JPH11343589A - Production of high-purity cobalt - Google Patents
Production of high-purity cobaltInfo
- Publication number
- JPH11343589A JPH11343589A JP15127398A JP15127398A JPH11343589A JP H11343589 A JPH11343589 A JP H11343589A JP 15127398 A JP15127398 A JP 15127398A JP 15127398 A JP15127398 A JP 15127398A JP H11343589 A JPH11343589 A JP H11343589A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- purity
- electrolyte
- electrolytic
- solution
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体製造用のコ
バルトスパッタリングターゲット材等として重要な電解
採取による５Ｎレベルの高純度コバルトの製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 5N-level high-purity cobalt by electrolytic extraction, which is important as a material for a cobalt sputtering target for semiconductor production.
【０００２】[0002]
【従来の技術】半導体デバイスのゲート電極材料として
近年コバルト（Ｃｏ）が検討されている。しかし、半導
体デバイスはスパッタリング法により目的の電極、ゲー
ト、配線その他を形成し製造するが、スパッタリング法
に用いられるスパッタリングターゲットの材料としては
５Ｎ以上の高純度Ｃｏが要求される。現在、５Ｎ以上の
高純度Ｃｏの製造方法である電解法として、電解精製
法、溶媒抽出法を組み合わせた方法及び電解採取法を挙
げることができる。電解精製法は、不純物を含むＣｏ金
属をアノードとし、アノードを電解液中で溶解しながら
カソードに精製したＣｏを電析するものである。しか
し、標準電極電位がＣｏに近い不純物、例えばニッケル
（Ｎｉ）や鉄（Ｆｅ）は分離が困難である。この問題点
を解決するために、例えば特開平６−１９２８７９号公
報には、電解精製法と溶媒抽出法を組み合わせ、電解精
製で分離の困難な金属を溶媒抽出で除去する電解液を用
いて高純度Ｃｏを得る方法が提案されている。一方、電
解採取法は、Ｃｏ水溶液に不溶性アノードを用いて、カ
ソードに電解液中のＣｏを電析させる方法である。とく
に、電解精製法と比較して、粗金属のような中間段階を
経ないで一挙に高純度の金属を得ることができ、また電
解液の循環利用ができる等の利点があるため金属Ｃｏの
製造法として広く利用されている。しかし、Ｃｏを精製
する場合、得られるＣｏの純度は３Ｎ程度であった。純
度を上げるために高純度に精製された電解液を用いる必
要がある。このため、例えば特開平７−３４８６号公報
には電解の各段階でＮｉ、Ｆｅ等の不純物を段階的に溶
媒抽出で除去する方法が提案されている。しかしなが
ら、高純度のＣｏを安定して容易に製造するために、炭
酸コバルトを添加して電解液のＣｏ濃度とＰＨの調整す
るなどの工夫が必要である。2. Description of the Related Art In recent years, cobalt (Co) has been studied as a gate electrode material for semiconductor devices. However, a semiconductor device is manufactured by forming target electrodes, gates, wirings, and the like by a sputtering method, and high purity Co of 5N or more is required as a material of a sputtering target used in the sputtering method. At present, as an electrolysis method which is a method for producing high-purity Co of 5N or more, a method combining an electrolytic refining method, a solvent extraction method, and an electrowinning method can be exemplified. In the electrolytic refining method, Co metal containing impurities is used as an anode, and purified Co is deposited on a cathode while the anode is dissolved in an electrolytic solution. However, impurities having a standard electrode potential close to Co, such as nickel (Ni) and iron (Fe), are difficult to separate. In order to solve this problem, for example, Japanese Patent Application Laid-Open No. 6-192879 discloses a combination of an electrolytic refining method and a solvent extraction method, which employs an electrolytic solution that removes metals difficult to separate by electrolytic refining by solvent extraction. A method for obtaining the purity Co has been proposed. On the other hand, the electrowinning method is a method of using an insoluble anode in a Co aqueous solution and depositing Co in an electrolytic solution on a cathode. In particular, compared with the electrolytic refining method, it is possible to obtain a high-purity metal at once without passing through an intermediate step such as a crude metal, and there are advantages such as the circulating use of an electrolytic solution. Widely used as a manufacturing method. However, when Co was purified, the purity of the obtained Co was about 3N. In order to increase the purity, it is necessary to use a highly purified electrolytic solution. For this reason, for example, Japanese Patent Application Laid-Open No. 7-3486 proposes a method of removing impurities such as Ni and Fe stepwise by solvent extraction at each stage of electrolysis. However, in order to stably and easily produce high-purity Co, it is necessary to add cobalt carbonate to adjust the Co concentration and PH of the electrolytic solution.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記提
案の方法では、以下のような問題がある。電解採取によ
る高純度Ｃｏの製造工程中に、溶媒抽出工程を付加す
る、又は挿入することは工程が複雑であり、コストが高
くなり実用性に乏しいものである。また、添加するため
の炭酸コバルトを作製するためには、炭酸コバルト形成
剤としてこれまで炭酸アンモニウムが用いられている。
炭酸アンモニウムを調整剤として用いる電解液により電
解採取すると、一部アンモニウム錯体を形成し収率が下
がる。一方、炭酸コバルト形成剤としてアンモニア水を
用いる場合よりもより収率が高くなる。その反面、炭酸
アンモニア使用の場合ＣＯ2 のぬけかたに時間を要し、
液が不安定になり、さらに生成する炭酸コバルトの沈殿
が微細で濾過が遅く生産効率が低くなるという問題があ
る。さらに使用薬品費が約１０倍となるため回収できる
Ｃｏのコストが非常に高くなるという問題がある。従っ
て、基本的に電解法で５Ｎ以上の高純度Ｃｏを製造する
ことは困難であった。However, the method proposed above has the following problems. Adding or inserting a solvent extraction step during the production process of high-purity Co by electrowinning is complicated, increases the cost, and is not practical. Further, in order to produce cobalt carbonate to be added, ammonium carbonate has been used as a cobalt carbonate-forming agent.
When electrowinning is performed with an electrolytic solution using ammonium carbonate as an adjusting agent, an ammonium complex is partially formed and the yield is reduced. On the other hand, the yield is higher than when ammonia water is used as the cobalt carbonate forming agent. On the other hand, when using ammonium carbonate, it takes time to remove CO 2 ,
There is a problem that the liquid becomes unstable, and that the produced cobalt carbonate precipitates finely, slows down filtration and lowers production efficiency. Further, there is a problem in that the cost of Co that can be recovered is extremely high because the cost of chemicals used is about 10 times. Therefore, it was basically difficult to produce high purity Co of 5N or more by the electrolytic method.
【０００４】本発明は、上記の問題点を鑑みてなされた
ものであり、その課題は、ターゲット材に適した５Ｎレ
ベルの高純度Ｃｏの高い製造効率を得るために、電解尾
液及び電解液を調整又精製する単純な工程を付加する電
解採取による高純度Ｃｏの製造方法を提供することであ
る。更に、電解採取の過程で不純物が除去された電解液
を用いて、電解尾液のＣｏ濃度とＰＨを調整し不純物の
少ない電解液を作製し利用する電解採取による高純度Ｃ
ｏの製造方法を提供することである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to obtain an electrolytic tail solution and an electrolytic solution in order to obtain a high production efficiency of high-purity 5N-level Co suitable for a target material. To provide a method for producing high-purity Co by electrolytic extraction, which adds a simple step of adjusting or purifying Co. Further, using the electrolytic solution from which impurities have been removed in the course of electrolytic sampling, the Co concentration and PH of the electrolytic tail solution are adjusted to produce and use an electrolytic solution with less impurities.
to provide a manufacturing method of o.
【０００５】[0005]
【課題を解決するための手段】上記問題点を解決するた
めに、請求項１に記載の発明は、硫酸コバルトを含有す
る水溶液を電解液として電解採取するＣｏの製造方法に
おいて、電解尾液のＣｏ濃度とＰＨを水酸化コバルトを
用いて調整し、電解時と調整時に不溶性不純物を除去精
製し、電解液として循環して使用する高純度Ｃｏの製造
方法である。請求項２に記載の発明は、請求項１に記載
の高純度Ｃｏの製造方法において、前記不溶性不純物が
Ｎｉ、Ｆｅ、Ｍｎ、Ａｌ、Ｃｕである高純度Ｃｏの製造
方法である。請求項３に記載の発明は、請求項１又は２
に記載の高純度Ｃｏの製造方法において、前記水酸化コ
バルトが硫酸コバルトにアンモニア水を添加して又はア
ンモニアガスを吹き込むことにより作製される高純度Ｃ
ｏの製造方法である。請求項４に記載の発明は、請求項
１ないし３に記載の高純度Ｃｏの製造方法において、前
記電解液のＣｏ濃度が５０〜９０ｇ／Ｌで、ＰＨが２〜
４である高純度Ｃｏの製造方法である。本発明におい
て、電解液及び電解尾液は硫酸等の酸性水溶液を用いる
ことが好ましい。Means for Solving the Problems In order to solve the above-mentioned problems, the invention according to claim 1 provides a method for producing Co by electrolytically collecting an aqueous solution containing cobalt sulfate as an electrolytic solution. This is a method for producing high-purity Co in which Co concentration and PH are adjusted using cobalt hydroxide, and insoluble impurities are removed and refined during electrolysis and adjustment, and circulated and used as an electrolytic solution. The invention according to claim 2 is the method for producing high-purity Co according to claim 1, wherein the insoluble impurities are Ni, Fe, Mn, Al, and Cu. The invention described in claim 3 is the invention according to claim 1 or 2
The method for producing high-purity Co according to the above, wherein the cobalt hydroxide is prepared by adding ammonia water to cobalt sulfate or blowing ammonia gas.
This is a manufacturing method of o. According to a fourth aspect of the present invention, in the method for producing high-purity Co according to the first to third aspects, the electrolytic solution has a Co concentration of 50 to 90 g / L and a PH of 2 to 90 g / L.
4 is a method for producing high-purity Co. In the present invention, it is preferable to use an acidic aqueous solution such as sulfuric acid as the electrolytic solution and the electrolytic tail solution.
【０００６】本発明は、電解尾液に可溶性でＣｏ濃度及
びＰＨを上げる調整剤として、炭酸コバルトの代わりに
水酸化コバルトを用いるものである。電解槽より排出さ
れる電解尾液は連続的に注入される電解液に比べ、Ｃｏ
濃度及びＰＨの低い液が排出されるが、この尾液は電解
液として循環使用するためには元の注液と同じＣｏ濃度
及びＰＨに調整する。In the present invention, cobalt hydroxide is used in place of cobalt carbonate as a regulator that is soluble in the electrolytic tail solution and increases the Co concentration and pH. The electrolytic tail solution discharged from the electrolytic cell has a higher Co content than the electrolytic solution continuously injected.
A liquid having a low concentration and low pH is discharged, but this tail liquid is adjusted to the same Co concentration and PH as the original injection liquid in order to be circulated and used as an electrolyte.
【０００７】さらに、本発明は、Ｃｏとともに電析する
主な元素としてＦｅ、Ｎｉ、Ｃｕ、Ｃｄ及び電着（電
析）せずに不溶物として電解液中に存在するものとして
Ｍｎ、Ａｌを除去精製するものである。Ｍｎ、Ａｌは、
Ｃｏとともに電解槽及びアノードでＣｏＯＯＨとともに
酸化されて不溶物として生成する又は電解尾液調整時に
電解液中に不溶物として生成する。この不溶物を濾過し
て除去することができる。Ｆｅは、電解液中に生成する
不溶物及び電解尾液を水酸化コバルトで調整するときに
生ずる不溶物とともに濾過除去され、電解液中のＦｅ濃
度を極微量まで低下することができる。Ｎｉは、電解中
の生成物にＮｉＯＯＨとして、また電解尾液調整時にＮ
ｉ（ＯＨ）2 として、また水酸化コバルト作製時に錯体
として系外に出されるため電解液中のＮｉ濃度を極微量
まで低下することができる。Ｃｕ、Ｃｄについては初期
電解が起こり電解液は循環を繰り返すごとに精製される
ため、電解液を循環使用することにより電解液中の濃度
を低減することができる。Further, the present invention provides Fe, Ni, Cu, Cd as main elements to be deposited together with Co, and Mn and Al as those present in the electrolyte as insoluble substances without electrodeposition (electrodeposition). It is to be removed and purified. Mn and Al are
It is oxidized with CoOOH in the electrolytic cell and the anode together with Co and is generated as an insoluble substance, or is generated as an insoluble substance in the electrolytic solution at the time of adjusting the electrolytic tail solution. This insoluble matter can be removed by filtration. Fe is removed by filtration together with insolubles generated in the electrolytic solution and insolubles generated when the electrolytic tail solution is adjusted with cobalt hydroxide, so that the Fe concentration in the electrolytic solution can be reduced to a trace amount. Ni is added to the product during electrolysis as NiOOH and N
Since i (OH) 2 and a complex are taken out of the system during the production of cobalt hydroxide, the Ni concentration in the electrolytic solution can be reduced to an extremely small amount. Initial electrolysis occurs for Cu and Cd, and the electrolytic solution is purified each time the circulation is repeated. Therefore, by circulating and using the electrolytic solution, the concentration in the electrolytic solution can be reduced.
【０００８】かくして電解液作製に用いた硫酸コバルト
溶液にアンモニア水を添加して又はアンモニアガスを吹
き込むことにより得られた水酸化コバルトを用い、電解
尾液のＣｏ濃度及びＰＨを目標値に調整し、さらに電解
中生成した不溶物及び水酸化コバルト中で一部酸化され
た少量の不溶物及びＰＨ調整時に生成する不溶物を濾過
することにより高度に生成された電解循環液を得ること
ができ、これを電解することにより高純度Ｃｏを効率よ
く安定に製造することができる。Thus, the cobalt concentration and PH of the electrolytic tail solution are adjusted to target values by using cobalt hydroxide obtained by adding ammonia water to the cobalt sulfate solution used for preparing the electrolytic solution or by blowing ammonia gas. In addition, by filtering insolubles generated during electrolysis and a small amount of insolubles partially oxidized in cobalt hydroxide and insolubles generated at the time of pH adjustment, a highly generated electrolysis circulating liquid can be obtained, By electrolyzing this, high-purity Co can be efficiently and stably produced.
【０００９】[0009]
【発明の実施の形態】本発明は、電解液のＣｏ濃度及び
ＰＨ調整のために用いる調整剤として水酸化コバルトを
用いる。水酸化コバルトを作成する方法として、苛性ソ
ーダ等の苛性アルカリを使用する方法とアンモニア水又
はアンモニアガスを使用する方法がある。苛性ソーダを
用いた場合Ｃｏの収率は高いが、濾過性が悪く、洗浄に
手間がかかりＮａの残留が問題となる。アンモニア水を
直接添加する場合とアンモニアガスを酸性水溶液中に吹
き込みアンモニア水を形成する場合と作用は同様で、Ｃ
ｏの一部が錯体を形成し液中に溶解するためにＣｏの収
率が悪くなるが、水酸化コバルトの濾過性は非常に良
く、更にアンモニアと錯体を形成するＣｕ、Ｎｉ等を低
減させる方向に作用する。ここに用いられる調整剤はス
タート時に電解液作製に用いられたコバルト塩の純度と
同等以上であることが望まれる。これらの望まれる調整
剤が得られない場合、電解液を作製したコバルト塩より
水酸化コバルトを作製すること、または、電解尾液の一
部を濾過した後に水酸化コバルトを作製することが好ま
しい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, cobalt hydroxide is used as an adjusting agent for adjusting the Co concentration and pH of an electrolytic solution. As a method for producing cobalt hydroxide, there are a method using caustic alkali such as caustic soda and a method using ammonia water or ammonia gas. When caustic soda is used, the yield of Co is high, but the filterability is poor, washing is troublesome, and there is a problem of residual Na. The operation is the same as when the ammonia water is directly added and when the ammonia gas is blown into the acidic aqueous solution to form the ammonia water.
Although a part of o forms a complex and dissolves in the liquid, the yield of Co is deteriorated, but the filtering property of cobalt hydroxide is very good, and further reduces Cu, Ni, etc. which form a complex with ammonia. Acts in the direction. It is desired that the adjusting agent used here has a purity equal to or higher than the purity of the cobalt salt used for preparing the electrolytic solution at the start. When these desired regulators cannot be obtained, it is preferable to prepare cobalt hydroxide from the cobalt salt from which the electrolytic solution was prepared, or to prepare cobalt hydroxide after filtering a part of the electrolytic tail solution.
【００１０】さらに、本発明は、電解液が電解時と調整
時に生成する不溶性不純物を除去精製するものである。
Ｃｏともに電析する主な元素としてＦｅ、Ｎｉ、Ｃｕ、
Ｃｄ等があり、電着（電析）せずに不溶物として電解液
中に生成するものとしてＭｎ、Ａｌがある。これのいず
れについても除去精製しなければ高純度Ｃｏを製造する
ことができない。Ｃｏの電着速度に対してＮｉは約１／
１０、Ｆｅは約２倍の速度で電着する。Ｍｎ、Ａｌは電
解槽及びアノードに少量酸化されて生成するＣｏＯＯＨ
とともに、液中に少量不溶物として生成し、また、電解
尾液調整時に不溶物として生成するので、濾過除去する
ことにより容易に精製することができる。ＦｅはＣｏと
電着速度が近いために、製品中の割合は電解液のＣｏの
濃度比とほぼ同じになるが、本法を用いることにより電
解液中に生成する不溶物及び電解尾液を水酸化コバルト
で調整するときに生ずる不溶物とともに濾過除去され、
結果として電析Ｃｏ中には、０．６ｐｐｍ以下（検出限
界以下）と極微量まで低下する。ＮｉはＣｏに対し約１
／１０の電着速度であるために電解液の濃度比より電析
Ｃｏ中の方が低くなる。Ｎｉは電解液中に濃縮されるた
めに、水酸化コバルトで調整することによりＦｅと同じ
ように電解中の生成物にＮｉＯＯＨとして、また電解尾
液調整時にＮｉ（ＯＨ）2 として、また水酸化コバルト
作製時に複錯体化合物として系外に出されるため電析Ｃ
ｏ中のＮｉ濃度は一定に安定している。Further, the present invention is to remove and purify insoluble impurities generated during the electrolysis and during the adjustment of the electrolytic solution.
Fe, Ni, Cu, and
There are Cd and the like, and Mn and Al are formed in the electrolyte as insolubles without being electrodeposited (deposited). Without removing and purifying any of these, high-purity Co cannot be produced. Ni is about 1 /
10. Fe is electrodeposited at about twice the speed. Mn and Al are oxidized in a small amount in the electrolytic cell and anode.
At the same time, it is produced as a small amount of insoluble matter in the solution, and is produced as an insoluble matter at the time of adjusting the electrolytic tail solution, so that it can be easily purified by filtration and removal. Since Fe has a similar electrodeposition rate to Co, the ratio in the product is almost the same as the concentration ratio of Co in the electrolytic solution. However, by using this method, insoluble matters and electrolytic tail solution generated in the electrolytic solution are reduced. It is removed by filtration together with insolubles generated when adjusting with cobalt hydroxide,
As a result, the content in the deposited Co is as low as 0.6 ppm or less (below the detection limit), which is a very small amount. Ni is about 1 for Co
Since the electrodeposition rate is / 10, the concentration in the deposited Co is lower than the concentration ratio of the electrolytic solution. Since Ni is concentrated in the electrolytic solution, by adjusting with cobalt hydroxide, NiOOH is added to the product being electrolyzed in the same manner as Fe, and Ni (OH) 2 is used in the preparation of the electrolytic tail solution. Electrodeposited C because it is taken out of the system as a complex compound during the production of cobalt
The Ni concentration in o is constant and stable.
【００１１】さらに、Ｃｕ、ＣｄはＣｏの電着速度に対
して７〜１０倍であり、電解液のＣｏの対する濃度比に
対し、電析Ｃｏ中で７〜１０倍となる。Ｃｕ、Ｃｄは初
期電析が起こり電解液は循環を繰り返すごとに精製され
るため、電解液を循環使用することにより電析Ｃｏ中の
Ｃｕ、Ｃｄの濃度を低下させることができる。これらの
ことから本発明により電解液を効率的に循環しながら高
純度Ｃｏを安定して製造することができる。Further, Cu and Cd are 7 to 10 times the electrodeposition rate of Co, and 7 to 10 times as high as the concentration ratio of Co in the electrolytic solution in electrodeposited Co. Initial deposition of Cu and Cd occurs, and the electrolytic solution is purified each time the circulation is repeated. Therefore, by circulating and using the electrolytic solution, the concentrations of Cu and Cd in the deposited Co can be reduced. From these facts, according to the present invention, high-purity Co can be stably produced while efficiently circulating the electrolytic solution.
【００１２】（実施例）電解槽は直方体でその壁上に共
通の導体を置き、これに導電用棹につり下げた不溶性陽
極と陰極を交互にを配置する。電解槽は鉄鋼材料で溶接
したものに塩化ビニール、強化プラスチックで内張りを
する。隔膜を電極間に使用するものであってもよい。浸
出した電解尾液を水酸化コバルト水溶液で調整し６時間
静置させたものの上澄み液を電解液とし、Ｃｏの電解採
取をする。また、ここで静置したものをフィルター濾過
して電解液として使用してもよい。不純物は沈殿物又は
濾過残渣中に濃縮されて、溢流は循環させて電解尾液と
して使用する。なお、ここで使用する水酸化コバルト
は、Ｃｏ濃度が７０ｇ／Ｌの硫酸コバルト溶液１Ｌに対
して、２９％のアンモニア水１４０ｇを添加することに
より作製したものである。電解条件は、陽極を不溶性
に、陰極にＡｌ箔を巻いたＳＵＳ板を用いる。建浴時、
電解液の主成分はＣｏＳＯ4 とＨ2 ＳＯ4 である。注入
する水酸化コバルトの水溶液はＣｏ濃度は７０ｇ／Ｌ、
ＰＨは３である。電解採取の電流密度は１５０〜３５０
Ａ／ｍ2 、浴電圧２〜６Voltで、操業中の温度は４５〜
６５℃でおこなう。得られたＣｏの主要な不純物の濃度
を以下の表に示す。(Embodiment) The electrolytic cell is a rectangular parallelepiped and a common conductor is placed on its wall, and an insoluble anode and a cathode suspended from a conductive rod are alternately arranged on the common conductor. The electrolytic cell is lined with vinyl chloride and reinforced plastic on a welded steel material. A diaphragm may be used between the electrodes. The leached electrolytic tail solution was adjusted with an aqueous solution of cobalt hydroxide and allowed to stand for 6 hours, and the supernatant was used as the electrolytic solution, and Co was sampled by electrolysis. In addition, what is left here may be filtered and used as an electrolyte. The impurities are concentrated in the sediment or the filtration residue, and the overflow is circulated and used as an electrolytic tail solution. The cobalt hydroxide used here was prepared by adding 140 g of 29% ammonia water to 1 L of a cobalt sulfate solution having a Co concentration of 70 g / L. As the electrolysis conditions, a SUS plate in which an anode is insoluble and an aluminum foil is wound on a cathode is used. At the time of bathing,
The main components of the electrolyte are CoSO 4 and H 2 SO 4 . The aqueous solution of cobalt hydroxide to be injected has a Co concentration of 70 g / L,
PH is 3. Current density of electrowinning is 150-350
A / m 2 , bath voltage 2-6 Volt, operating temperature 45-
Perform at 65 ° C. The following table shows the concentrations of the main impurities of Co thus obtained.
【００１３】[0013]
【表１】 なお、アンモニアガスの場合は、溶液１Ｌ当たり１００
％のＮＨ3 ガスを１２０Ｌ／分で２５〜３０分吹き込む
ことにより作製されるものを用いることができる。いず
れの水酸化コバルトを用いても同様の不純物濃度とな
る。[Table 1] In the case of ammonia gas, 100 L per 1 L of solution is used.
% NH 3 gas is blown at 120 L / min for 25 to 30 minutes. The same impurity concentration is obtained by using any of the cobalt hydroxides.
【００１４】（比較例）実施例１と同様の電解尾液を水
酸化コバルトを含む水溶液で調整せず、さらに循環しな
いで、Ｃｏの電解採取をする。得られたＣｏの不純物濃
度を表２に示す。(Comparative Example) The same electrolytic tail solution as in Example 1 was not adjusted with an aqueous solution containing cobalt hydroxide, and Co was sampled without circulation. Table 2 shows the obtained Co impurity concentrations.
【表２】 [Table 2]
【００１５】この電解採取中に、陽極表面に付着する黒
色物を分離回収して分析した。また、電解槽底に沈降す
る黒色物を濾過分離して回収し同様に分析した。分析装
置はＸ線回折装置を用いた。陽極付着物は、（Ｃｏ，Ｍ
ｎ）ＯＯＨ、ＣｏＯＯＨである。また、電解槽沈殿黒色
物は、（Ｃｏ，Ｍｎ）ＯＯＨ、ＣｏＯＯＨ、ＡｌＯＯＨ
である。これにより、Ｍｎ，Ａｌを不溶物として濾過に
より分離回収できることがわかる。During the electrowinning, black matter adhering to the anode surface was separated and collected for analysis. Further, a black substance settling at the bottom of the electrolytic cell was separated by filtration, collected and analyzed in the same manner. The analyzer used was an X-ray diffractometer. The anode deposit is (Co, M
n) OOH, CoOOH. In addition, black matter deposited in the electrolytic cell is (Co, Mn) OOH, CoOOH, AlOOH
It is. This indicates that Mn and Al can be separated and recovered by filtration as insolubles.
【００１６】ここで、電解液は硫酸を使用する。Ｃｏ等
の鉱石に酸化鉱、硫化鉱が多く、または硫酸等の酸浸出
の方が反応が早く、さらに硫酸の入手が容易だからであ
る。電解液中のＣｏ濃度は５０〜９０ｇ／Ｌがよい。５
０ｇ／Ｌ以下及び９０ｇ／Ｌ以上では電流効率が低下す
るためである。とくに、６０〜８０ｇ／Ｌの範囲が好ま
しい。電解液のＰＨは、２〜４の範囲がよい。ＰＨが２
以下では電流効率が低下し、４以上ではＣｏの残渣ロス
が大きくなるためである。とくに、２．５〜３．５の範
囲が好ましい。Here, sulfuric acid is used as the electrolyte. This is because an ore such as Co contains a large amount of oxidized ore or sulfide ore, or acid leaching with sulfuric acid or the like is faster in reaction and further facilitates the acquisition of sulfuric acid. The Co concentration in the electrolyte is preferably 50 to 90 g / L. 5
This is because the current efficiency decreases at 0 g / L or less and 90 g / L or more. In particular, a range of 60 to 80 g / L is preferable. The pH of the electrolyte is preferably in the range of 2 to 4. PH is 2
This is because the current efficiency is reduced below, and the residue loss of Co is increased above 4 when it is 4 or more. In particular, a range of 2.5 to 3.5 is preferable.
【００１７】[0017]
【発明の効果】本発明は特殊な薬品を使用することな
く、かつ精製のための特別な工程を経ることがないため
設備的にも安価に、電解採取により高純度Ｃｏを製造す
ることができる。さらに、電解液の循環使用により、高
度に精製された電解液の電解採取により高純度Ｃｏを安
定して製造することができる。According to the present invention, it is possible to produce high-purity Co by electrowinning at low cost in terms of equipment without using a special chemical and without passing through a special step for purification. . In addition, by circulating the electrolyte, it is possible to stably produce high-purity Co by electrowinning a highly purified electrolyte.
Claims (4)
取によるコバルトの製造方法において、 電解尾液のコバルト濃度とＰＨを水酸化コバルトを用い
て調整し、電解時と調整時に生成する不溶性不純物を除
去精製し、電解液として循環使用することを特徴とする
高純度コバルトの製造方法。1. A method for producing cobalt by electrolytic extraction from an electrolytic solution containing cobalt sulfate, wherein the cobalt concentration and PH of an electrolytic tail solution are adjusted using cobalt hydroxide to remove insoluble impurities generated during electrolysis and during the adjustment. A method for producing high-purity cobalt, comprising removing and purifying and circulating and using it as an electrolyte.
方法において、 前記不溶性不純物がニッケル（Ｎｉ）、鉄（Ｆｅ）、マ
ンガン（Ｍｎ）、アルミニウム（Ａｌ）、銅（Ｃｕ）で
あることを特徴とする高純度コバルトの製造方法。2. The method for producing high-purity cobalt according to claim 1, wherein the insoluble impurities are nickel (Ni), iron (Fe), manganese (Mn), aluminum (Al), and copper (Cu). A method for producing high-purity cobalt, characterized by the following.
の製造方法において、前記水酸化コバルトを硫酸コバル
ト水溶液にアンモニア水を添加して又はアンモニアガス
を吹き込むことにより作製することを特徴とする高純度
コバルトの製造方法。3. The method for producing high-purity cobalt according to claim 1, wherein the cobalt hydroxide is produced by adding ammonia water to a cobalt sulfate aqueous solution or by blowing ammonia gas. Production method of high purity cobalt.
純度コバルトの製造方法において、 前記電解液のコバルト濃度を５０〜９０ｇ／Ｌで、ＰＨ
が２〜４にすることを特徴とする高純度コバルトの製造
方法。4. The method for producing high-purity cobalt according to claim 1, wherein the electrolytic solution has a cobalt concentration of 50 to 90 g / L and a pH of PH.
Is 2 to 4. A method for producing high-purity cobalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15127398A JP4049886B2 (en) | 1998-06-01 | 1998-06-01 | Method for producing high purity cobalt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15127398A JP4049886B2 (en) | 1998-06-01 | 1998-06-01 | Method for producing high purity cobalt |
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| Publication Number | Publication Date |
|---|---|
| JPH11343589A true JPH11343589A (en) | 1999-12-14 |
| JP4049886B2 JP4049886B2 (en) | 2008-02-20 |
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ID=15515077
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15127398A Expired - Fee Related JP4049886B2 (en) | 1998-06-01 | 1998-06-01 | Method for producing high purity cobalt |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950598A (en) * | 2018-07-13 | 2018-12-07 | 有研亿金新材料有限公司 | Preparation method of electrolytic cobalt with low gas content |
| CN110669931A (en) * | 2019-09-25 | 2020-01-10 | 宁波弗镁瑞环保科技有限公司 | Method for removing cobalt by oxidizing nickel sulfate solution |
| CN113186409A (en) * | 2021-04-29 | 2021-07-30 | 金川集团镍盐有限公司 | Method for deeply removing cadmium from cobalt sulfate solution |
-
1998
- 1998-06-01 JP JP15127398A patent/JP4049886B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950598A (en) * | 2018-07-13 | 2018-12-07 | 有研亿金新材料有限公司 | Preparation method of electrolytic cobalt with low gas content |
| CN108950598B (en) * | 2018-07-13 | 2020-03-27 | 有研亿金新材料有限公司 | Preparation method of electrolytic cobalt with low gas content |
| CN110669931A (en) * | 2019-09-25 | 2020-01-10 | 宁波弗镁瑞环保科技有限公司 | Method for removing cobalt by oxidizing nickel sulfate solution |
| CN110669931B (en) * | 2019-09-25 | 2021-04-27 | 宁波弗镁瑞环保科技有限公司 | Method for removing cobalt by oxidizing nickel sulfate solution |
| CN113186409A (en) * | 2021-04-29 | 2021-07-30 | 金川集团镍盐有限公司 | Method for deeply removing cadmium from cobalt sulfate solution |
| CN113186409B (en) * | 2021-04-29 | 2022-11-25 | 金川集团镍盐有限公司 | Method for deeply removing cadmium from cobalt sulfate solution |
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| Publication number | Publication date |
|---|---|
| JP4049886B2 (en) | 2008-02-20 |
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