JP3792525B2 - Manufacturing method of high purity nickel - Google Patents
Manufacturing method of high purity nickel Download PDFInfo
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- JP3792525B2 JP3792525B2 JP2001087866A JP2001087866A JP3792525B2 JP 3792525 B2 JP3792525 B2 JP 3792525B2 JP 2001087866 A JP2001087866 A JP 2001087866A JP 2001087866 A JP2001087866 A JP 2001087866A JP 3792525 B2 JP3792525 B2 JP 3792525B2
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Description
【0001】
【発明の属する技術分野】
この発明は、硫酸ニッケル溶液を用いて電解精製により純度5N(99.999wt%)以上の高純度ニッケルを製造する方法に関する。
【0002】
【従来の技術】
一般に、5Nレベルの高純度ニッケルを製造する場合に、硫酸ニッケル溶液を用いて電解精製法を用いて製造するのが効率的であると考えられる。
しかし、硫酸ニッケル溶液のみを電解浴とした場合、アノードから酸素ガスが発生してpHが低下し、電流効率が非常に悪化する現象があるという問題があった。このためpH低下を抑制するために、アンモニア等を添加する必要があるが、このアンモニア添加は硫安等が次第に蓄積され、電解に困難をきたしていた。
【0003】
このような電解における問題は必ずしも明確ではないが、アノードに用いたニッケル原料の表面が不働態化し、電気が通らなくなってしまうことが原因と考えられる。
しかし、従来このような問題を解決できる方策が、特に講じられている分けではなく、硫酸ニッケル溶液を用いて電解精製しようとする場合、必ずしも効率的であるとは言えなかった。
【0004】
【発明が解決しようとする課題】
本発明は、硫酸ニッケル溶液を用いて電解精製する場合、アノードからの酸素ガス発生を抑制し電流効率の低下を防止して、効率的に高純度ニッケルを製造する方法を提供することを目的としたものである。
【0005】
【課題を解決するための手段】
上記問題点を解決するため、硫酸ニッケル溶液の浴組成を改善することにより、アノードからの酸素ガス発生を抑制できるとの知見を得た。
この知見に基づき、本発明は
1. 電解液として硫酸ニッケル溶液を用い、これにハロゲン化水素酸を添加して電解精製することを特徴とする高純度ニッケルの製造方法。
2. ハロゲン化水素酸の濃度が0.1〜10mol/Lであることを特徴とする上記1記載の高純度ニッケルの製造方法。
3. 電析ニッケル中の酸素含有量が30ppm以下、硫黄含有量が1ppm以下であることを特徴とする上記1又は2記載の高純度ニッケルの製造方法。
を提供するものである。
【0006】
【発明の実施の形態】
図1に示す電解槽を用い、4Nレベルの塊状のニッケルをアノードとし、カソードに4Nレベルのニッケルを使用して電解を行う。
浴温10〜70°C、硫酸系電解液を使用し、該電解液に塩酸、臭化水素酸又は弗酸から選択したハロゲン化水素酸を0.1〜10mol/L添加する。ニッケル濃度20〜120g/L、電流密度0.1〜10A/dm2で実施する。電流密度0.1A/dm2未満では生産性が悪く、また10A/dm2を超えるとノジュールが発生してしまい、アノードとカソードが接触するため好ましくないので、電流密度は0.1〜10A/dm2の範囲とする。
【0007】
これにより、電流効率は80〜100%となる。純度5Nの電析ニッケル(カソードに析出)が得られる。また、電析ニッケル中のガス成分も減少し、酸素は30ppm以下、硫黄は1ppm以下とすることができる。
このように、微量のハロゲン化水素酸を添加することにより、電解がスムーズにいく。この原因は必ずしも明確ではないが、原料ニッケルの表面が不働態化するのを防止しているものと考えられる。
ハロゲン化水素酸を0.1mol/L未満では添加の効果がなく、従来同様にpHが低下し、電流効率が急速に悪化する。またハロゲン化水素酸10.0mol/Lを超えると電析ニッケルの純度が悪くなる。したがって、ハロゲン化水素酸の添加量は0.1〜10.0mol/Lとする。
【0008】
【実施例及び比較例】
次に、本発明の実施例について説明する。なお、本実施例はあくまで一例であり、この例に制限されるものではない。すなわち、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。
【0009】
(実施例1)
図1に示すような電解槽1を用い、4Nレベルの塊状のニッケル原料2をアノード5とし、カソード4に4Nレベルのニッケルを使用して電解を行った。符号2はアノードバスケットである。
浴温40°C、硫酸系電解液で弗酸を1mol/Lを添加し、ニッケル濃度50g/L、電流密度2A/dm2、電解時間40hr実施した。
これにより、pHが次第に上昇し、pH1.5から2に上昇した。電流効率92%であり、電析ニッケル(カソードに析出)約1kgを得た。純度は5Nを達成した。電析ニッケル中の酸素は10ppm以下、硫黄は1ppm以下であった。
以上の結果を表1に示す。
【0010】
(実施例2)
実施例1と同じ電解槽を用い、4Nレベルの塊状のニッケルをアノードとし、カソードに4Nレベルのニッケルを使用して電解を行った。
浴温40°C、硫酸系電解液で弗酸を5mol/Lを添加し、ニッケル濃度50g/L、電流密度2A/dm2、電解時間40hr実施した。
この結果、pHが1.5から2.2に上昇した。電流効率94%であり、電析ニッケル(カソードに析出)約1.0kgを得た。純度は5Nを達成した。電析ニッケル中の酸素は20ppm以下、硫黄は0.1ppm以下であった。以上の結果を同様に表1に示す。
【0011】
(実施例3)
実施例1と同じ電解槽を用い、4Nレベルの塊状のニッケルをアノードとし、カソードに4Nレベルのニッケルを使用して電解を行った。
浴温40°C、硫酸系電解液で臭化水素酸を1mol/Lを添加し、ニッケル濃度50g/L、電流密度2A/dm2、電解時間40hr実施した。
この結果、pHが1.5から2に上昇した。電流効率90%であり、電析ニッケル(カソードに析出)約0.98kgを得た。純度は5Nを達成した。電析ニッケル中の酸素は15ppm以下、硫黄は0.8ppm以下であった。以上の結果を同様に表1に示す。
【0012】
(比較例1)
弗酸、塩酸、臭化水素酸等のハロゲン化水素酸を一切添加せず、実施例1と同じ電解槽を用い、4Nレベルの塊状のニッケルをアノードとし、カソードに4Nレベルのニッケルを使用して硫酸系電解液で電解を行った。
浴温40°C、ニッケル濃度50g/L、電流密度2A/dm2、電解時間40hr実施した。この結果pHは1.5からpH1.0に低下し、電流効率は65%に低下した。また、電析ニッケル中の酸素は50ppm、硫黄は2ppmとなり、ガス成分の増加があった。
以上の結果を同様に表1に示す。
【0013】
【表1】
【0014】
表1に示すように、弗酸又は臭化水素酸を添加した実施例1〜3では電流効率が90%以上と高く、電析ニッケル中の酸素は30ppm以下、硫黄は1ppm以下となり、高純度のニッケルが得られた。この外、塩酸等の他のハロゲン化水素酸を添加したものでも同様の結果が得られた。
これに対し、弗酸、塩酸、臭化水素酸等のハロゲン化水素酸を一切添加しない比較例1では電流効率は65%に低下し、また電析ニッケル中の酸素及び硫黄の増加があった。
【0015】
【発明の効果】
以上に示すように、電解液として硫酸ニッケル溶液を用い、これにハロゲン化水素酸を添加して電解精製することにより、アノードからの酸素ガス発生を抑制し電流効率の低下を防止して、効率的に高純度ニッケルを製造することができるという著しい効果を有する。
【図面の簡単な説明】
【図1】電解工程の概要を示す図である。
【符号の説明】
1 電解槽
2 塊状のニッケル原料
3 アノードバスケット
4 カソード
5 アノード[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing high-purity nickel having a purity of 5N (99.999 wt%) or more by electrolytic purification using a nickel sulfate solution.
[0002]
[Prior art]
In general, when producing 5N level high-purity nickel, it is considered efficient to produce it using an electrolytic purification method using a nickel sulfate solution.
However, when only the nickel sulfate solution is used as the electrolytic bath, there is a problem that oxygen gas is generated from the anode, the pH is lowered, and the current efficiency is extremely deteriorated. For this reason, it is necessary to add ammonia or the like in order to suppress a decrease in pH. However, this ammonia addition gradually accumulates ammonium sulfate and makes electrolysis difficult.
[0003]
Although the problem in such electrolysis is not necessarily clear, it is thought that the cause is that the surface of the nickel raw material used for the anode is passivated and cannot conduct electricity.
However, measures that can solve such problems have not been particularly taken, and it has not always been efficient to attempt electrolytic purification using a nickel sulfate solution.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for efficiently producing high-purity nickel by suppressing generation of oxygen gas from an anode and preventing a decrease in current efficiency when electrolytic purification is performed using a nickel sulfate solution. It is a thing.
[0005]
[Means for Solving the Problems]
In order to solve the above problems, the inventors have obtained knowledge that the generation of oxygen gas from the anode can be suppressed by improving the bath composition of the nickel sulfate solution.
Based on this finding, the present invention provides 1. A method for producing high-purity nickel, characterized in that a nickel sulfate solution is used as an electrolytic solution, and hydrohalic acid is added thereto for electrolytic purification.
2. 2. The method for producing high-purity nickel as described in 1 above, wherein the concentration of hydrohalic acid is 0.1 to 10 mol / L.
3. 3. The method for producing high-purity nickel as described in 1 or 2 above, wherein the electrodeposited nickel has an oxygen content of 30 ppm or less and a sulfur content of 1 ppm or less.
Is to provide.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Using the electrolytic cell shown in FIG. 1, electrolysis is performed using 4N level bulk nickel as the anode and 4N level nickel as the cathode.
A sulfuric acid electrolyte solution is used at a bath temperature of 10 to 70 ° C., and a hydrohalic acid selected from hydrochloric acid, hydrobromic acid or hydrofluoric acid is added to the electrolyte solution in an amount of 0.1 to 10 mol / L. Nickel concentration 20 to 120 g / L, carried out at a current density of 0.1 to 10 A / dm 2. If the current density is less than 0.1 A / dm 2 , the productivity is poor, and if it exceeds 10 A / dm 2 , nodules are generated and the anode and cathode come into contact with each other. the range of dm 2.
[0007]
Thereby, the current efficiency is 80 to 100%. Electrodeposited nickel (deposited on the cathode) with a purity of 5N is obtained. Moreover, the gas component in electrodeposition nickel also reduces, oxygen can be 30 ppm or less, and sulfur can be 1 ppm or less.
Thus, electrolysis proceeds smoothly by adding a small amount of hydrohalic acid. Although this cause is not necessarily clear, it is considered that the surface of the raw material nickel is prevented from being passivated.
If the hydrohalic acid is less than 0.1 mol / L, there is no effect of addition, the pH is lowered as in the conventional case, and the current efficiency is rapidly deteriorated. Moreover, when it exceeds 10.0 mol / L of hydrohalic acid, the purity of electrodeposited nickel will worsen. Therefore, the addition amount of hydrohalic acid is 0.1 to 10.0 mol / L.
[0008]
[Examples and Comparative Examples]
Next, examples of the present invention will be described. In addition, a present Example is an example to the last, and is not restrict | limited to this example. That is, all aspects or modifications other than the embodiments are included within the scope of the technical idea of the present invention.
[0009]
Example 1
Using an electrolytic cell 1 as shown in FIG. 1, electrolysis was performed using 4N level
The bath temperature was 40 ° C., 1 mol / L of hydrofluoric acid was added with a sulfuric acid electrolyte, the nickel concentration was 50 g / L, the current density was 2 A / dm 2 , and the electrolysis time was 40 hours.
As a result, the pH gradually increased and rose from pH 1.5 to 2. The current efficiency was 92%, and about 1 kg of electrodeposited nickel (deposited on the cathode) was obtained. Purity achieved 5N. The oxygen in the electrodeposited nickel was 10 ppm or less, and the sulfur was 1 ppm or less.
The results are shown in Table 1.
[0010]
(Example 2)
Using the same electrolytic cell as in Example 1, 4N level bulk nickel was used as the anode, and 4N level nickel was used as the cathode for electrolysis.
The bath temperature was 40 ° C., 5 mol / L of hydrofluoric acid was added as a sulfuric acid electrolyte, the nickel concentration was 50 g / L, the current density was 2 A / dm 2 , and the electrolysis time was 40 hours.
As a result, the pH increased from 1.5 to 2.2. The current efficiency was 94%, and about 1.0 kg of electrodeposited nickel (deposited on the cathode) was obtained. Purity achieved 5N. The oxygen in the electrodeposited nickel was 20 ppm or less, and the sulfur was 0.1 ppm or less. The above results are similarly shown in Table 1.
[0011]
Example 3
Using the same electrolytic cell as in Example 1, 4N level bulk nickel was used as the anode, and 4N level nickel was used as the cathode for electrolysis.
The bath temperature was 40 ° C., 1 mol / L of hydrobromic acid was added as a sulfuric acid electrolyte, the nickel concentration was 50 g / L, the current density was 2 A / dm 2 , and the electrolysis time was 40 hours.
As a result, the pH increased from 1.5 to 2. The current efficiency was 90%, and about 0.98 kg of electrodeposited nickel (deposited on the cathode) was obtained. Purity achieved 5N. The oxygen in the electrodeposited nickel was 15 ppm or less, and the sulfur was 0.8 ppm or less. The above results are similarly shown in Table 1.
[0012]
(Comparative Example 1)
No hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or the like was added, the same electrolytic cell as in Example 1 was used, 4N level bulk nickel was used as the anode, and 4N level nickel was used as the cathode. Then, electrolysis was performed with a sulfuric acid electrolyte.
The bath temperature was 40 ° C., the nickel concentration was 50 g / L, the current density was 2 A / dm 2 , and the electrolysis time was 40 hours. As a result, the pH decreased from 1.5 to pH 1.0, and the current efficiency decreased to 65%. Moreover, oxygen in electrodeposited nickel was 50 ppm, sulfur was 2 ppm, and there was an increase in gas components.
The above results are similarly shown in Table 1.
[0013]
[Table 1]
[0014]
As shown in Table 1, in Examples 1 to 3 to which hydrofluoric acid or hydrobromic acid was added, the current efficiency was as high as 90% or higher, oxygen in the electrodeposited nickel was 30 ppm or less, sulfur was 1 ppm or less, and high purity. Of nickel was obtained. In addition, similar results were obtained with the addition of other hydrohalic acids such as hydrochloric acid.
In contrast, in Comparative Example 1 in which no hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or the like was added, the current efficiency was reduced to 65%, and oxygen and sulfur in the electrodeposited nickel were increased. .
[0015]
【The invention's effect】
As shown above, a nickel sulfate solution is used as the electrolytic solution, and hydrohalic acid is added to the electrolytic solution for electrolytic purification, thereby suppressing oxygen gas generation from the anode and preventing a decrease in current efficiency. In particular, it has a remarkable effect that high-purity nickel can be produced.
[Brief description of the drawings]
FIG. 1 is a diagram showing an outline of an electrolysis process.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1
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JP2001087866A JP3792525B2 (en) | 2001-03-26 | 2001-03-26 | Manufacturing method of high purity nickel |
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JP2001087866A JP3792525B2 (en) | 2001-03-26 | 2001-03-26 | Manufacturing method of high purity nickel |
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JP3792525B2 true JP3792525B2 (en) | 2006-07-05 |
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