WO2019107287A1 - Procédé de production de cuivre électrolytique - Google Patents

Procédé de production de cuivre électrolytique 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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WO
WIPO (PCT)
Prior art keywords
copper
concentration
electrolytic
anode
electrolytic solution
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PCT/JP2018/043288
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English (en)
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2018167944A external-priority patent/JP6816076B2/ja
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/zh
Publication of WO2019107287A1 publication Critical patent/WO2019107287A1/fr

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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%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

L'invention concerne un procédé de production de cuivre électrolytique qui donne une bonne efficacité de production même à des concentrations élevées en nickel dans le cuivre brut utilisé en tant qu'anode. Le procédé de production de cuivre électrolytique comprend une étape de réalisation d'une électrolyse à l'aide de cuivre brut contenant du Ni pour une anode tout en maintenant la concentration de Ni dans la solution d'électrolyse ne dépassant pas 15 g/l.
PCT/JP2018/043288 2017-11-29 2018-11-22 Procédé de production de cuivre électrolytique WO2019107287A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201880034523.4A CN110662857A (zh) 2017-11-29 2018-11-22 电解铜的制造方法

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Application Number Priority Date Filing Date Title
JP2017229662 2017-11-29
JP2017-229662 2017-11-29
JP2018167944A JP6816076B2 (ja) 2017-11-29 2018-09-07 電気銅の製造方法
JP2018-167944 2018-09-07

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WO2019107287A1 true WO2019107287A1 (fr) 2019-06-06

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0978284A (ja) * 1995-09-19 1997-03-25 Nikko Kinzoku Kk 銅電解液の浄液方法
JP2012092417A (ja) * 2010-09-29 2012-05-17 Pan Pacific Copper Co Ltd 転炉スラグの処理方法及び銅の製錬方法
JP2014145093A (ja) * 2013-01-28 2014-08-14 Sumitomo Metal Mining Co Ltd 電解液の給液装置および給液方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0978284A (ja) * 1995-09-19 1997-03-25 Nikko Kinzoku Kk 銅電解液の浄液方法
JP2012092417A (ja) * 2010-09-29 2012-05-17 Pan Pacific Copper Co Ltd 転炉スラグの処理方法及び銅の製錬方法
JP2014145093A (ja) * 2013-01-28 2014-08-14 Sumitomo Metal Mining Co Ltd 電解液の給液装置および給液方法

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