less, the effect of reducing hydrogen overvoltage is insufficient, and at a concentration of 1.5 mol or more, the adhesion of the activated nickel plating to the nickel plating decreases. It is also possible to use separately prepared nickel plating baths containing nickel salts and activated nickel plating baths containing nickel salts and sulfur-containing compounds. After nickel plating is performed in a nickel plating bath containing a nickel salt, an active nickel plating bath prepared by dissolving a sulfur-containing compound in the used nickel plating bath can be used.

本発明においては、要はニッケルメッキした後に、含硫
黄化合物を含む活性ニッケルメッキ浴に活性ニッケルメ
ッキをすれば、いかなる態様も採用しうることは勿論で
ある。
In the present invention, it goes without saying that any embodiment can be adopted as long as active nickel plating is performed in an active nickel plating bath containing a sulfur-containing compound after nickel plating.

また、電気メッキ法によよりニッケルメッキおよび活性
ニッケルメッキを行なうときの電流密度は必ずしも同一
である必要はなく、適宜選択し得るが、通常0.1A/
Dm2以上10A/Dm2以下の範囲で行なわれる。
In addition, the current density when performing nickel plating and active nickel plating by electroplating does not necessarily have to be the same and can be selected as appropriate, but is usually 0.1A/
It is carried out in the range of Dm2 or more and 10 A/Dm2 or less.

これまでイオン交換膜法について3主として言及してき
たが、本発明の電解槽はアスベスト等の隔膜法にも適用
しうることは言うまでもない。以上のように、陰極室内
面、陰極およびその他の陰極室内部材表面すべてにニッ
ケル塩を含む二4ツケルメツキ浴からニッケルメッキを
施した後、ニッケル塩と含硫黄化合物を含む活性ニッケ
ルメッキ浴を用いて活性ニッケルメッキを施すことによ
り、鉄の露出部分が無く、従つて鉄の溶出が防止され、
かつ活性被膜を有する陰極室と極めて低い水素過電圧を
長期間にわたつて安定して保つ陰極を有する電解槽を製
造することがてきる。
Although the ion exchange membrane method has been mainly mentioned so far, it goes without saying that the electrolytic cell of the present invention can also be applied to the diaphragm method for asbestos and the like. As described above, after applying nickel plating to the inside of the cathode chamber, the cathode, and all other surfaces of the cathode chamber components using a 24-layer bath containing nickel salts, nickel plating was applied using an activated nickel plating bath containing nickel salts and sulfur-containing compounds. By applying activated nickel plating, there is no exposed iron part, thus preventing iron elution.
Furthermore, it is possible to manufacture an electrolytic cell having a cathode chamber having an active coating and a cathode that stably maintains an extremely low hydrogen overvoltage over a long period of time.

即ち、本発明は極めて簡便な方法により採用している鉄
系金属製陰極室を有する電解槽をなんら変更なくして、
高温、高アルカリ濃度という厳しい条件下においても、
水素過電圧の上昇なく、しかも苛性アルカリ中への鉄の
溶出を来たすことなくして、長期間安定して極めて少な
い消費電力で苛性アルカリを製造するに有効な電解槽で
ある。以下、本発明を実施例によつて詳細に説明する。
実施例1 内面が鉄からなる陰極室、鉄製エキスパンドメタルから
なる陰極およびその他の陰極室内部材表面すべてをアル
カリ脱脂、酸洗後、表1に示したニッケルメッキ浴を用
いて表2に示した条件でニッケルメッキを行なつた。
That is, the present invention uses an extremely simple method to produce an electrolytic cell having an iron-based metal cathode chamber without any modification.
Even under harsh conditions of high temperature and high alkali concentration,
This is an effective electrolytic cell for producing caustic alkali stably for a long period of time and with extremely low power consumption, without increasing hydrogen overvoltage and without elution of iron into caustic alkali. Hereinafter, the present invention will be explained in detail with reference to Examples.
Example 1 After alkaline degreasing and pickling of the cathode chamber whose inner surface is made of iron, the cathode made of iron expanded metal, and all other surfaces of the cathode chamber members, the conditions shown in Table 2 are applied using the nickel plating bath shown in Table 1. Nickel plating was performed.

表1 ニッケルメッキ浴組成 硫酸ニッケル 0.91m01/e塩化ニ
ッケル 0.19rr101/eホウ酸
0.4911101/l表2 ニ
ッケルメッキ条件浴温
60℃電流密度 6A/陰極投影面積Dm2メ
ッキ時間 3紛しかる後、表3
に示した活性ニッケルメッキ浴を用いて表4に示した条
件で活性ニッケルメッキを行なつた。
Table 1 Nickel plating bath composition Nickel sulfate 0.91m01/e Nickel chloride 0.19rr101/e Boric acid
0.4911101/l Table 2 Nickel plating conditions bath temperature
60℃ Current density 6A/Cathode projected area Dm2 Plating time 3 After confusion, Table 3
Active nickel plating was carried out under the conditions shown in Table 4 using the active nickel plating bath shown in Table 4.

表3 塩化ニッケル 0.5m01/e塩化ア
ンモニウム 1.0rT101/eチオ尿素
0.2rT101/e表4浴温
50℃電流密度
1.5A/陰極投影面積Dm2メッキ時間
3時間かくして得られた陰極室および陰極を
パーフロロスルホン酸イオン交換膜を介して、チタンラ
ス上に酸化ルテニウムをコーティングした陽極を有す陽
極室と組合せて電解槽を構成し、表5に示す電解条件に
て食塩水の電解を行なつた。
Table 3 Nickel chloride 0.5m01/e Ammonium chloride 1.0rT101/e Thiourea
0.2rT101/e Table 4 Bath temperature
50℃ current density
1.5A/cathode projected area Dm2 plating time
The cathode chamber and cathode thus obtained for 3 hours were combined with an anode chamber having an anode made of titanium lath coated with ruthenium oxide via a perfluorosulfonic acid ion exchange membrane to form an electrolytic cell, and the electrolysis shown in Table 5 was carried out. Salt water was electrolyzed under the following conditions.

その結果表6に示す。表5 陰極室NaOH濃度 32%温度
80℃電流密度
30A/Dm2比較例1内面が鉄からなる陰
極室および陰極を、パーフロロスルホン酸イオン交換膜
を介して、チタンラス上に酸化ルテニウムをコーティン
グした陽極を有する陽極室と組合せて電解槽を構成し、
表5に示した電解条件で食塩水の電解を行なつた。
The results are shown in Table 6. Table 5 Cathode chamber NaOH concentration 32% temperature
80℃ current density
30A/Dm2 Comparative Example 1 An electrolytic cell is constructed by combining a cathode chamber and cathode whose inner surface is made of iron with an anode chamber having an anode made of titanium lath coated with ruthenium oxide via a perfluorosulfonic acid ion exchange membrane,
Salt water was electrolyzed under the electrolytic conditions shown in Table 5.

比較例2内面が鉄からなる陰極室、陰極およびその他の
陰極室内部材表面すべてを実施例1の表3に示した活性
ニッケルメッキ浴を用いて、表4に示した条件で活性ニ
ッケルメッキを施した。
Comparative Example 2 The cathode chamber whose inner surface was made of iron, the cathode, and all other surfaces of the cathode chamber members were subjected to active nickel plating using the active nickel plating bath shown in Table 3 of Example 1 under the conditions shown in Table 4. did.

かくして得られた陰極室及び陰極を、パーフロロスルホ
ン酸イオン交換膜を介してチタンラス上に酸化ルテニウ
ムをコーティングした陽極を有する陽極室と組合せて電
解槽を構成し、表5に示した電解条件で電解を行なつた
。その結果を表6に示す。比較例3 鉄製エキスパンドメタルからなる陰極のみを実施例1の
表1に示したニッケルメッキ浴を用いて、表2に示した
メッキ条件でニッケルメッキを行なつた。
An electrolytic cell was constructed by combining the thus obtained cathode chamber and cathode with an anode chamber having an anode made of titanium lath coated with ruthenium oxide through a perfluorosulfonic acid ion exchange membrane, and under the electrolytic conditions shown in Table 5. I did electrolysis. The results are shown in Table 6. Comparative Example 3 Only the cathode made of expanded iron was plated with nickel using the nickel plating bath shown in Table 1 of Example 1 under the plating conditions shown in Table 2.

次いで表3に示した活性ニッケルメッキ浴を用いて表4
に示したメッキ条件で活性ニッケルメッキを施した。か
くして得られた陰極を内面が鉄からなる陰極に溶接によ
つて取付けた。しかる後にパーフロロスルホン酸イオン
交換膜を介して、チタンラス上に酸化ルテニウムをコー
ティングした陽極を有する陽極室と組合せて電解槽を構
成し表5に示した電解条件て食塩水の電解を行なつた。
その結果を表6に示す。実施例2 内面が鉄からなる陰極室及び鉄製エキスパンドメタルか
らなる陰極を、アルカリ脱脂、酸洗後、実施例1表1に
示したニッケルメッキ浴を用い、実施例1表2に示した
条件でニッケルメッキを行なつた。
Then, using the activated nickel plating bath shown in Table 3,
Activated nickel plating was applied under the plating conditions shown in . The cathode thus obtained was attached by welding to a cathode whose inner surface was made of iron. This was then combined with an anode chamber having an anode made of ruthenium oxide coated on titanium glass via a perfluorosulfonic acid ion exchange membrane to form an electrolytic cell, and electrolysis of saline water was carried out under the electrolytic conditions shown in Table 5. .
The results are shown in Table 6. Example 2 A cathode chamber whose inner surface was made of iron and a cathode made of expanded iron metal were degreased with alkali, acid washed, and then treated under the conditions shown in Table 2 of Example 1 using the nickel plating bath shown in Table 1 of Example 1. Nickel plating was performed.

次いで表7に示した活性ニッケルメッキ浴を用い、表4
に示した条件で活性ニッケルメッキを施した。表7 硫酸ニッケル 0.46rT101/e
塩化ニッケル 0.10m01/e ホ
ウ酸 0.49rT101/l チ
オ尿素 0.20rT101/eかく
して得られた陰極室および陰極を、パーフロロスルホン
酸イオン交換膜を介して、チタンラス上に酸化ルテニウ
ムをコーティングした陽極を有する陽極室と組合せて電
解槽を構成し、実施例1表5に示した条件で食塩水の電
解を行なつた。
Next, using the activated nickel plating bath shown in Table 7, Table 4
Activated nickel plating was applied under the conditions shown in . Table 7 Nickel sulfate 0.46rT101/e
Nickel chloride 0.10m01/e Boric acid 0.49rT101/l Thiourea 0.20rT101/e The thus obtained cathode chamber and cathode were coated with ruthenium oxide on a titanium lath through a perfluorosulfonic acid ion exchange membrane. In combination with an anode chamber having an anode, an electrolytic cell was constructed, and saline solution was electrolyzed under the conditions shown in Table 5 of Example 1.

q摺電圧およびNaOH中の鉄濃度の経時変化を表8に
示す。実施例3 内面が鉄からなる陰極室及び鉄製エキスパンド5メタル
からなる陰極を、アルカリ脱脂、酸洗後、実施例1表1
に示したニッケルメッキ浴を用い、実施例1表2に示し
た条件でニッケルメッキを行なつた。
Table 8 shows the changes over time in the q-sliding voltage and the iron concentration in NaOH. Example 3 After alkali degreasing and pickling, a cathode chamber whose inner surface is made of iron and a cathode made of expanded iron 5 metal are prepared as shown in Table 1 of Example 1.
Using the nickel plating bath shown in Example 1, nickel plating was carried out under the conditions shown in Table 2.

次いで表9に示した活性ニッケルメッキ浴を用い、表4
に示した条件で活性ニツケルメツθキを施した。表9 硫酸ニッケル 0.91m01/l 塩
化ニッケル 0.19rr101/′ ホ
ウ酸 0.49rT101/eチオ尿
素 0.201T101/lかくして
得られた陰極室及び陰極をパーフロロスルホン酸イオン
交換膜を介して、チタンラス上に酸化ルテニウムをコー
ティングした陽極を有する陽極室と組合せて表5に示し
た条件て食塩水の電解を行なつた。
Next, using the activated nickel plating bath shown in Table 9, Table 4
Active nickel metal θ-kiing was performed under the conditions shown in . Table 9 Nickel sulfate 0.91m01/l Nickel chloride 0.19rr101/' Boric acid 0.49rT101/e Thiourea 0.201T101/l The cathode chamber and cathode thus obtained were passed through a perfluorosulfonic acid ion exchange membrane. In combination with an anode chamber having an anode made of a titanium lath coated with ruthenium oxide, electrolysis of saline water was carried out under the conditions shown in Table 5.

電摺電圧およびNaOH中の鉄濃度の経時変化を表10
に示す。実施例4 内面が鉄からなる陰極室及び鉄製エキスパンドメタルか
らなる陰極を、アルカリ脱脂、酸洗後、カニゼンブルー
シユーマー無電解ニッケルメッキ液を用い90℃で3吟
間電解ニッケルメッキを施した。
Table 10 shows the changes over time in electric sliding voltage and iron concentration in NaOH.
Shown below. Example 4 After alkali degreasing and pickling, a cathode chamber whose inner surface was made of iron and a cathode made of iron expanded metal were subjected to electrolytic nickel plating at 90°C for 3 minutes using Kanisen Blue Schumer electroless nickel plating solution. .

次いで実施例3表9に示した活性ニッケルメッキ浴を用
い、表4に示した条件で活性ニッケルメッキを行なつた
。かくして得られた陰極室及び陰極を、パーフロロスル
ホン酸イオン交換膜を介してチタンラス上に酸化ルテニ
ウムをコーティングした陽極を有する陽極室と組合せた
電解槽を構成し、表5に示した条件で食塩水の電解を行
なつた。電摺電圧及びNaOH中の鉄濃度の経時変化を
表11に示す。表11。
Next, active nickel plating was carried out using the active nickel plating bath shown in Table 9 of Example 3 under the conditions shown in Table 4. An electrolytic cell was constructed in which the cathode chamber and cathode thus obtained were combined with an anode chamber having an anode made of titanium lath coated with ruthenium oxide through a perfluorosulfonic acid ion exchange membrane, and salt was added under the conditions shown in Table 5. Performed water electrolysis. Table 11 shows the changes over time in the electric sliding voltage and the iron concentration in NaOH. Table 11.

実施例5 内面が鉄からなる陰極室及び鉄製エキスパンドメタルか
らなる陰極をアルカリ脱脂、酸洗後、カニゼンブルーシ
ユーマー無電解ニッケルメッキ液を用い、90シCで2
紛間無電解ニッケルメッキを行なつた。
Example 5 A cathode chamber whose inner surface was made of iron and a cathode made of iron expanded metal were degreased with alkaline and washed with acid, and then plated at 90C for 2 hours using Kanisen Blue Schumer electroless nickel plating solution.
Performed electroless nickel plating.

次いで実施例1表1に示したニッケルメッキ浴を用い、
表2に示した条件でニッケルメッキを行なつた。しかる
後、実施例3表9に示した活性ニッケルメッキ浴を用い
、表4に示した条件で活性ニッケルメッキを施した。か
くして得られた陰極室および陰極を、パーフロロスルホ
ン酸イオン交換膜を介して、チタンラス上に酸化ルテニ
ウムをコーティングした陽極を有する陽極室と組合せて
電解槽を構成し、実施例1表5に示した条件で食塩水の
電解を行なつた。 電摺電圧及びNaOH中の鉄濃度の
経時変化を表12に示す。
Next, using the nickel plating bath shown in Table 1 of Example 1,
Nickel plating was performed under the conditions shown in Table 2. Thereafter, active nickel plating was performed using the active nickel plating bath shown in Table 9 of Example 3 under the conditions shown in Table 4. The cathode chamber and cathode thus obtained were combined with an anode chamber having an anode made of titanium lath coated with ruthenium oxide via a perfluorosulfonic acid ion exchange membrane to constitute an electrolytic cell, and the electrolytic cell was constructed as shown in Table 5 of Example 1. Electrolysis of saline water was carried out under the following conditions. Table 12 shows the changes over time in the electric sliding voltage and the iron concentration in NaOH.

712゜゛9ォー 一ー 参考例 30CTn×50αの鉄製平板を用い、アルカリ脱脂、
酸洗を行なつた後、カニゼンブルーシユーマー無電解ニ
ッケルメッキ液を用い、90℃で3紛間無電解ニッケル
メッキを施した。
712゜゛9゜ - Reference Example Using a flat iron plate of 30CTn x 50α, alkaline degreasing,
After pickling, three-powder electroless nickel plating was performed at 90° C. using Kanisen Blue Schumer electroless nickel plating solution.

次いで実施例1表1に示したニッケルメッキ浴を用い、
表13に示した条件でニッケルメッキを施した。 表1
3 浴温 60℃ 電流密
度 2A/Dm2メッキ時間
3吟 しかる後、実施例3表9に示
した活性ニッケルメッキ浴を用い表14に示した条件で
活性ニッケルメッキを行なつた。
Next, using the nickel plating bath shown in Table 1 of Example 1,
Nickel plating was performed under the conditions shown in Table 13. Table 1
3 Bath temperature 60℃ Current density 2A/Dm2 Plating time
After that, active nickel plating was performed using the active nickel plating bath shown in Table 9 of Example 3 under the conditions shown in Table 14.

表14 浴温 60゜C電流密度
0.5A/Dm2メッキ時間
3時間90度曲げ試験による密着性
の試験結果を表15に示す。
Table 14 Bath temperature 60°C current density
0.5A/Dm2 plating time
Table 15 shows the adhesion test results by a 3 hour 90 degree bending test.

参考比較例 330cm×50CTnの鉄製平板を用い、アルカリ脱
脂、酸洗の後、実施例3表9に示した活性ニッケルメッ
キ浴を用い、表14に示した条件で活性ニッケルメッキ
を施した。
Reference Comparative Example 3 After alkaline degreasing and pickling, an iron flat plate of 30 cm x 50 CTn was subjected to active nickel plating using the active nickel plating bath shown in Table 9 of Example 3 under the conditions shown in Table 14.

90度曲げ試験による密着性の試験結果を表15に示す
Table 15 shows the adhesion test results by 90 degree bending test.

4 表15 参考例 10回の曲げ試験でも剥離せず。4 Table 15 Reference example No peeling even after 10 bending tests.

参考比較例2回の曲け試験で剥離。 Reference Comparative Example Peeled off in two bending tests.

Claims (1)

【特許請求の範囲】[Claims] 1 隔膜を用い陽極室と陰極室とを区割し、陽極室に塩
化アルカリ水溶液を供給して陽極室より塩素、陰極室よ
り水素並びに苛性アルカリを取得するに用いる電解槽に
於て、鉄または鉄系金属よりなる陰極室、陰極及びその
他の陰極室内部材表面の全てに、ニッケル塩を含むニッ
ケルメッキ浴を用いてニッケルメッキを施し、次いでニ
ッケル塩と含硫黄化合物とを含む活性ニッケルメッキ浴
にて活性ニッケルメッキを施して成る電解槽。
1. In an electrolytic cell used to separate an anode chamber and a cathode chamber using a diaphragm and supply an aqueous alkali chloride solution to the anode chamber to obtain chlorine from the anode chamber and hydrogen and caustic alkali from the cathode chamber, iron or All surfaces of the cathode chamber, cathode, and other cathode chamber components made of iron-based metals are nickel-plated using a nickel plating bath containing nickel salts, and then in an activated nickel plating bath containing nickel salts and sulfur-containing compounds. An electrolytic cell made of activated nickel plating.
JP56107104A 1981-07-10 1981-07-10 electrolytic cell Expired JPS6045710B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP56107104A JPS6045710B2 (en) 1981-07-10 1981-07-10 electrolytic cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP56107104A JPS6045710B2 (en) 1981-07-10 1981-07-10 electrolytic cell

Publications (2)

Publication Number Publication Date
JPS589988A JPS589988A (en) 1983-01-20
JPS6045710B2 true JPS6045710B2 (en) 1985-10-11

Family

ID=14450554

Family Applications (1)

Application Number Title Priority Date Filing Date
JP56107104A Expired JPS6045710B2 (en) 1981-07-10 1981-07-10 electrolytic cell

Country Status (1)

Country Link
JP (1) JPS6045710B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07317016A (en) * 1994-05-23 1995-12-05 Unitec Kk Vibratory compactor

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6065393A (en) * 1983-09-20 1985-04-15 松下電器産業株式会社 Coin selector
JPS606834A (en) * 1984-04-25 1985-01-14 Toshiba Corp Propriety discriminating device for printed matter
JPS60230288A (en) * 1984-04-27 1985-11-15 株式会社東芝 Discriminator for print
JPS62137695A (en) * 1985-12-11 1987-06-20 沖電気工業株式会社 Sheet paper discriminator

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07317016A (en) * 1994-05-23 1995-12-05 Unitec Kk Vibratory compactor

Also Published As

Publication number Publication date
JPS589988A (en) 1983-01-20

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