WO2020050418A1 - 電気銅の製造方法 - Google Patents

電気銅の製造方法 Download PDF

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Publication number
WO2020050418A1
WO2020050418A1 PCT/JP2019/035274 JP2019035274W WO2020050418A1 WO 2020050418 A1 WO2020050418 A1 WO 2020050418A1 JP 2019035274 W JP2019035274 W JP 2019035274W WO 2020050418 A1 WO2020050418 A1 WO 2020050418A1
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WO
WIPO (PCT)
Prior art keywords
copper
electrolytic
concentration
anode
electrolytic solution
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PCT/JP2019/035274
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English (en)
French (fr)
Japanese (ja)
Inventor
邦男 渡辺
惇貴 佐渡
Original Assignee
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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Publication date
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 JP2020541325A priority Critical patent/JP7041275B2/ja
Priority to CN201980057957.0A priority patent/CN112654736B/zh
Publication of WO2020050418A1 publication Critical patent/WO2020050418A1/ja

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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
    • 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 for producing electrolytic copper.
  • copper is leached from a raw material such as ore into a solution and electrolytically reduced to metal to obtain electrolytic copper by electrolytic copper refining. More specifically, raw materials such as ores are refined to produce crude copper, which is used as an anode for electrolytic purification in an electrolytic solution.
  • Patent Document 1 In recent years, there has been an increasing need to use recycled products such as electronic devices (mainly scrap copper) as raw materials for electrolytic copper extraction and recover copper from the recycled products.
  • crude copper used as an anode in copper electrolytic refining contains impurities such as arsenic, bismuth, antimony, and nickel, and these impurities elute into the electrolytic solution.
  • Antimony contained as impurities in the blister copper (anode) forms Sb 2 O 5 as floating slime in the electrolytic solution during electrolysis. If the floating slime derived from antimony is formed in the electrolytic solution, it will adhere to the cathode. When floating slime derived from antimony adheres to the cathode, there is a problem that antimony is taken into electrolytic copper and the quality of electrolytic copper deteriorates. Further, since floating slime adheres to the surface of the cathode, a starting point of a hump occurs on the surface of the cathode. If the electrolysis is continued, current concentrates on the starting point of the floating slime adhering to the cathode, and the electrodeposit may extend to the anode, possibly causing a short circuit, and the production efficiency of electrolytic copper is reduced.
  • the inventors of the present invention have conducted various studies in order to solve the above-mentioned problems, and found that by controlling the concentration of antimony in the electrolytic solution in copper electrolytic refining, even if the concentration of antimony in the blister copper used as the anode was high, the It has been found that copper production efficiency is improved.
  • the present invention which has been completed on the basis of the above findings, includes, in one aspect, a step of performing electrolysis while using a blister copper containing Sb as an anode and maintaining the Sb concentration in an electrolytic solution at 0.25 g / L or less, This is a method for producing electrolytic copper in which the Sb concentration in the anode is 200 ppm or more.
  • the electrolytic solution is an aqueous copper sulfate solution.
  • the current efficiency in the electrolysis defined by the following formula is 96% or more.
  • Current efficiency (%) (amount of generated copper / theoretical copper) ⁇ 100
  • the present invention it is possible to provide a method for producing electrolytic copper in which the production efficiency is improved even when the concentration of antimony in blister copper used as an anode is high.
  • 4 is a graph of current efficiency versus Sb quality in an anode according to Example 1.
  • 4 is a graph of current efficiency versus Sb quality in an anode according to Comparative Example 1.
  • the anode used for electrolytic refining in the electrolytic copper production method according to the present invention typically oxidizes blister copper having a copper grade of about 93 to 99% by mass or 97 to 99% by mass obtained in a converter step. It is cast after smelting and reduction treatment, and is usually plate-shaped.
  • the blister copper of the anode contains Sb as an impurity.
  • the Sb concentration in the blister copper is, for example, 200 ppm or more, 270 ppm or more, or 350 ppm or more. There may be.
  • impurities such as Ni, As, Bi, and Sb may be contained in the blister copper.
  • the cathode used for electrolytic refining in the method for producing electrolytic copper according to the present invention is not limited, and in addition to the method using a seed plate, a permanent electrodepositing copper on the surface using a stainless steel plate
  • An example is a method called a cathode method (PC method).
  • PC method cathode method
  • the material of the permanent cathode but titanium or stainless steel is generally used because it is insoluble in the electrolytic solution, and stainless steel is preferably used because the 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 hardening stainless steel may be used.
  • a sulfuric acid-based electrolytic solution can be used in order to perform electrolytic refining of copper.
  • an aqueous solution of copper sulfate is preferably used as the electrolytic solution.
  • the sulfuric acid concentration is in the range of 120-220 g / L and the Cu ion concentration is in the range of 40-60 g / L.
  • the sulfuric acid concentration ranges from 160 to 180 g / L and the Cu ion concentration ranges from 45 to 55 g / L.
  • an additive is generally added to the electrolytic solution.
  • the additive is used for improving the state of copper deposition on the cathode plate.
  • an additive that forms a protective colloid such as glue, gelatin, and lignin (pulp waste liquid), and an organic substance having a functional group such as thiourea or aloin are commonly used.
  • glue, gelatin, and lignin pulp waste liquid
  • lignin lignin
  • an organic substance having a functional group such as thiourea or aloin
  • ⁇ Electrolytic refining> In an industrial electrolytic copper manufacturing process, a plurality of electrolytic cells in which a plurality of cathodes and anodes (for example, 40 to 60 sheets each) are installed are provided, and a copper electrolytic solution is continuously supplied to the electrolytic cells. , Are continuously discharged by overflow.
  • electrolysis in electrolytic refining, electrolysis is performed while maintaining the Sb concentration in the electrolytic solution at 0.25 g / L or less.
  • Sb concentration in the electrolytic solution at 0.25 g / L or less as described above, it is possible to suppress a voltage increase due to an increase in the liquid resistance of the electrolytic solution, reduce power consumption, and improve the production efficiency of electrolytic copper. Go up.
  • the formation of floating slime of antimony can be suppressed, and as a result, poor electrodeposition of copper can be suppressed, and the production efficiency of copper can be improved.
  • the electrolytic refining in the electrolytic refining, it is preferable to perform electrolysis while maintaining the Sb concentration in the electrolytic solution at 0.22 g / L or less. More preferably, it is performed. By performing such control, the possibility of occurrence of bumps on the surface of the electrolytic copper is reduced, and electrolytic copper having a smooth surface can be stably manufactured.
  • the current density is not particularly limited, and may be, for example, 300 to 360 A / m 2 .
  • a general method for removing impurities from the electrolytic solution can be used.
  • control of the Sb concentration by a method using a chelate resin will be described. Specifically, an electrolytic solution is passed through a resin tower filled with a chelate resin, and Sb in the electrolytic solution is adsorbed on the chelate resin. After completion of the adsorption step, hydrochloric acid is passed through to elute Sb adsorbed on the resin. The Sb dissolved in the eluent is neutralized with slaked lime and then dehydrated, and removed out of the system as a neutralized chelate slag.
  • the electrolytic solution after the Sb is adsorbed on the chelate resin can be used as the electrolytic solution after the removal of Sb in the electrolytic refining of the method for producing electrolytic copper of the present invention.
  • the Sb concentration of the electrolytic solution at the time of electrolysis is monitored, and if necessary, Sb is removed as described above, thereby performing electrolysis while maintaining the Sb concentration in the electrolytic solution at 0.25 g / L or less. be able to.
  • the current efficiency in the electrolysis defined by the following formula is 96% or more.
  • Current efficiency (%) (amount of generated copper / theoretical copper) ⁇ 100
  • the current efficiency is more preferably 96% or more, even more preferably 96.5% or more, and even more preferably 97% or more.
  • Electrolysis was performed in an electrolytic solution under the following conditions using a plate-shaped crude copper having a copper grade of 99% by mass as an anode and a stainless steel plate as a cathode.
  • -Composition of electrolytic solution copper 40 to 60 g / L, nickel 15.5 to 17.0 g / L, sulfuric acid: 120 to 220 g / L, arsenic: 3 to 10 g / L, antimony: 0.23 to 0.25 g / L L, bismuth: 0.1-0.5 g / L ⁇ Current density: 320 to 322 A / m 2
  • the Sb concentration in the electrolytic solution was monitored and controlled so that the Sb concentration was always maintained at 0.25 g / L or less during electrolysis. Specifically, the electrolyte solution is taken out when necessary, the Sb component is removed by the chelate resin method described in the embodiment, and the electrolyte solution having a reduced Sb concentration is used again, so that the Sb concentration of the electrolyte solution is reduced. It controlled so that it might be maintained at 0.25 g / L or less.
  • Electrolysis was performed in an electrolytic solution under the following conditions using a plate-shaped crude copper having a copper grade of 99% by mass as an anode and a stainless steel plate as a cathode.
  • -Composition of electrolytic solution copper 40 to 60 g / L, nickel 15.5 to 17.0 g / L, sulfuric acid: 120 to 220 g / L, arsenic: 3 to 10 g / L, antimony: 0.26 to 0.29 g / L L, bismuth: 0.1-0.5 g / L ⁇ Current density: 320 to 322 A / m 2
  • the Sb concentration in the electrolytic solution was monitored and controlled so that the Sb concentration was always maintained at 0.26 g / L or more during electrolysis.
  • the current efficiency was calculated in the same manner as in Example 1.
  • FIGS. 1 and Comparative Example 1 are shown in FIGS.
  • FIG. 1 is a graph showing the relationship between the current efficiency and the Sb quality in the anode when the Sb concentration in the electrolytic solution according to Example 1 is 0.23 to 0.25 g / L. More specifically, as shown in Table 1, the current efficiency in FIG. 1 indicates the average current efficiency for each Sb grade in the anode.
  • FIG. 2 is a graph showing current efficiency versus Sb quality in the anode when the Sb concentration in the electrolytic solution according to Comparative Example 1 is 0.26 to 0.29 g / L.
  • Example 1 uses blister copper containing Sb as the anode and performs electrolysis while maintaining the Sb concentration in the electrolytic solution at 0.25 g / L or less, so that the Sb quality in the anode exceeds 200 ppm. There was no change in current efficiency, and the average current efficiency during the operation period was as good as 96% or more even when it was as high as 270 ppm or more. Further, no bumps were generated due to SS (suspension substance) in which Sb was formed in the manufactured electrolytic copper. On the other hand, Comparative Example 1 is a case in which blister copper containing Sb was used as the anode and electrolysis was performed while maintaining the Sb concentration in the electrolytic solution at more than 0.25 g / L.
  • the higher the Sb grade in the anode the higher the current.
  • the current efficiency tends to decrease when the Sb grade in the anode is 200 ppm or more.
  • the efficiency is high as 270 ppm or more, the current efficiency decreases. The result was less than 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)
PCT/JP2019/035274 2018-09-07 2019-09-06 電気銅の製造方法 WO2020050418A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2020541325A JP7041275B2 (ja) 2018-09-07 2019-09-06 電気銅の製造方法
CN201980057957.0A CN112654736B (zh) 2018-09-07 2019-09-06 电解铜的制造方法

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JP2018-167957 2018-09-07
JP2018167957 2018-09-07

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5414052B2 (zh) * 1970-05-28 1979-06-04
JPS54119327A (en) * 1977-10-11 1979-09-17 Outokumpu Oy Selective removal of antimony and bismuth from electrolysis solution
JP2007231363A (ja) * 2006-03-01 2007-09-13 Nikko Kinzoku Kk 銅の電解精製方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1028658C (zh) * 1992-12-02 1995-05-31 北京有色金属研究总院 一种铜电解液净化的工艺方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5414052B2 (zh) * 1970-05-28 1979-06-04
JPS54119327A (en) * 1977-10-11 1979-09-17 Outokumpu Oy Selective removal of antimony and bismuth from electrolysis solution
JP2007231363A (ja) * 2006-03-01 2007-09-13 Nikko Kinzoku Kk 銅の電解精製方法

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JPWO2020050418A1 (ja) 2021-05-13
CN112654736A (zh) 2021-04-13
CN112654736B (zh) 2024-01-16
JP7041275B2 (ja) 2022-03-23

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