WO2019107287A1 - Method for producing electrolytic copper - Google Patents

Method for producing electrolytic copper Download PDF

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Publication number
WO2019107287A1
WO2019107287A1 PCT/JP2018/043288 JP2018043288W WO2019107287A1 WO 2019107287 A1 WO2019107287 A1 WO 2019107287A1 JP 2018043288 W JP2018043288 W JP 2018043288W WO 2019107287 A1 WO2019107287 A1 WO 2019107287A1
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Prior art keywords
copper
concentration
electrolytic
anode
electrolytic solution
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PCT/JP2018/043288
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French (fr)
Japanese (ja)
Inventor
邦男 渡辺
惇貴 佐渡
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パンパシフィック・カッパー株式会社
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Priority claimed from JP2018167944A external-priority patent/JP6816076B2/en
Application filed by パンパシフィック・カッパー株式会社 filed Critical パンパシフィック・カッパー株式会社
Priority to CN201880034523.4A priority Critical patent/CN110662857A/en
Publication of WO2019107287A1 publication Critical patent/WO2019107287A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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

Definitions

  • the present invention relates to a method of producing electrolytic copper.
  • copper electrowinning involves leaching copper from a raw material such as ore into a solution and electrolytically reducing it to metal to obtain electrolytic copper by copper electrorefining. More specifically, raw materials such as ore and the like are purified to produce crude copper, which is used as an anode and electrolytically purified in an electrolytic solution.
  • Patent Document 1 In recent years, there has been an increasing need to use recycled products (mainly scrap copper) such as electronic devices as raw materials for copper electrowinning and recover copper from the recycled products.
  • crude copper used as an anode in copper electrorefining contains impurities such as arsenic, bismuth, antimony and nickel, and these impurities elute in the electrolyte.
  • nickel has an electrodeposition potential extremely lower than that of copper and is particularly easily concentrated in the electrolytic solution.
  • the concentration of nickel in the electrolytic solution increases, the voltage increase due to the increase in the liquid resistance of the electrolytic solution occurs, and the power consumption increases, which causes a problem that the production efficiency of the electrolytic copper decreases.
  • the concentration of nickel in the electrolytic solution is too high, a slime layer will be formed on the anode surface, so-called passivation will occur, the elution of copper ions will be impeded, and this will cause a decrease in the production efficiency of electrolytic copper.
  • this invention makes it a subject to provide the manufacturing method of the electric copper from which manufacturing efficiency becomes favorable, even if the density
  • the present inventors repeated studies to solve the above-mentioned problems.
  • concentration of nickel in the electrolytic solution in copper electrorefining even if the concentration of nickel in the crude copper used as the anode is high, electricity It has been found that the production efficiency of copper is good.
  • the present invention completed on the basis of the above findings, according to one aspect, uses a crude copper containing Ni as an anode, and includes the steps of performing electrolysis while maintaining the Ni concentration in the electrolyte at 15 g / L or less. It is a method.
  • the Ni concentration in the anode is at least 1800 ppm.
  • the Ni concentration held in the electrolytic solution is 12 g / L or less.
  • the electrolytic solution is a copper sulfate aqueous solution.
  • the current efficiency defined by the following formula in the electrolysis is 96% or more.
  • Current efficiency (%) (amount of generated copper / theoretical amount of copper) ⁇ 100
  • the present invention it is possible to provide a method of producing electric copper in which the production efficiency is good even if the concentration of nickel in the crude copper used as the anode is high.
  • FIG. 7 is a graph of current efficiency-grade of Ni in anode according to Example 1.
  • FIG. 15 is a graph of current efficiency-grade of Ni in anode according to Example 2.
  • FIG. 16 is a graph of current efficiency-grade of Ni in anode according to Example 3.
  • FIG. 16 is a graph of current efficiency-grade of Ni in anode according to Example 4.
  • FIG. 16 is a graph of current efficiency-grade of Ni in anode according to Comparative Example 1.
  • the anode used for electrolytic refining in the method of producing electric copper according to the present invention typically oxidizes about 93 to 99 mass% of copper grade obtained in the converter process or 97 to 99 mass% of crude copper. It is cast after smelting and reduction treatment, and is usually plate-like.
  • the crude copper of the anode contains Ni as an impurity.
  • the production efficiency of electric copper is good even if the concentration of Ni in the crude copper is high, so for example, the concentration of Ni in the crude copper is, for example, 1800 ppm or more, 2400 ppm or more, or 3000 ppm It may be more than.
  • the crude copper may contain impurities such as As, Bi and Sb.
  • the cathode used for the electrolytic purification in the method for producing electrolytic copper according to the present invention is not limited, but is a permanent metal for electrodepositing copper on the surface using a stainless steel plate besides the method using a seed plate A method based on a method called a cathode method (PC method) is mentioned.
  • the material of the permanent cathode is not particularly limited, but titanium and stainless steel are generally used because they are insoluble in the electrolytic solution, and stainless steel is preferable because cost is low.
  • the stainless steel is not particularly limited, and any of martensitic stainless steel, ferritic stainless steel, austenitic stainless steel, austenitic-ferritic duplex stainless steel, and precipitation hardened stainless steel may be used.
  • a sulfuric acid-based electrolytic solution can be used to electrolytically purify copper, and for example, it is preferable to use a copper sulfate aqueous solution as the electrolytic solution.
  • the concentration of sulfuric acid is in the range of 120 to 220 g / L
  • the concentration of Cu ion is in the range of 40 to 60 g / L, but not limited thereto.
  • the sulfuric acid concentration is in the range of 160 to 180 g / L
  • the Cu ion concentration is in the range of 45 to 55 g / L.
  • an additive is generally added to the electrolytic solution.
  • the additive is used to improve the deposition of copper on the cathode plate.
  • an additive that forms a protective colloid such as glue, gelatin, lignin (pulp waste solution), etc. and an organic substance having a functional group such as thiourea or aloin are used in common.
  • Ru an organic substance having a functional group such as thiourea or aloin.
  • the activation polarization during deposition is increased by the additive, and the homogeneity of electrodeposition is improved by increasing the polarization, so that the deposited metal can be dense and the surface can be uniform.
  • Electrolytic purification> In an industrial electrolytic copper production process, a plurality of electrolytic cells in which a plurality of cathodes and anodes (for example, 40 to 60 sheets each) are charged are installed, and copper electrolytic solution is continuously supplied to the electrolytic cells. , Is discharged continuously by the overflow.
  • electrolysis is performed while maintaining the Ni concentration in the electrolytic solution at 15 g / L or less.
  • a voltage increase due to an increase in the liquid resistance of the electrolytic solution can be suppressed, power consumption is reduced, and the production efficiency of electrolytic copper is increased.
  • the generation of the passive state in which the slime layer is formed on the anode surface can be suppressed, the elution of copper ions is not disturbed, and the production efficiency of electrolytic copper is improved.
  • the Ni concentration in the electrolyte is 15 g / L or less.
  • the production efficiency of electric copper is improved also by electrolysis under such a condition.
  • the electrolytic refining in the electrolytic refining, it is preferable to carry out the electrolysis while maintaining the Ni concentration in the electrolytic solution at 14 g / L or less, and it is more preferable to carry out the electrolysis while holding at 13 g / L or less It is still more preferable to perform electrolysis, preferably, while keeping it at 12 g / L or less.
  • the current efficiency in the electrolysis described later can be controlled to 97% or more.
  • the lower the Ni concentration of the electrolytic solution the better.
  • the current density is not particularly limited in electrolytic purification, and can be, for example, 300 to 360 A / m 2 .
  • the electrolytic solution was stored in a frozen crystal tank or the like, cooled at about -15 ° C. to be crystallized, drained by a centrifugal separator, and further dried by a dryer to contain Ni. Get a crystal.
  • the crystal containing Ni is NiSO 4 .6H 2 O (nickel sulfate hexahydrate).
  • the liquid obtained by the above-mentioned centrifugal separator can be used as an electrolytic solution after Ni removal, in the electrolytic purification of the method for producing electrolytic copper of the present invention.
  • electrolysis can be performed while maintaining the Ni concentration in the electrolyte at 15 g / L or less. it can.
  • the current efficiency defined by the following formula in electrolysis is preferably 96% or more.
  • Current efficiency (%) (amount of generated copper / theoretical amount of copper) ⁇ 100
  • the current efficiency is more preferably 96% or more, still more preferably 96.5% or more, and still more preferably 97% or more.
  • Example 1 Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
  • the concentration of Ni in the electrolytic solution was monitored and controlled so that the concentration of Ni was always maintained at 14.5 g / L or less during electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be kept at 14.5 g / L or less.
  • Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
  • Composition of electrolyte 40 to 60 g / L of copper, 13.6 to 14.0 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L ⁇ Current density: 322A / dm 2
  • the concentration of Ni in the electrolytic solution was monitored and controlled so that the concentration of Ni was always maintained at 14.0 g / L or less during the electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be kept at 14.0 g / L or less. Further, the current efficiency was calculated in the same manner as in Example 1.
  • Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
  • Composition of electrolyte 40 to 60 g / L of copper, 13.2 to 13.5 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L ⁇ Current density: 322A / dm 2
  • the concentration of Ni in the electrolytic solution was monitored and controlled so that the concentration of Ni was always kept at 13.4 g / L or less during the electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be held at 13.5 g / L or less. Further, the current efficiency was calculated in the same manner as in Example 1.
  • Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
  • Composition of electrolyte 40 to 60 g / L of copper, 11.0 to 12.0 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L ⁇ Current density: 322A / dm 2
  • the Ni concentration in the electrolytic solution was monitored, and controlled so that the Ni concentration was always maintained at 12.0 g / L or less during the electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be held at 12.0 g / L or less. Further, the current efficiency was calculated in the same manner as in Example 1.
  • Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
  • Composition of electrolyte 40 to 60 g / L of copper, 15.5 to 17.0 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L ⁇ Current density: 322A / dm 2
  • the concentration of Ni in the electrolyte was monitored and controlled so that the concentration of Ni was always maintained at 15.5 g / L or more during electrolysis. Further, the current efficiency was calculated in the same manner as in Example 1.
  • FIG. 1 is a graph of current efficiency-grade of Ni in an anode at an Ni concentration of 14.1 to 14.6 g / L in an electrolyte according to Example 1.
  • FIG. FIG. 2 is a graph of current efficiency-grade of Ni in the anode at a Ni concentration of 13.6 to 14.0 g / L in the electrolyte according to Example 2.
  • FIG. 3 is a graph of current efficiency-grade of Ni in the anode at an Ni concentration of 13.2 to 13.5 g / L in the electrolyte according to Example 3.
  • FIG. 1 is a graph of current efficiency-grade of Ni in an anode at an Ni concentration of 14.1 to 14.6 g / L in an electrolyte according to Example 1.
  • FIG. 3 is a graph of current efficiency-grade of Ni in the anode at a Ni concentration of 133.6 to 14.0 g / L in the electrolyte according to Example 3.
  • FIG. 4 is a graph of current efficiency-grade of Ni in the anode at an Ni concentration of 11.0 to 12.0 g / L in the electrolytic solution according to Example 4.
  • FIG. 5 is a graph of current efficiency-grade of Ni in the anode at a Ni concentration of 15.5 to 17.0 g / L in the electrolytic solution according to Comparative Example 1.
  • the grade of Ni in the anode is as high as 1800 ppm or more. Also, the current efficiency was as good as at least 96%.
  • Example 4 current efficiency is high even if the Ni grade in the anode is as high as 1800 ppm or more by performing electrolysis using crude copper containing Ni as the anode and maintaining the Ni concentration in the electrolytic solution at 12 g / L or less. All were good with 97% or more.
  • Comparative Example 1 electrolysis was performed using crude copper containing Ni as the anode and maintaining the Ni concentration in the electrolyte solution at more than 15 g / L, so current efficiency is particularly high when the grade of Ni in the anode is high Fell below 96%.

Abstract

Provided is a method for producing electrolytic copper that gives a good production efficiency even at high nickel concentrations in the crude copper used as the anode. The method for producing electrolytic copper comprises a step for carrying out electrolysis using Ni-containing crude copper for an anode while maintaining the Ni concentration in the electrolysis solution at not more than 15 g/L.

Description

電気銅の製造方法Method of manufacturing electrolytic copper
　本発明は電気銅の製造方法に関する。 The present invention relates to a method of producing electrolytic copper.
　一般に、銅の電解採取は、鉱石等の原料から銅を溶液中に浸出させ、これを電解的に金属に還元する銅電解精製によって電気銅とするものである。より具体的には、鉱石等の原料を精製して粗銅を作製し、これをアノードとして用いて電解液中で電解精製する。 In general, copper electrowinning involves leaching copper from a raw material such as ore into a solution and electrolytically reducing it to metal to obtain electrolytic copper by copper electrorefining. More specifically, raw materials such as ore and the like are purified to produce crude copper, which is used as an anode and electrolytically purified in an electrolytic solution.
　近年、電子機器等のリサイクル品（主にスクラップ銅）を銅の電解採取の原料とし、当該リサイクル品から銅を回収するニーズが高まっている（特許文献１）。 In recent years, there has been an increasing need to use recycled products (mainly scrap copper) such as electronic devices as raw materials for copper electrowinning and recover copper from the recycled products (Patent Document 1).
特開２００９－２８７０９６号公報JP, 2009-287096, A
　一般に銅電解精製においてアノードとして使用する粗銅には砒素、ビスマス、アンチモン、ニッケル等の不純物が含まれており、これらの不純物は電解液中に溶出する。 In general, crude copper used as an anode in copper electrorefining contains impurities such as arsenic, bismuth, antimony and nickel, and these impurities elute in the electrolyte.
　不純物の中でもニッケルは電析電位が銅の電析電位に比べて極端に低く、電解液中に特に濃縮されやすい。電解液中のニッケル濃度が上昇すると、電解液の液抵抗増加による電圧上昇が起きるため、消費電力が増加し、電気銅の製造効率が低下するという問題が生じる。また、電解液中のニッケル濃度が上昇しすぎると、スライム層がアノード表面に形成され、いわゆる不動態化が起こり、銅イオンの溶出が妨害され、電気銅の製造効率が低下する原因となる。 Among the impurities, nickel has an electrodeposition potential extremely lower than that of copper and is particularly easily concentrated in the electrolytic solution. When the concentration of nickel in the electrolytic solution increases, the voltage increase due to the increase in the liquid resistance of the electrolytic solution occurs, and the power consumption increases, which causes a problem that the production efficiency of the electrolytic copper decreases. Also, if the concentration of nickel in the electrolytic solution is too high, a slime layer will be formed on the anode surface, so-called passivation will occur, the elution of copper ions will be impeded, and this will cause a decrease in the production efficiency of electrolytic copper.
　特にリサイクル品を原料とする場合、アノードとして使用する粗銅中のニッケルの濃度が高い傾向にあるため、特に電流密度が高い領域での操業に於いては、上記のような電気銅の製造効率の低下がより大きな問題となる。 In particular, when recycled products are used as raw materials, the concentration of nickel in the crude copper used as the anode tends to be high. Therefore, in the operation particularly in the region of high current density, the production efficiency of the above-mentioned electric copper The decline is a bigger problem.
　そこで、本発明はアノードとして使用する粗銅中のニッケルの濃度が高くても製造効率が良好となる電気銅の製造方法を提供することを課題とする。 Then, this invention makes it a subject to provide the manufacturing method of the electric copper from which manufacturing efficiency becomes favorable, even if the density | concentration of nickel in the crude copper used as an anode is high.
　本発明者は、上記の課題を解決するために検討を重ねたところ、銅電解精製における電解液中のニッケル濃度を制御することで、アノードとして使用する粗銅中のニッケルの濃度が高くても電気銅の製造効率が良好となることを見出した。 The present inventors repeated studies to solve the above-mentioned problems. By controlling the concentration of nickel in the electrolytic solution in copper electrorefining, even if the concentration of nickel in the crude copper used as the anode is high, electricity It has been found that the production efficiency of copper is good.
　上記の知見を基礎として完成した本発明は、一側面において、Ｎｉを含む粗銅をアノードとして用い、電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持しながら電解を行う工程を含む電気銅の製造方法である。 The present invention completed on the basis of the above findings, according to one aspect, uses a crude copper containing Ni as an anode, and includes the steps of performing electrolysis while maintaining the Ni concentration in the electrolyte at 15 g / L or less. It is a method.
　本発明の電気銅の製造方法は一実施形態において、前記アノード中のＮｉ濃度が１８００ｐｐｍ以上である。 In one embodiment of the method for producing electrolytic copper of the present invention, the Ni concentration in the anode is at least 1800 ppm.
　本発明の電気銅の製造方法は別の一実施形態において、前記電解を行う工程において、前記電解液中で保持されるＮｉ濃度が１２ｇ／Ｌ以下である。 In another embodiment of the method for producing electrolytic copper of the present invention, in the step of performing the electrolysis, the Ni concentration held in the electrolytic solution is 12 g / L or less.
　本発明の電気銅の製造方法は更に別の一実施形態において、前記電解液が硫酸銅水溶液である。 In still another embodiment of the method for producing electrolytic copper of the present invention, the electrolytic solution is a copper sulfate aqueous solution.
　本発明の電気銅の製造方法は更に別の一実施形態において、前記電解における下記式で規定される電流効率が９６％以上である。
　電流効率（％）＝（生成された電気銅量／理論電気銅量）×１００ In still another embodiment of the method for producing electrolytic copper of the present invention, the current efficiency defined by the following formula in the electrolysis is 96% or more.
Current efficiency (%) = (amount of generated copper / theoretical amount of copper) × 100
　本発明によれば、アノードとして使用する粗銅中のニッケルの濃度が高くても製造効率が良好となる電気銅の製造方法を提供することが可能となる。 According to the present invention, it is possible to provide a method of producing electric copper in which the production efficiency is good even if the concentration of nickel in the crude copper used as the anode is high.
実施例１に係る電流効率－アノード中Ｎｉ品位のグラフである。7 is a graph of current efficiency-grade of Ni in anode according to Example 1. FIG. 実施例２に係る電流効率－アノード中Ｎｉ品位のグラフである。15 is a graph of current efficiency-grade of Ni in anode according to Example 2. FIG. 実施例３に係る電流効率－アノード中Ｎｉ品位のグラフである。FIG. 16 is a graph of current efficiency-grade of Ni in anode according to Example 3. FIG. 実施例４に係る電流効率－アノード中Ｎｉ品位のグラフである。FIG. 16 is a graph of current efficiency-grade of Ni in anode according to Example 4. FIG. 比較例１に係る電流効率－アノード中Ｎｉ品位のグラフである。FIG. 16 is a graph of current efficiency-grade of Ni in anode according to Comparative Example 1. FIG.
　以下に、本発明に係る電気銅の製造方法の実施形態を詳細に説明する。
　＜アノード＞
　本発明に係る電気銅の製造方法における電解精製に使用されるアノードは、典型的には、転炉工程で得られる銅品位９３～９９質量％程度、或いは、９７～９９質量％の粗銅を酸化製錬、還元処理をした後に鋳造したものであり、通常は板状である。 Below, embodiment of the manufacturing method of the electrolytic copper which concerns on this invention is described in detail.
<Anode>
The anode used for electrolytic refining in the method of producing electric copper according to the present invention typically oxidizes about 93 to 99 mass% of copper grade obtained in the converter process or 97 to 99 mass% of crude copper. It is cast after smelting and reduction treatment, and is usually plate-like.
　当該アノードの粗銅にはＮｉが不純物として含まれている。本発明に係る電気銅の製造方法では、粗銅中のＮｉ濃度が高くても電気銅の製造効率が良好となるため、例えば、粗銅中のＮｉ濃度は、例えば、１８００ｐｐｍ以上、２４００ｐｐｍ以上、または３０００ｐｐｍ以上であってもよい。また、粗銅中にはＡｓ、Ｂｉ、Ｓｂ等の不純物が含まれていてもよい。 The crude copper of the anode contains Ni as an impurity. In the method of producing electric copper according to the present invention, the production efficiency of electric copper is good even if the concentration of Ni in the crude copper is high, so for example, the concentration of Ni in the crude copper is, for example, 1800 ppm or more, 2400 ppm or more, or 3000 ppm It may be more than. In addition, the crude copper may contain impurities such as As, Bi and Sb.
　＜カソード＞
　本発明に係る電気銅の製造方法における電解精製に使用されるカソードとしては、限定的ではないが、種板を使用する方法の他、ステンレス板を使用してその表面に銅を電着させるパーマネントカソード法（ＰＣ法）と呼ばれる方式によるものが挙げられる。パーマネントカソードの材料としては特に制限はないが、電解液に対して不溶性であることからチタンやステンレスを用いるのが一般的であり、コストが安価で済むことからステンレスを用いるのが好ましい。ステンレスとしては特に制限はなく、マルテンサイト系ステンレス鋼、フェライト系ステンレス鋼、オーステナイト系ステンレス鋼、オーステナイト・フェライト二相ステンレス鋼、及び析出硬化ステンレス鋼の何れを用いてもよい。 <Cathode>
The cathode used for the electrolytic purification in the method for producing electrolytic copper according to the present invention is not limited, but is a permanent metal for electrodepositing copper on the surface using a stainless steel plate besides the method using a seed plate A method based on a method called a cathode method (PC method) is mentioned. The material of the permanent cathode is not particularly limited, but titanium and stainless steel are generally used because they are insoluble in the electrolytic solution, and stainless steel is preferable because cost is low. The stainless steel is not particularly limited, and any of martensitic stainless steel, ferritic stainless steel, austenitic stainless steel, austenitic-ferritic duplex stainless steel, and precipitation hardened stainless steel may be used.
　＜電解液＞
　本発明に係る電気銅の製造方法では、銅の電解精製を行うため、硫酸系電解液を使用することができ、例えば硫酸銅水溶液を電解液として用いることが好ましい。限定的ではないが、一般には、硫酸濃度は１２０～２２０ｇ／Ｌ、Ｃｕイオン濃度は４０～６０ｇ／Ｌの範囲にある。典型的には、硫酸濃度は１６０～１８０ｇ／Ｌ、Ｃｕイオン濃度は４５～５５ｇ／Ｌの範囲にある。 <Electrolyte solution>
In the method for producing electrolytic copper according to the present invention, a sulfuric acid-based electrolytic solution can be used to electrolytically purify copper, and for example, it is preferable to use a copper sulfate aqueous solution as the electrolytic solution. Generally, the concentration of sulfuric acid is in the range of 120 to 220 g / L, and the concentration of Cu ion is in the range of 40 to 60 g / L, but not limited thereto. Typically, the sulfuric acid concentration is in the range of 160 to 180 g / L, and the Cu ion concentration is in the range of 45 to 55 g / L.
　銅の電解精製を行う場合には、一般的に、電解液中に添加剤が添加される。添加剤は、陰極板における銅の析出状態改善等のために用いられる。例えば、有機物系の添加剤としては、ニカワ、ゼラチン、リグニン（パルプ廃液）などのように保護コロイドを形成するような添加剤と、チオ尿素やアロインのような官能基を有する有機物などが共用される。一般に、析出の際の活性化分極は添加剤によって増加し、分極を大きくすることで均一電着性が向上するので、析出金属は緻密で表面が均一なものを得ることができる。 In the case of electrolytic refining of copper, an additive is generally added to the electrolytic solution. The additive is used to improve the deposition of copper on the cathode plate. For example, as an organic additive, an additive that forms a protective colloid such as glue, gelatin, lignin (pulp waste solution), etc. and an organic substance having a functional group such as thiourea or aloin are used in common. Ru. Generally, the activation polarization during deposition is increased by the additive, and the homogeneity of electrodeposition is improved by increasing the polarization, so that the deposited metal can be dense and the surface can be uniform.
　＜電解精製＞
　工業的な電気銅製造プロセスにおいては、カソードとアノードとが複数（例えば、各４０～６０枚）装入された電解槽が複数設置されており、銅電解液が電解槽に連続的に供給され、オーバーフローにより連続的に排出される。 <Electrolytic purification>
In an industrial electrolytic copper production process, a plurality of electrolytic cells in which a plurality of cathodes and anodes (for example, 40 to 60 sheets each) are charged are installed, and copper electrolytic solution is continuously supplied to the electrolytic cells. , Is discharged continuously by the overflow.
　本発明の電気銅の製造方法では、電解精製において、電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持しながら電解を行う。このように電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持することで、電解液の液抵抗増加による電圧上昇を抑制することができ、消費電力が減少し、電気銅の製造効率が上がる。また、スライム層がアノード表面に形成される不動態の発生を抑制することができ、銅イオンの溶出が妨害されず、電気銅の製造効率が良好となる。
　特に、増産目的で電流密度を通常より上げる必要がある場合、リサイクル原料が増えるとＮｉ品位が高くなり電流効率が悪くなるが、本発明によれば電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持しながら電解を行うため、このような状況下における電解によっても電気銅の製造効率が良好となる。 In the method for producing electrolytic copper of the present invention, in electrolytic refining, electrolysis is performed while maintaining the Ni concentration in the electrolytic solution at 15 g / L or less. As described above, by maintaining the Ni concentration in the electrolytic solution at 15 g / L or less, a voltage increase due to an increase in the liquid resistance of the electrolytic solution can be suppressed, power consumption is reduced, and the production efficiency of electrolytic copper is increased. In addition, the generation of the passive state in which the slime layer is formed on the anode surface can be suppressed, the elution of copper ions is not disturbed, and the production efficiency of electrolytic copper is improved.
In particular, when it is necessary to increase the current density more than usual for the purpose of increasing production, the Ni grade increases and the current efficiency worsens when the recycling material increases, but according to the present invention, the Ni concentration in the electrolyte is 15 g / L or less. In order to carry out electrolysis while holding it, the production efficiency of electric copper is improved also by electrolysis under such a condition.
　本発明の電気銅の製造方法では、電解精製において、電解液中のＮｉ濃度を１４ｇ／Ｌ以下に保持しながら電解を行うのが好ましく、１３ｇ／Ｌ以下に保持しながら電解を行うのがより好ましく、１２ｇ／Ｌ以下に保持しながら電解を行うのが更により好ましい。特に、電解液中のＮｉ濃度を１２ｇ／Ｌ以下に保持しながら電解を行うことで、後述する電解における電流効率を９７％以上に制御することができる。なお、後工程で過冷却により硫酸Ｎｉとして結晶化させて抜き出すことを考慮する場合は、電解液のＮｉ濃度は低ければ低いほどよいわけではない。 In the method for producing electric copper of the present invention, in the electrolytic refining, it is preferable to carry out the electrolysis while maintaining the Ni concentration in the electrolytic solution at 14 g / L or less, and it is more preferable to carry out the electrolysis while holding at 13 g / L or less It is still more preferable to perform electrolysis, preferably, while keeping it at 12 g / L or less. In particular, by performing electrolysis while maintaining the Ni concentration in the electrolytic solution at 12 g / L or less, the current efficiency in the electrolysis described later can be controlled to 97% or more. In addition, when considering that it is crystallized as Ni sulfate and extracted by overcooling in a post process, the lower the Ni concentration of the electrolytic solution, the better.
　本発明の電気銅の製造方法では、電解精製において、電流密度は特に限定するものでは無く、例えば３００～３６０Ａ／ｍ2とすることができる。 In the method for producing electrolytic copper of the present invention, the current density is not particularly limited in electrolytic purification, and can be, for example, 300 to 360 A / m 2 .
　電解精製における電解液中のＮｉ濃度の制御手段としては、電解液から不純物を除去する一般的な方法を用いることができる。例として、冷凍結晶法によるＮｉ濃度の制御を説明する。具体的には、まず電解液を冷凍結晶槽等に貯めて－１５℃程度で冷却して結晶化させた後、遠心分離機で脱液し、さらに乾燥機で乾燥させることでＮｉを含んだ結晶を得る。電解液として硫酸銅水溶液を用いる場合は、当該Ｎｉを含んだ結晶はＮｉＳＯ4・６Ｈ2Ｏ（硫酸ニッケル六水和物）となっている。続いて、上述の遠心分離機で得られた脱液を、Ｎｉ除去後の電解液として本発明の電気銅の製造方法の電解精製における電解液として使用することができる。電解時の電解液のＮｉ濃度をモニターしておき、必要であれば上記のようにＮｉの除去を行うことで、電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持しながら電解を行うことができる。 As a control means of the Ni concentration in the electrolytic solution in the electrolytic purification, a general method of removing impurities from the electrolytic solution can be used. As an example, control of the Ni concentration by the frozen crystal method will be described. Specifically, first, the electrolytic solution was stored in a frozen crystal tank or the like, cooled at about -15 ° C. to be crystallized, drained by a centrifugal separator, and further dried by a dryer to contain Ni. Get a crystal. In the case of using a copper sulfate aqueous solution as the electrolytic solution, the crystal containing Ni is NiSO 4 .6H 2 O (nickel sulfate hexahydrate). Subsequently, the liquid obtained by the above-mentioned centrifugal separator can be used as an electrolytic solution after Ni removal, in the electrolytic purification of the method for producing electrolytic copper of the present invention. By monitoring the Ni concentration of the electrolyte during electrolysis and removing Ni as described above if necessary, electrolysis can be performed while maintaining the Ni concentration in the electrolyte at 15 g / L or less. it can.
　本発明の電気銅の製造方法では、電解における下記式で規定される電流効率が９６％以上であるのが好ましい。
　電流効率（％）＝（生成された電気銅量／理論電気銅量）×１００
　このような構成により、アノードとして使用する粗銅中のＮｉ濃度が１８００ｐｐｍ以上という高い濃度において、高電流密度下における電解によっても電気銅の製造効率がより良好となる。また、扱う銅原料の許容度（すなわち、銅原料に含まれるＮｉという電気銅生産の阻害元素の許容量）を大きくしながらも銅の需要に合わせた電気銅の増産が可能となる。当該電流効率は９６％以上であるのがより好ましく、９６．５％以上であるのが更により好ましく、９７％以上であるのが更により好ましい。 In the method for producing electrolytic copper of the present invention, the current efficiency defined by the following formula in electrolysis is preferably 96% or more.
Current efficiency (%) = (amount of generated copper / theoretical amount of copper) × 100
With such a configuration, at a concentration as high as 1800 ppm or more of Ni concentration in the crude copper used as an anode, the production efficiency of electric copper becomes better even by electrolysis under high current density. In addition, it is possible to increase the production of electrolytic copper in accordance with the demand for copper while increasing the tolerance of the copper material to be handled (that is, the allowable amount of the inhibiting element of electrolytic copper production called Ni contained in the copper material). The current efficiency is more preferably 96% or more, still more preferably 96.5% or more, and still more preferably 97% or more.
　以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。 Examples of the present invention are given below together with comparative examples, but these examples are provided to better understand the present invention and its advantages, and are not intended to limit the invention.
　（実施例１）
　銅品位９９質量％の板状の粗銅をアノードとし、ステンレス板をカソードとして、以下の条件により電解液中で電解分解を行った。
　・アノードの粗銅中のＮｉ濃度（Ｎｉ品位）：９００～２０００ｐｐｍ
　・電解液の組成：銅４０～６０ｇ／Ｌ、ニッケル１４．１～１４．６ｇ／Ｌ、硫酸：１２０～２２０ｇ／Ｌ、砒素：３～１０ｇ／Ｌ、アンチモン：０．１～０．５ｇ／Ｌ、ビスマス：０．１～０．５ｇ／Ｌ
　・電流密度：３２２Ａ／ｄｍ2 Example 1
Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
・ Ni concentration in crude copper of anode (Ni grade): 900 to 2000 ppm
Composition of electrolyte: 40 to 60 g / L of copper, 14.1 to 14.6 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L
・ Current density: 322A / dm 2
　電解液中のＮｉ濃度はモニターしておき、電解中は常にＮｉ濃度が１４．５ｇ／Ｌ以下に保持されるように制御した。具体的には、必要なときに電解液を取り出して、実施形態でも述べた冷凍結晶法でＮｉ成分を除去し、Ｎｉ濃度が減少した電解液を再び使用することで、電解液のＮｉ濃度が１４．５ｇ／Ｌ以下に保持されるように制御した。 The concentration of Ni in the electrolytic solution was monitored and controlled so that the concentration of Ni was always maintained at 14.5 g / L or less during electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be kept at 14.5 g / L or less.
　また、電解によってカソードに生成した電気銅を採取し、下記式に基づいて電流効率（％）を算出した。
　電流効率（％）＝（生成された電気銅量／理論電気銅量）×１００ Moreover, the electric copper produced | generated at the cathode by electrolysis was extract | collected, and the current efficiency (%) was computed based on the following formula.
Current efficiency (%) = (amount of generated copper / theoretical amount of copper) × 100
　（実施例２）
　銅品位９９質量％の板状の粗銅をアノードとし、ステンレス板をカソードとして、以下の条件により電解液中で電解分解を行った。
　・アノードの粗銅中のＮｉ濃度（Ｎｉ品位）：１０００～２１００ｐｐｍ
　・電解液の組成：銅４０～６０ｇ／Ｌ、ニッケル１３．６～１４．０ｇ／Ｌ、硫酸：１２０～２２０ｇ／Ｌ、砒素：３～１０ｇ／Ｌ、アンチモン：０．１～０．５ｇ／Ｌ、ビスマス：０．１～０．５ｇ／Ｌ
　・電流密度：３２２Ａ／ｄｍ2 (Example 2)
Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
・ Ni concentration in crude copper of anode (Ni grade): 1000 to 2100 ppm
Composition of electrolyte: 40 to 60 g / L of copper, 13.6 to 14.0 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L
・ Current density: 322A / dm 2
　電解液中のＮｉ濃度はモニターしておき、電解中は常にＮｉ濃度が１４．０ｇ／Ｌ以下に保持されるように制御した。具体的には、必要なときに電解液を取り出して、実施形態でも述べた冷凍結晶法でＮｉ成分を除去し、Ｎｉ濃度が減少した電解液を再び使用することで、電解液のＮｉ濃度が１４．０ｇ／Ｌ以下に保持されるように制御した。
　また、実施例１と同様にして電流効率を算出した。 The concentration of Ni in the electrolytic solution was monitored and controlled so that the concentration of Ni was always maintained at 14.0 g / L or less during the electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be kept at 14.0 g / L or less.
Further, the current efficiency was calculated in the same manner as in Example 1.
　（実施例３）
　銅品位９９質量％の板状の粗銅をアノードとし、ステンレス板をカソードとして、以下の条件により電解液中で電解分解を行った。
　・アノードの粗銅中のＮｉ濃度（Ｎｉ品位）：１１００～１９００ｐｐｍ
　・電解液の組成：銅４０～６０ｇ／Ｌ、ニッケル１３．２～１３．５ｇ／Ｌ、硫酸：１２０～２２０ｇ／Ｌ、砒素：３～１０ｇ／Ｌ、アンチモン：０．１～０．５ｇ／Ｌ、ビスマス：０．１～０．５ｇ／Ｌ
　・電流密度：３２２Ａ／ｄｍ2 (Example 3)
Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
・ Ni concentration in crude copper of anode (Ni grade): 1100 to 1900 ppm
Composition of electrolyte: 40 to 60 g / L of copper, 13.2 to 13.5 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L
・ Current density: 322A / dm 2
　電解液中のＮｉ濃度はモニターしておき、電解中は常にＮｉ濃度が１３．４ｇ／Ｌ以下に保持されるように制御した。具体的には、必要なときに電解液を取り出して、実施形態でも述べた冷凍結晶法でＮｉ成分を除去し、Ｎｉ濃度が減少した電解液を再び使用することで、電解液のＮｉ濃度が１３．５ｇ／Ｌ以下に保持されるように制御した。
　また、実施例１と同様にして電流効率を算出した。 The concentration of Ni in the electrolytic solution was monitored and controlled so that the concentration of Ni was always kept at 13.4 g / L or less during the electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be held at 13.5 g / L or less.
Further, the current efficiency was calculated in the same manner as in Example 1.
　（実施例４）
　銅品位９９質量％の板状の粗銅をアノードとし、ステンレス板をカソードとして、以下の条件により電解液中で電解分解を行った。
　・アノードの粗銅中のＮｉ濃度（Ｎｉ品位）：１１００～１９００ｐｐｍ
　・電解液の組成：銅４０～６０ｇ／Ｌ、ニッケル１１．０～１２．０ｇ／Ｌ、硫酸：１２０～２２０ｇ／Ｌ、砒素：３～１０ｇ／Ｌ、アンチモン：０．１～０．５ｇ／Ｌ、ビスマス：０．１～０．５ｇ／Ｌ
　・電流密度：３２２Ａ／ｄｍ2 (Example 4)
Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
・ Ni concentration in crude copper of anode (Ni grade): 1100 to 1900 ppm
Composition of electrolyte: 40 to 60 g / L of copper, 11.0 to 12.0 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L
・ Current density: 322A / dm 2
　電解液中のＮｉ濃度はモニターしておき、電解中は常にＮｉ濃度が１２．０ｇ／Ｌ以下に保持されるように制御した。具体的には、必要なときに電解液を取り出して、実施形態でも述べた冷凍結晶法でＮｉ成分を除去し、Ｎｉ濃度が減少した電解液を再び使用することで、電解液のＮｉ濃度が１２．０ｇ／Ｌ以下に保持されるように制御した。
　また、実施例１と同様にして電流効率を算出した。 The Ni concentration in the electrolytic solution was monitored, and controlled so that the Ni concentration was always maintained at 12.0 g / L or less during the electrolysis. Specifically, the electrolytic solution is taken out when necessary, the Ni component is removed by the frozen crystal method described in the embodiment, and the electrolytic solution having a reduced Ni concentration is used again to obtain the Ni concentration of the electrolytic solution. It was controlled to be held at 12.0 g / L or less.
Further, the current efficiency was calculated in the same manner as in Example 1.
　（比較例１）
　銅品位９９質量％の板状の粗銅をアノードとし、ステンレス板をカソードとして、以下の条件により電解液中で電解分解を行った。
　・アノードの粗銅中のＮｉ濃度（Ｎｉ品位）：１４００～２４００ｐｐｍ
　・電解液の組成：銅４０～６０ｇ／Ｌ、ニッケル１５．５～１７．０ｇ／Ｌ、硫酸：１２０～２２０ｇ／Ｌ、砒素：３～１０ｇ／Ｌ、アンチモン：０．１～０．５ｇ／Ｌ、ビスマス：０．１～０．５ｇ／Ｌ
　・電流密度：３２２Ａ／ｄｍ2 (Comparative example 1)
Electrolytic decomposition was performed in an electrolytic solution under the following conditions, using a plate-like crude copper of 99% by mass of copper grade as an anode and a stainless steel plate as a cathode.
・ Ni concentration in crude copper of anode (Ni grade): 1400 to 2400 ppm
Composition of electrolyte: 40 to 60 g / L of copper, 15.5 to 17.0 g / L of nickel, 120 to 220 g / L of sulfuric acid, 3 to 10 g / L of arsenic, 0.1 to 0.5 g of antimony L, bismuth: 0.1 to 0.5 g / L
・ Current density: 322A / dm 2
　電解液中のＮｉ濃度はモニターしておき、電解中は常にＮｉ濃度が１５．５ｇ／Ｌ以上に保持されるように制御した。
　また、実施例１と同様にして電流効率を算出した。 The concentration of Ni in the electrolyte was monitored and controlled so that the concentration of Ni was always maintained at 15.5 g / L or more during electrolysis.
Further, the current efficiency was calculated in the same manner as in Example 1.
　実施例１～４及び比較例１の評価結果を図１～５に示す。図１は実施例１に係る電解液中のＮｉ濃度１４．１～１４．６ｇ／Ｌにおける電流効率－アノード中Ｎｉ品位のグラフである。図２は実施例２に係る電解液中のＮｉ濃度１３．６～１４．０ｇ／Ｌにおける電流効率－アノード中Ｎｉ品位のグラフである。図３は実施例３に係る電解液中のＮｉ濃度１３．２～１３．５ｇ／Ｌにおける電流効率－アノード中Ｎｉ品位のグラフである。図４は実施例４に係る電解液中のＮｉ濃度１１．０～１２．０ｇ／Ｌにおける電流効率－アノード中Ｎｉ品位のグラフである。図５は比較例１に係る電解液中のＮｉ濃度１５．５～１７．０ｇ／Ｌにおける電流効率－アノード中Ｎｉ品位のグラフである。
　このように、実施例１～３はＮｉを含む粗銅をアノードとして用い、電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持しながら電解を行うことで、アノード中Ｎｉ品位が１８００ｐｐｍ以上と高くても電流効率がいずれも９６％以上と良好であった。
　また、実施例４はＮｉを含む粗銅をアノードとして用い、電解液中のＮｉ濃度を１２ｇ／Ｌ以下に保持しながら電解を行うことで、アノード中Ｎｉ品位が１８００ｐｐｍ以上と高くても電流効率がいずれも９７％以上と良好であった。
　一方、比較例１はＮｉを含む粗銅をアノードとして用い、電解液中のＮｉ濃度を１５ｇ／Ｌを超えて保持しながら電解を行ったため、特にアノード中Ｎｉ品位が１８００ｐｐｍ以上と高い場合、電流効率が９６％を下回った。 The evaluation results of Examples 1 to 4 and Comparative Example 1 are shown in FIGS. FIG. 1 is a graph of current efficiency-grade of Ni in an anode at an Ni concentration of 14.1 to 14.6 g / L in an electrolyte according to Example 1. FIG. FIG. 2 is a graph of current efficiency-grade of Ni in the anode at a Ni concentration of 13.6 to 14.0 g / L in the electrolyte according to Example 2. FIG. 3 is a graph of current efficiency-grade of Ni in the anode at an Ni concentration of 13.2 to 13.5 g / L in the electrolyte according to Example 3. FIG. 4 is a graph of current efficiency-grade of Ni in the anode at an Ni concentration of 11.0 to 12.0 g / L in the electrolytic solution according to Example 4. FIG. 5 is a graph of current efficiency-grade of Ni in the anode at a Ni concentration of 15.5 to 17.0 g / L in the electrolytic solution according to Comparative Example 1.
Thus, in Examples 1 to 3, by performing electrolysis while using crude copper containing Ni as an anode and maintaining the Ni concentration in the electrolytic solution at 15 g / L or less, the grade of Ni in the anode is as high as 1800 ppm or more. Also, the current efficiency was as good as at least 96%.
In Example 4, current efficiency is high even if the Ni grade in the anode is as high as 1800 ppm or more by performing electrolysis using crude copper containing Ni as the anode and maintaining the Ni concentration in the electrolytic solution at 12 g / L or less. All were good with 97% or more.
On the other hand, in Comparative Example 1, electrolysis was performed using crude copper containing Ni as the anode and maintaining the Ni concentration in the electrolyte solution at more than 15 g / L, so current efficiency is particularly high when the grade of Ni in the anode is high Fell below 96%.

Claims (5)

  1. 　Ｎｉを含む粗銅をアノードとして用い、電解液中のＮｉ濃度を１５ｇ／Ｌ以下に保持しながら電解を行う工程を含む電気銅の製造方法。 A method for producing electrolytic copper, comprising the steps of performing electrolysis using crude copper containing Ni as an anode and maintaining the Ni concentration in the electrolytic solution at 15 g / L or less.
  2. 　前記アノード中のＮｉ濃度が１８００ｐｐｍ以上である請求項１に記載の電気銅の製造方法。 The method according to claim 1, wherein the Ni concentration in the anode is at least 1,800 ppm.
  3. 　前記電解を行う工程において、前記電解液中で保持されるＮｉ濃度が１２ｇ／Ｌ以下である請求項１または２に記載の電気銅の製造方法。 The method for producing electric copper according to claim 1 or 2, wherein in the step of performing the electrolysis, the Ni concentration held in the electrolytic solution is 12 g / L or less.
  4. 　前記電解液が硫酸銅水溶液である請求項１～３のいずれか一項に記載の電気銅の製造方法。 The method for producing electrolytic copper according to any one of claims 1 to 3, wherein the electrolytic solution is a copper sulfate aqueous solution.
  5. 　前記電解における下記式で規定される電流効率が９６％以上である請求項１～４のいずれか一項に記載の電気銅の製造方法。
    　電流効率（％）＝（生成された電気銅量／理論電気銅量）×１００     The method for producing electric copper according to any one of claims 1 to 4, wherein the current efficiency defined by the following formula in the electrolysis is 96% or more.
    Current efficiency (%) = (amount of generated copper / theoretical amount of copper) × 100
PCT/JP2018/043288 2017-11-29 2018-11-22 Method for producing electrolytic copper WO2019107287A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0978284A (en) * 1995-09-19 1997-03-25 Nikko Kinzoku Kk Method for purifying copper electrolyte
JP2012092417A (en) * 2010-09-29 2012-05-17 Pan Pacific Copper Co Ltd Treatment method of converter slag, and method for smelting copper
JP2014145093A (en) * 2013-01-28 2014-08-14 Sumitomo Metal Mining Co Ltd Supply device and supply method of an electrolytic solution

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0978284A (en) * 1995-09-19 1997-03-25 Nikko Kinzoku Kk Method for purifying copper electrolyte
JP2012092417A (en) * 2010-09-29 2012-05-17 Pan Pacific Copper Co Ltd Treatment method of converter slag, and method for smelting copper
JP2014145093A (en) * 2013-01-28 2014-08-14 Sumitomo Metal Mining Co Ltd Supply device and supply method of an electrolytic solution

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