JPH0210233B2 - - Google Patents
Info
- Publication number
- JPH0210233B2 JPH0210233B2 JP10935883A JP10935883A JPH0210233B2 JP H0210233 B2 JPH0210233 B2 JP H0210233B2 JP 10935883 A JP10935883 A JP 10935883A JP 10935883 A JP10935883 A JP 10935883A JP H0210233 B2 JPH0210233 B2 JP H0210233B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- aqueous solution
- deposits
- present
- anode
- 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
Links
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 238000005363 electrowinning Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 description 15
- 238000007654 immersion Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 230000007420 reactivation Effects 0.000 description 3
- 238000007430 reference method Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- -1 platinum group metal oxide Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electrolytic Production Of Metals (AREA)
Description
本発明は、付着物により低活性化した不溶性電
極の再活性化方法に関する。
従来、金属チタン等の基体上に白金族金属酸化
物等を含有する活性被覆を設けた不溶性電極がコ
バルト等の電解採取において陽極として用いられ
ている。
コバルトの電解採取は通常、塩化コバルト水溶
液を用い、PH１〜２、電流密度２〜3A／ｄm2、
温度55℃程度の電解条件で行われるが、ある期
間、電解を継続すると、前記の陽極に不良導体物
等が付着し、電極が低活性化するため、電流効率
が大巾に低下する等の現象が生ずる。
このような付着物は、分析の結果、主に水酸化
コバルトCo（OH）3であり、使用されている不溶
性電極表面に強固に付着・堆積して行き、陰極５
〜10ライフで１〜２mmの厚さに達し、電流効率を
著しく低下させる。
そこで、従来、該水酸化コバルトを溶解する方
法として、アンモニアと硫酸アンモニウムの混合
液で処理する方法、硫酸酸性下のSO2による還元
処理法、硫酸酸性下のメタノールによる還元処理
法等が提案されているが、いずれの方法も一長一
短があり、簡単な方法で効率良く不溶性電極上の
付着物を除去することが困難であつた。
本発明は、上記の問題を解決するためになされ
たもので、該付着物を効率良く容易に溶解洗浄
し、不活性化した不溶性電極を容易に再活性化す
る方法を提供することを目的とする。
本発明者等は、かかる付着物の各種の溶解剤に
ついて、鋭意検討したところ有機酸と鉱酸とを混
合した水溶液が、実際の操業で陽極に生じた付着
物に極めて効果的に反応することを見出し、本発
明に到達した。
すなわち、本発明は、不溶性電極の再活性化方
法において、低活性化した不溶性電極を有機酸と
鉱酸とを含有する水溶液を用いて溶解洗浄するこ
とを特徴とする。
以下、本発明をより詳細に説明する。
コバルト等の電解採取において通常使用される
不溶性電極として、特公昭48−3954号、特公昭46
−21884号に記載の如き白金族金属酸化物含有被
覆電極が知られている。これらは、例えば金属チ
タン上にルテニウム及びチタン等の金属酸化物を
被覆したもので、勿論、他の不溶性電極に本発明
を適用することは可能である。
このような不溶性電極を陽極とし、塩化コバル
ト水溶液を電解液として通常の電解条件でコバル
トの電解精製を一定期間行い、その結果、陽極に
堆積した付着物により電流効率が低下するので、
電極を再活性化するため、有機酸と鉱酸を含む水
溶液で溶解洗浄する。
有機酸としては、種々のものを用い得るが、蓚
酸、クエン酸又は酒石酸が好適である。また該有
機酸と混合して用いる鉱酸としては、塩酸又は硫
酸が好ましい。硝酸は有毒ガス発生のおそれがあ
るのでこの点で好ましくない。上記有機酸は、少
くともその一種を重量で１％以上水溶液として含
むことが短時間で効果を達成する上で望ましく、
通常10％以下で十分である。鉱酸の含量は１〜10
％程度とすることが好適である。本発明において
は、水溶液として有機酸と鉱酸の両者を含むこと
が必要であり、それぞれ単独では効果が不十分で
ある。
電解採取に使用して、付着物により不活性化し
た電極を、このような有機酸と鉱酸とを含む混合
水溶液を常温以上好ましくは50〜80℃に保持した
浸漬槽に浸漬し、ガスの発生が見られなくなる程
度迄十分溶解洗浄した後、浸漬槽から引き揚げ、
水洗した後、再活性化した陽極として再び使用す
る。実際の操業上、通常陰極５〜10ライフ（１ラ
イフ８日）の電解を行うと陽極に平均約１〜２mm
の不良導体物が付着するので、この時期毎に本発
明の電極の再活性化処理を行うことが好ましい。
本発明の処理方法においては、溶解反応時に気
泡の発生を伴うが、比較的穏やかに進行し、溶解
は支障なく短時間で完了する。
本発明の方法によれば、従来法に見られた、高
温での処理や、複雑な処理操作をする必要がな
く、該付着物の厚さが約１〜２mmの場合20〜50分
程度で溶解が完了し、付着物により低活性化した
不溶性電極を効率良く容易に再活性化することが
できる。また本発明の処理により電極が損傷され
ることもない。
以下に示す第１表は、コバルト電解採取に使用
した陽極の付着物を乾燥剥離したもの各２ｇを、
５％の塩酸（No.４のみ５％硫酸）と各種溶解剤と
の混合水溶液100mlを用いて50℃で溶解試験した
結果である。
The present invention relates to a method for reactivating an insoluble electrode whose activation level has been reduced due to deposits. Conventionally, an insoluble electrode in which an active coating containing a platinum group metal oxide or the like is provided on a substrate such as metallic titanium has been used as an anode in the electrowinning of cobalt or the like. Cobalt electrowinning usually uses an aqueous cobalt chloride solution, with a pH of 1 to 2 and a current density of 2 to 3 A/dm 2 .
Electrolysis is carried out at a temperature of approximately 55°C, but if electrolysis is continued for a certain period of time, poor conductors will adhere to the anode, resulting in low activation of the electrode, resulting in a significant drop in current efficiency, etc. A phenomenon occurs. As a result of analysis, such deposits are mainly composed of cobalt hydroxide Co(OH) 3 , which firmly adheres and accumulates on the surface of the insoluble electrode being used, and the cathode 5.
It reaches a thickness of 1-2 mm in ~10 lives, significantly reducing current efficiency. Therefore, conventional methods for dissolving cobalt hydroxide have been proposed, such as treatment with a mixed solution of ammonia and ammonium sulfate, reduction treatment with SO 2 under acidic sulfuric acid, and reduction treatment with methanol under acidic sulfuric acid. However, each method has advantages and disadvantages, and it has been difficult to efficiently remove deposits on insoluble electrodes using a simple method. The present invention was made in order to solve the above problems, and aims to provide a method for efficiently and easily dissolving and cleaning the deposits and easily reactivating an inactivated insoluble electrode. do. The present inventors conducted extensive studies on various agents for dissolving such deposits, and found that an aqueous solution containing a mixture of an organic acid and a mineral acid reacts extremely effectively with deposits formed on the anode during actual operation. They discovered this and arrived at the present invention. That is, the present invention is characterized in that a method for reactivating an insoluble electrode includes dissolving and cleaning a low-activated insoluble electrode using an aqueous solution containing an organic acid and a mineral acid. The present invention will be explained in more detail below. As an insoluble electrode usually used in electrolytic extraction of cobalt etc.,
Coated electrodes containing platinum group metal oxides are known, such as those described in No. 21884. These are, for example, metal titanium coated with metal oxides such as ruthenium and titanium, but it is of course possible to apply the present invention to other insoluble electrodes. Using such an insoluble electrode as an anode and using an aqueous cobalt chloride solution as an electrolyte, electrolytic refining of cobalt is performed for a certain period of time under normal electrolytic conditions.As a result, the current efficiency decreases due to deposits deposited on the anode.
To reactivate the electrode, it is dissolved and cleaned with an aqueous solution containing organic and mineral acids. Various organic acids can be used, but oxalic acid, citric acid, or tartaric acid are preferred. The mineral acid used in combination with the organic acid is preferably hydrochloric acid or sulfuric acid. Nitric acid is not preferred in this respect because it may generate toxic gas. In order to achieve the effect in a short time, it is preferable that the above-mentioned organic acid contains at least one of them as an aqueous solution of 1% or more by weight.
Usually 10% or less is sufficient. The content of mineral acids is 1-10
% is preferable. In the present invention, it is necessary that the aqueous solution contains both an organic acid and a mineral acid, and each alone is insufficiently effective. An electrode used for electrowinning and inactivated by deposits is immersed in an immersion bath in which a mixed aqueous solution containing an organic acid and a mineral acid is kept at room temperature or higher, preferably 50 to 80°C, and the gas is removed. After thoroughly dissolving and cleaning to the extent that no generation can be seen, it is removed from the soaking tank.
After washing with water, it is used again as a reactivated anode. In actual operation, when electrolysis is performed for 5 to 10 lives (1 life is 8 days) on the cathode, the average length of the anode is approximately 1 to 2 mm.
Therefore, it is preferable to perform the reactivation treatment of the electrode of the present invention at each of these times. In the treatment method of the present invention, bubbles are generated during the dissolution reaction, but the process proceeds relatively gently and the dissolution is completed in a short time without any problems. According to the method of the present invention, there is no need for high-temperature treatment or complicated treatment operations that were found in conventional methods, and when the thickness of the deposit is about 1 to 2 mm, it can be done in about 20 to 50 minutes. After the dissolution is completed, the insoluble electrode, which has become low in activation due to deposits, can be efficiently and easily reactivated. Further, the electrodes are not damaged by the treatment of the present invention. Table 1 below shows that 2g of each of the deposits on the anode used for cobalt electrowinning are dried and peeled off.
These are the results of a dissolution test at 50°C using 100 ml of a mixed aqueous solution of 5% hydrochloric acid (5% sulfuric acid for No. 4) and various dissolving agents.
【表】
※ エチレン・ジアミン・テトラアセテート
第１表より明らかなように、クエン酸、酒石酸
及び蓚酸と塩酸又は硫酸との混合水溶液が最も溶
解作用が強力で、かつ支障がなかつた。また、No.
４は塩酸の代りに同濃度の硫酸を用いたものであ
るがNo.１とほぼ同様の結果が得られている。
以下実施例により説明するが本発明はこれらに
限定されるものではない。
実施例 １
50〜55ｇ／の塩化コバルト水溶液を電解液と
し、液温55℃、給液PH1.2、電流密度2.0A／ｄm2、
槽電圧1.0Vとし、陽極はチタン基体上にルテニ
ウム酸化物及びチタン酸化物を主成分とする被覆
を有する不溶性電極（ペルメレツク電極(株)製）を
アノードボツクスに収納し、陰極はステンレス板
を夫々使用して電解操作を行つた。この電解精製
を継続して８日毎に陰極を引き揚げてコバルトを
採取し、この陰極ライフの８ライフ目には、陰極
のほかに、別途陽極をアノードボツクスと共に引
き揚げ、これを所定の溶解剤の入つた浸漬槽に１
回に19本同時に浸漬して付着物の溶解洗浄処理を
行つた。
このようにして、多数の電極再活性化処理を各
条件で行い、その結果を各回とも平均値で第２表
に示す。
再活性化の手順は、先ず陽極を常温の水洗槽に
浸漬し、次に60〜70℃に保温された浸漬槽に移
し、反応が終了した後、再び水洗槽に浸漬して付
着物の除去を完了し、自然乾燥して陽極として再
び使用するという方法によつた。尚、反応の終了
は気泡発生の有無により判定した。
第２表より明らかなように、本発明の方法によ
れば電解条件等により陽極への不良導体物等の付
着量は多少の変動があるとしても、その除去に要
する時間は１時間以内であり、短時間で効率良く
電極の再活性化を行うことができる。また実操業
では、必ずしも付着物を完全に除去する必要はな
いので、実際には処理時間は更に短縮される。[Table] * Ethylene Diamine Tetraacetate As is clear from Table 1, a mixed aqueous solution of citric acid, tartaric acid, and oxalic acid with hydrochloric acid or sulfuric acid had the strongest dissolving action and caused no problems. Also, No.
No. 4 used sulfuric acid of the same concentration instead of hydrochloric acid, but almost the same results as No. 1 were obtained. Examples will be described below, but the present invention is not limited thereto. Example 1 A 50-55 g cobalt chloride aqueous solution was used as the electrolyte, the liquid temperature was 55°C, the supply liquid pH was 1.2, the current density was 2.0 A/dm 2 ,
The cell voltage was set to 1.0 V, the anode was an insoluble electrode (manufactured by Pelmerek Electrode Co., Ltd.) having a titanium base coated with ruthenium oxide and titanium oxide as main components, and the cathode was a stainless steel plate. The electrolytic operation was carried out using Continuing this electrolytic refining, the cathode is withdrawn every 8 days to collect cobalt, and in the 8th life of the cathode, in addition to the cathode, the anode is withdrawn together with the anode box, and this is filled with a prescribed dissolving agent. 1 in the ivy soaking tank
At the same time, 19 tubes were immersed at the same time to dissolve and clean the deposits. In this way, a large number of electrode reactivation treatments were performed under various conditions, and the results are shown in Table 2 as average values for each time. The reactivation procedure is to first immerse the anode in a washing tank at room temperature, then transfer it to a soaking tank kept at 60 to 70°C, and after the reaction is complete, immerse it in the washing tank again to remove the deposits. The method was to complete the process, air dry it, and use it again as an anode. The completion of the reaction was determined by the presence or absence of bubble generation. As is clear from Table 2, according to the method of the present invention, even though the amount of bad conductors adhering to the anode varies slightly depending on the electrolytic conditions, etc., the time required to remove them is within one hour. , the electrode can be reactivated efficiently in a short time. Furthermore, in actual operation, it is not always necessary to completely remove deposits, so the processing time is actually further shortened.
【表】
実施例 ２
実施例１に記載の如き通常のコバルト電解採取
に約６ケ月使用した黒色の表面付着物が多量につ
いた不溶性電極を５％蓚酸及び５％塩酸混合水溶
液により溶解洗浄し、電極の再活性化を行つた。
該溶解洗浄は、20℃の上記混合水溶液に該電極
を浸漬して行い、付着物の除去程度は、蛍光Ｘ線
法により確認した。
別途、参考として(1)10％蓚酸水溶液、及び(2)10
％塩酸水溶液各単味での溶解洗浄を行つた。
その結果得られた付着物の除去率（Coの残留
率として示す）と浸漬時間の関係は第１図の通り
であつた。
図中１は本発明の方法によるCo残留率と蓚酸
＋塩酸混合水溶液中の浸漬時間の関係を示す曲
線、２は10％蓚酸水溶液処理による曲線、３は10
％塩酸水溶液処理による曲線である。第１図から
明らかのように本発明による混合水溶液処理で
は、30分で70％以上、60分で約95％付着物が除去
されたが、蓚酸又は塩酸各単味の水溶液処理で
は、180分の浸漬でも夫々15％及び20％程度の除
去しかできなかつた。
実施例 ３
実施例２と同じ不活性化した不溶性電極を酸の
混合割合を変えた蓚酸＋塩酸混合水溶液を用いて
溶解洗浄し再活性化を行つた。溶解洗浄は40℃の
各液に浸漬して行い、付着物の除去率は蛍光Ｘ線
法により測定した。
参考として10％蓚酸水溶液及び10％塩酸水溶液
各単味での溶解洗浄を同時に行つた。
各液での浸漬５分後及び10分後の洗浄結果を第
３表に示す。[Table] Example 2 An insoluble electrode with a large amount of black surface deposits that had been used for ordinary cobalt electrowinning as described in Example 1 for about 6 months was dissolved and cleaned with a mixed aqueous solution of 5% oxalic acid and 5% hydrochloric acid. The electrode was reactivated. The dissolution and cleaning was performed by immersing the electrode in the above mixed aqueous solution at 20° C., and the degree of removal of deposits was confirmed by fluorescent X-ray method. Separately, for reference, (1) 10% oxalic acid aqueous solution, and (2) 10
% aqueous hydrochloric acid solution was used for dissolution and cleaning. The relationship between the removal rate of deposits (expressed as the residual rate of Co) and the immersion time was as shown in Figure 1. In the figure, 1 is a curve showing the relationship between Co residual rate and immersion time in a mixed aqueous solution of oxalic acid and hydrochloric acid according to the method of the present invention, 2 is a curve obtained by treatment with a 10% oxalic acid aqueous solution, and 3 is a curve of 10% oxalic acid aqueous solution treatment.
% hydrochloric acid aqueous solution treatment. As is clear from Figure 1, in the mixed aqueous solution treatment according to the present invention, more than 70% of the deposits were removed in 30 minutes and about 95% in 60 minutes, but in the aqueous solution treatment with oxalic acid or hydrochloric acid alone, it took 180 minutes. Even with immersion, only about 15% and 20% could be removed, respectively. Example 3 The same inactivated insoluble electrode as in Example 2 was reactivated by dissolving and cleaning it using a mixed aqueous solution of oxalic acid and hydrochloric acid with different mixing ratios of acids. Dissolution and cleaning was performed by immersion in each solution at 40°C, and the removal rate of deposits was measured by fluorescent X-ray method. As a reference, dissolving and cleaning with a 10% oxalic acid aqueous solution and a 10% hydrochloric acid aqueous solution was simultaneously performed. Table 3 shows the cleaning results after 5 minutes and 10 minutes of immersion in each solution.
【表】
第３表の結果から明らかのように、本発明によ
る混合酸水溶液での溶解洗浄では10分間の浸漬で
80％以上の付着物の除去が可能であつたが、各酸
単味の洗浄では除去率が20％以下であつた。尚、
本処理により電極の損傷は全く認められなかつ
た。
以上のとおり、本発明の方法により、効率良く
短時間で容易に不溶性電極を再活性化でき、定期
的に陽極の該洗浄処理を行えば、コバルト等の電
解精製を効率良く長期に亘つて行うことができる
ので、本発明の工業的価値は極めて大きい。[Table] As is clear from the results in Table 3, when dissolving and cleaning with the mixed acid aqueous solution according to the present invention, 10 minutes of immersion was enough.
Although it was possible to remove more than 80% of deposits, the removal rate was less than 20% when cleaning with each acid alone. still,
No damage to the electrodes was observed as a result of this treatment. As described above, by the method of the present invention, an insoluble electrode can be easily reactivated efficiently and in a short time, and if the anode is periodically cleaned, electrolytic refining of cobalt etc. can be carried out efficiently and over a long period of time. Therefore, the industrial value of the present invention is extremely large.
第１図は、本発明方法及び参考方法による効果
を対比して例示する測定グラフである。
１：本発明方法による曲線、２：参考方法(1)に
よる曲線、３：参考方法(2)による曲線。
FIG. 1 is a measurement graph illustrating the effects of the method of the present invention and the reference method in comparison. 1: Curve according to the method of the present invention, 2: Curve according to the reference method (1), 3: Curve according to the reference method (2).
Claims (1)
酸と鉱酸とを含有する水溶液を用いて溶解洗浄す
ることを特徴とする不溶性電極の再活性化方法。 ２ 有機酸が蓚酸、クエン酸及び酒石酸から選ば
れた少くとも一種である特許請求の範囲第１項に
記載の方法。 ３ 鉱酸が塩酸又は硫酸である特許請求の範囲第
１項または第２項に記載の方法。 ４ コバルトの電解採取に使用した不溶性電極を
用いる特許請求の範囲第１項に記載の方法。[Scope of Claims] 1. A method for reactivating an insoluble electrode, which comprises dissolving and cleaning an insoluble electrode whose activation level has been reduced due to deposits using an aqueous solution containing an organic acid and a mineral acid. 2. The method according to claim 1, wherein the organic acid is at least one selected from oxalic acid, citric acid, and tartaric acid. 3. The method according to claim 1 or 2, wherein the mineral acid is hydrochloric acid or sulfuric acid. 4. The method according to claim 1, which uses an insoluble electrode used for electrowinning of cobalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10935883A JPS602684A (en) | 1983-06-20 | 1983-06-20 | Reactivating method of insoluble electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10935883A JPS602684A (en) | 1983-06-20 | 1983-06-20 | Reactivating method of insoluble electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS602684A JPS602684A (en) | 1985-01-08 |
| JPH0210233B2 true JPH0210233B2 (en) | 1990-03-07 |
Family
ID=14508200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10935883A Granted JPS602684A (en) | 1983-06-20 | 1983-06-20 | Reactivating method of insoluble electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS602684A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8420430D0 (en) * | 1983-08-22 | 1984-09-12 | Ici Plc | Treatment of cathodes |
| JPH02101199A (en) * | 1988-10-08 | 1990-04-12 | Idemitsu Kosan Co Ltd | Method for washing electrode |
| US20080115810A1 (en) * | 2006-11-20 | 2008-05-22 | Permelec Electrode Ltd. | Method of reactivating electrode for electrolysis |
| JP6142848B2 (en) * | 2014-06-16 | 2017-06-07 | 住友金属鉱山株式会社 | Method for removing deposits from insoluble electrodes |
| JP2017164409A (en) * | 2016-03-18 | 2017-09-21 | セイコーエプソン株式会社 | Ultrasonic probe |
| JP7067215B2 (en) * | 2018-02-28 | 2022-05-16 | 住友金属鉱山株式会社 | Cobalt electrowinning method |
| CN111349961B (en) * | 2020-04-29 | 2021-05-07 | 宝鸡钛普锐斯钛阳极科技有限公司 | Method for cleaning waste titanium anode plate for foil forming machine and removing and recycling precious metal |
-
1983
- 1983-06-20 JP JP10935883A patent/JPS602684A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS602684A (en) | 1985-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109023399A (en) | The regeneration method of regeneration treatment liquid of electrolytic copper foil Ni―Ti anode and preparation method thereof and Ni―Ti anode | |
| JP4462513B2 (en) | Electrolyzed water manufacturing method, cleaning water, and cleaning method | |
| JPH0210233B2 (en) | ||
| US2945791A (en) | Inert lead dioxide anode and process of production | |
| GB2204325A (en) | A method of electrolytically treating metals and an electrode for use in the method | |
| CN114540824B (en) | Method for regenerating titanium anode plate by using waste acid solution | |
| CN106835163A (en) | For the cleaning of Ni―Ti anode noble metal surface plated film | |
| JP3867913B2 (en) | Cathode activation | |
| JPH03257199A (en) | Production of aluminum base for printing plate | |
| CN112573626A (en) | Titanium electrode and preparation method and application thereof | |
| JP4103209B2 (en) | Cleaning method for low hydrogen overvoltage electrode | |
| JPH0211775A (en) | Treatment to prevent sticking of plating metal to stainless steel which comes in contact with electroless plating liquid | |
| JPH0713320B2 (en) | Electrolytic pickling method for strips of special steel | |
| EP1303647B1 (en) | A process for improving an electrode | |
| JP3235216B2 (en) | Cleaning method for insoluble electrode and / or electroplating tank | |
| JP3855121B2 (en) | Method for producing electrode assembly for polymer electrolyte water electrolysis | |
| KR960004271B1 (en) | Method for removing a metallic nickel during zn-ni plating | |
| CN110965115A (en) | Method for removing oxide layer on surface of titanium alloy | |
| JPH09256184A (en) | Regenerating solution for electrolytic electrode and regenerating method therefor | |
| SU1211346A1 (en) | Method of removing active coating off oxide ruthenium-titanium anodes | |
| US5019172A (en) | Chemical treatment of aluminum cathodes in zinc electrowinning | |
| CN117107249A (en) | Method for removing insoluble coating on surface of titanium-based lead dioxide anode | |
| JPH07324198A (en) | Cleaning composition and method for cleaning semiconductor substrate using the same | |
| JPS63121692A (en) | Method for activating base material of ic lead frame | |
| US3484928A (en) | Interconnection of lead parts |