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WO2010003906A1 - Procédé de production de cuivre à partir de composés sulfureux - Google Patents

Procédé de production de cuivre à partir de composés sulfureux Download PDF

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Publication number
WO2010003906A1
WO2010003906A1 PCT/EP2009/058446 EP2009058446W WO2010003906A1 WO 2010003906 A1 WO2010003906 A1 WO 2010003906A1 EP 2009058446 W EP2009058446 W EP 2009058446W WO 2010003906 A1 WO2010003906 A1 WO 2010003906A1
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WO
WIPO (PCT)
Prior art keywords
copper
anode
process according
previous
cathode
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.)
Ceased
Application number
PCT/EP2009/058446
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English (en)
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
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Filing date
Publication date
Application filed by Universite Libre de Bruxelles ULB filed Critical Universite Libre de Bruxelles ULB
Publication of WO2010003906A1 publication Critical patent/WO2010003906A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
  • a certain amount of iron sulphide is transferred to the slag in the form of iron oxide so that the resulting matte is enriched in copper.
  • SO2 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 SO2 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.
  • the document US-A-3, 616, 340 discloses a method to refine impure molten copper.
  • sulphur is removed from impure molten copper placed at the cathode of an electrolytic cell.
  • the anode in this process is inert, and copper is not transferred from one electrode to the other.
  • the aim of this process is the removal of small amount of impurities from molten copper cathode.
  • This document does not disclose a process able to refine copper directly from copper matte.
  • 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 SO2 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. Summary of the Invention
  • 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: the molten salt is selected from the group consisting of NaF, AIF3, CuCl and NaCl or mixing thereof; the raw material used for said molten salt is cryolithe; - the anodic dissolution process generates elemental sulphur as a by-product at the anode; the process temperature is higher than copper melting temperature (1085 0 C) . the recovered copper metal has a purity higher than 99%; precious metals of the group consisting of Ag, Au, Pt, Pd are recovered at the anode.
  • heating is mainly obtained by the joule effect produced by electrolysis current; the process is performed continuously the surfaces of the anode container in contact with the electrolyte essentially consists of a nitride refractory compound, preferably, said surfaces of the anode container are obtained by coating the surface with a nitride refractory compound, and preferably, said nitride compound is boron nitride and/or silicon nitride; - the anode container essentially consists of a nitride refractory compound, preferably, boron nitride and/or silicon nitride.
  • 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. [0020] To achieve the process of the present invention, it is necessary to use temperatures above the melting temperature of both CU2S and metallic copper, so that the cathode is in the form of liquid copper, and the anode is in the form of liquid copper sulphide (possibly containing other impurities, such as other metal sulphides) .
  • 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 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.
  • Example 1 A graphite crucible 10 of 4500 cm 3 capacity, that acted as container and contact for a molten cathode 2, was filled with 6Kg of a salt mixture 3 of cryolite (60%Wt Na 3 AlF 6 ) and sodium chloride (40%Wt NaCl), (See Fig. 2) [0027] The crucible was heated in an induction furnace. The salt mixture was melted at 780 0 C.
  • An anode container 11 was fabricated in graphite to contain the liquid CU2S. Once the salt mixture was melted at 780 0 C the anode container 11 filled up with CU2S was completely immersed, the temperature was increased up to 1180 0 C and the liquid CU2S anode 1 was 2cm under the electrolyte level. The surface of the liquid CU2S anode 1 in contact with the electrolyte was of 68cm 2 ' [0029] When the temperature was stabilized a potential of 2 V and a current of IOOA was applied for 120 minutes. The current density calculated from the anode surface was 147 A/dm 2 and no anode effect was detected.
  • a graphite crucible 10 of 300cm3 capacity that acted as cathode was filled with 320gr of a salt mixture of cryolite (80%Wt Na3AlF6) and sodium chloride (20%Wt NaCl), (See Fig. 3)
  • a cleaning electrolysis was performed to eliminate 0-2 ions and others impurities from the electrolyte.
  • the crucible was heated in an induction furnace .
  • the salt mixture was melted at 1000 0 C and a graphite rod of lcm diameter that acted as anode was immersed in the liquid bath.
  • the cleaning electrolysis was performed until a potential rise that indicates the beginning of electrolyte decomposition was observed.
  • the graphite anode was removed and replaced by a Boron Nitride anode container 12 filled with Cu2S and completely immersed into the electrolyte (See Fig. 3) .
  • the anode contact 4 was insulated from the electrolyte bath by means of an insulating jacket 13 made of boron nitride. The temperature was increased up to 1200 0 C. The surface of the liquid Cu2S pool in contact with the electrolyte was 4.12 10 ⁇ 2 dm 2 [0037] When the temperature was stabilized electrolysis was performed at a potential of 2 V and a current of 5A during 50 minutes. The current density calculated from the anode surface was 121A/dm 2 . [0038] Once the electrolysis process finished the anode was removed from the bath and the current efficiency of the electrolysis was estimated to be approximately to 55%. Figure Keys
  • Liquid anode (copper sulphide containing metal matte)

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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

La présente invention concerne un procédé de production de cuivre à partir d’une matte de forme liquide placée au pôle positif dans une cellule électrolytique. L’électrolyte de ladite cellule comprend du sel fondu, et du cuivre liquide est produit au pôle négatif.
PCT/EP2009/058446 2008-07-11 2009-07-03 Procédé de production de cuivre à partir de composés sulfureux Ceased WO2010003906A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08160260A EP2143827A1 (fr) 2008-07-11 2008-07-11 Procédé pour la production de cuivre à partir de composés de soufre
EP08160260.9 2008-07-11

Publications (1)

Publication Number Publication Date
WO2010003906A1 true WO2010003906A1 (fr) 2010-01-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/058446 Ceased WO2010003906A1 (fr) 2008-07-11 2009-07-03 Procédé de production de cuivre à partir de composés sulfureux

Country Status (2)

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EP (1) EP2143827A1 (fr)
WO (1) WO2010003906A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110863218B (zh) * 2019-11-27 2021-11-30 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 (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4828658A (en) * 1987-04-21 1989-05-09 Aluminium Pechiney Process for the preparation of mother alloys of iron and neodymium by electrolysis of oxygen-bearing salts in a medium of molten fluorides
WO2004044268A2 (fr) * 2002-11-14 2004-05-27 Moltech Invent S.A. Production de materiau contenant de l'hematite

Family Cites Families (1)

* 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4828658A (en) * 1987-04-21 1989-05-09 Aluminium Pechiney Process for the preparation of mother alloys of iron and neodymium by electrolysis of oxygen-bearing salts in a medium of molten fluorides
WO2004044268A2 (fr) * 2002-11-14 2004-05-27 Moltech Invent S.A. Production de materiau contenant de l'hematite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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 *

Also Published As

Publication number Publication date
EP2143827A1 (fr) 2010-01-13

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