EP2143827A1 - Verfahren zur Herstellung von Kupfer aus Sulfidverbindungen - Google Patents

Verfahren zur Herstellung von Kupfer aus Sulfidverbindungen Download PDF

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Publication number
EP2143827A1
EP2143827A1 EP08160260A EP08160260A EP2143827A1 EP 2143827 A1 EP2143827 A1 EP 2143827A1 EP 08160260 A EP08160260 A EP 08160260A EP 08160260 A EP08160260 A EP 08160260A EP 2143827 A1 EP2143827 A1 EP 2143827A1
Authority
EP
European Patent Office
Prior art keywords
copper
anode
cathode
previous
matte
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.)
Withdrawn
Application number
EP08160260A
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English (en)
French (fr)
Inventor
Luc Segers
Henry Wilson Choque Huyhua
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universite Libre de Bruxelles ULB
Original Assignee
Universite Libre de Bruxelles ULB
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.)
Filing date
Publication date
Application filed by Universite Libre de Bruxelles ULB filed Critical Universite Libre de Bruxelles ULB
Priority to EP08160260A priority Critical patent/EP2143827A1/de
Priority to PCT/EP2009/058446 priority patent/WO2010003906A1/en
Publication of EP2143827A1 publication Critical patent/EP2143827A1/de
Withdrawn legal-status Critical Current

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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
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • 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

Definitions

  • the present invention is related to a process for the production of copper and sulphur from copper sulphide compounds.
  • the pyrometallurgical routes to produce copper from sulphide containing raw or secondary materials consist generally of two main steps described hereafter.
  • a first step the materials are melted in such conditions that a sulphide melt is produced, called matte (composition belonging mainly to the binary Cu 2 S-FeS system), which is liquid at working temperature and separates from the slag.
  • matte composition belonging mainly to the binary Cu 2 S-FeS system
  • iron sulphide is transferred to the slag in the form of iron oxide so that the resulting matte is enriched in copper.
  • SO 2 is produced and generally used to produce sulphuric acid.
  • a matte is generally defined, in the field of pyrometallurgy, as the molten metal sulfide phases typically formed during smelting of copper, nickel, and other base metals.
  • an oxidation atmosphere is produced by air, enriched air or pure oxygen in order to transform copper sulphide into copper and iron sulphide into iron oxide dissolved in a silicate slag. It is generally a batch process generating large amounts of SO 2 containing gases. In batch mode, the slag is poured several times. The slag returns to the matte smelting furnace (first step) to recover copper losses and the copper phase (called blister ( ⁇ 97%Cu) is further processed for refining processing.
  • Electrochemical alternative methods have also been described in prior art for the converting of Copper.
  • the document US3326644 describes a process for the electrolytic deposition of copper from a molten salt electrolyte mixture.
  • eutectic mixtures of chloride salts such as KCl/NaCl are used to minimise the cell temperature, which is comprised between 800 and 900°C.
  • the copper deposit is in the form of intermeshed filaments having a "wool-like" appearance. This structure needs to be washed out with water before further processing in order to get rid of the salts which are trapped by capillary forces when getting the deposit out of the electrolyte.
  • the present invention aims to provide a process for the production of copper from copper sulphide containing matte.
  • the present invention further aims to reduce the emission of pollutant such as SO 2 in the production process of copper from copper sulphide containing matte.
  • the present invention also aims to provide a process for the production of copper from copper sulphide containing matte wherein the sulphur by-products can be valued at least partly in its elemental chemical form.
  • the present invention further aims to provide copper in the liquid form, without the drawbacks of the solid deposit.
  • the present invention discloses an anodic dissolution process at high temperature for the electrowinning of copper from a matte comprising Cu 2 S, said process comprising the steps of:
  • the invention further discloses at least one or a suitable combination of the following features:
  • Fig. 1 represents a particular arrangement for an industrial electrolytic cell suitable for performing the production process of the present invention.
  • Fig. 2 represents the electrolytic cell arrangement of the example.
  • the basic step of the present invention is the conversion of copper sulphide containing matte into copper and elemental sulphur by electrolysis in fused salts, using liquid cathodes and anodes. Copper is produced at the cathode of a cell and refined afterwards if necessary by conventional methods used for blister copper. Sulphur is removed at the anode as a separate product, in its elemental form.
  • the cathode is in the form of liquid copper
  • the anode is in the form of liquid Sulphide copper (possibly containing other impurities, such as other metal sulphides).
  • This has several advantages, such as the possibility to work at high current density and avoiding the appearance of spikes on the electrode surfaces. Those spikes producing particular inhomogeneous current densities, which can be detrimental to the process control.
  • there is no need for a washing step as described in US3326644 the copper being directly drawn off from the cell in the liquid from, no impurities being included by capillary forces.
  • the sulphide compounds can be continuously fed in the molten anode, rendering the process particularly suitable for a continuous operation.
  • the melting temperature of copper is higher than the vaporisation temperature of sulphur, sulphur escapes from the bath in gaseous form, avoiding the passivation of the anode which is the case with low temperature processes such as those in aqueous solution.
  • the fused salt comprises a mixture of fluoride salts such as NaF and AlF 3 .
  • a particular composition could be that of cryolite (Na 3 AlF 6 ).
  • the process was further improved by the addition of chloride salts, such as NaCl and CuCl.
  • the process is used for the recovery of copper from white metal.
  • Said white metal is a matte almost free of iron.
  • the white metal is first produced by a conventional method using state of the art pyrometallurgical processes. Then, the white metal 9 is fed into an anodic container, and said white metal is melted, forming a liquid anode 1.
  • An electrolytic cell is used containing the fused salt 3 at the desired temperature, where copper from the anode 1 is dissolved by passing a direct current in the cell between the anode and the cathode 2. Liquid copper is deposited at the cathode 2.
  • a continuous process is used essentially without external heating, the heating being produced by joule effect due to the electrolytic current. If necessary, for example at initial melting, additional heating can be provided by means of heater 7.
  • Undissolved impurities from the anode 1 such as precious metals (Ag, Au, Pt, Pd%) are additionally recovered from the anode 1.
  • FIG. 1 represents a particular arrangement of an industrial electrolytic cell suitable for performing the process of the present invention.
  • the copper sulphide containing matte 9 is fed through an inlet at the liquid anode 1.
  • This anode 1 is connected to the positive pole of a current source by means of an anode contact 4.
  • liquid copper forms the cathode 2, and is connected to the negative pole of the current source by means of a cathode contact 5.
  • Both electrodes are separated by insulating refractory 6, the insulating refractory being suitable for being maintained in contact with the electrolyte at process temperature.
  • boron nitride or boron nitride coated parts could be used.
  • the crucible was heated in an induction furnace.
  • the salt mixture was melted at 780°C.
  • An anode container 11 was fabricated in graphite to contain the liquid Cu 2 S. Once the salt mixture was melted at 780 °C the anode container 11 filled up with Cu 2 S was completely immersed, the temperature was increased up to 1180 °C and the liquid Cu 2 S anode 1 was 2cm under the electrolyte level. The surface of the liquid Cu 2 S anode 1 in contact with the electrolyte was of 68 cm 2 .
  • the anode container was removed from the bath and the casting of the overall melt (electrolyte + liquid copper) was made to allow cooling.

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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)
EP08160260A 2008-07-11 2008-07-11 Verfahren zur Herstellung von Kupfer aus Sulfidverbindungen Withdrawn EP2143827A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08160260A EP2143827A1 (de) 2008-07-11 2008-07-11 Verfahren zur Herstellung von Kupfer aus Sulfidverbindungen
PCT/EP2009/058446 WO2010003906A1 (en) 2008-07-11 2009-07-03 Process for the production of copper from sulphide compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08160260A EP2143827A1 (de) 2008-07-11 2008-07-11 Verfahren zur Herstellung von Kupfer aus Sulfidverbindungen

Publications (1)

Publication Number Publication Date
EP2143827A1 true EP2143827A1 (de) 2010-01-13

Family

ID=40076589

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08160260A Withdrawn EP2143827A1 (de) 2008-07-11 2008-07-11 Verfahren zur Herstellung von Kupfer aus Sulfidverbindungen

Country Status (2)

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EP (1) EP2143827A1 (de)
WO (1) WO2010003906A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110863218A (zh) * 2019-11-27 2020-03-06 东北大学 一种采用熔盐电解富集提取金的方法
KR102493791B1 (ko) * 2022-06-20 2023-02-06 한국지질자원연구원 용융염 전해제련법을 이용한 휘동광으로부터 구리 및 단체황 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3326644A (en) 1963-12-12 1967-06-20 American Metal Climax Inc Electrowinning copper and product thereof
US3616340A (en) * 1969-07-14 1971-10-26 Kennecott Copper Corp Refining of liquid copper
US3777011A (en) * 1970-10-02 1973-12-04 Int Erfinder & Patentanstalt Process for extracting metal plating,scrap or ore in a fused electrolyte cell
US4405415A (en) * 1980-10-07 1983-09-20 Alcan International Limited Electrolytic refining of molten metal

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2614319B1 (fr) * 1987-04-21 1989-06-30 Pechiney Aluminium Procede de preparation d'alliages mere de fer et de neodyme par electrolyse de sels oxygenes en milieu fluorures fondus.
AU2003280106A1 (en) * 2002-11-14 2004-06-03 Moltech Invent S.A. The production of hematite-containing material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3326644A (en) 1963-12-12 1967-06-20 American Metal Climax Inc Electrowinning copper and product thereof
US3616340A (en) * 1969-07-14 1971-10-26 Kennecott Copper Corp Refining of liquid copper
US3777011A (en) * 1970-10-02 1973-12-04 Int Erfinder & Patentanstalt Process for extracting metal plating,scrap or ore in a fused electrolyte cell
US4405415A (en) * 1980-10-07 1983-09-20 Alcan International Limited Electrolytic refining of molten metal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BERTRAM ET AL.: "Trans. Instn. Min. Metall.", C: MINERAL PROCESS. EXTR. METALL., 1983
BERTRAM R ET AL: "Anodic dissolution of Copper Sulphide Ores in Molten ZnCl2-KCl", TRANSACTIONS OF THE INSTITUTE OF MINING AND METALLURGY,, 1 January 1983 (1983-01-01), pages C169 - C171, XP009109791 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110863218A (zh) * 2019-11-27 2020-03-06 东北大学 一种采用熔盐电解富集提取金的方法
KR102493791B1 (ko) * 2022-06-20 2023-02-06 한국지질자원연구원 용융염 전해제련법을 이용한 휘동광으로부터 구리 및 단체황 제조 방법

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WO2010003906A1 (en) 2010-01-14

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