WO2009030811A1 - Procédé de valorisation d'un concentré de cuivre - Google Patents

Procédé de valorisation d'un concentré de cuivre Download PDF

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Publication number
WO2009030811A1
WO2009030811A1 PCT/FI2008/050483 FI2008050483W WO2009030811A1 WO 2009030811 A1 WO2009030811 A1 WO 2009030811A1 FI 2008050483 W FI2008050483 W FI 2008050483W WO 2009030811 A1 WO2009030811 A1 WO 2009030811A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
concentrate
zinc
leaching
leach
Prior art date
Application number
PCT/FI2008/050483
Other languages
English (en)
Inventor
Jari Tiihonen
Heikki Takala
Jaakko Leppinen
Original Assignee
Outotec Oyj
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 Outotec Oyj filed Critical Outotec Oyj
Priority to CN200880105783.2A priority Critical patent/CN101796204B/zh
Priority to EA201000293A priority patent/EA017095B1/ru
Priority to CA2697187A priority patent/CA2697187C/fr
Publication of WO2009030811A1 publication Critical patent/WO2009030811A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/0004—Preliminary treatment without modification of the copper constituent
    • C22B15/0008—Preliminary treatment without modification of the copper constituent by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts 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 invention relates to a method for the preparation of a copper concentrate suitable for pyrometallurgical treatment from a concentrate in which zinc is present as an impurity.
  • zinc is leached from the concentrate with a solution containing sulphuric acid in oxidising conditions at atmospheric temperature and pressure.
  • the conditions are regulated to be such that any copper that may have dissolved will be precipitated.
  • Complex copper sulphide concentrates contain other non-ferrous metals besides copper, such as zinc.
  • sulphide concentrate intended for pyrometallurgical recovery of copper contains zinc, for example, it complicates the process.
  • the zinc contained in the concentrate evaporates and enters the fine dust as zinc oxide, from which it should be recovered separately.
  • Current smelters charge a penalty for impurities in concentrate, for instance the zinc content of copper concentrate should be below 3%.
  • Another method is to treat the concentrate first at such a temperature that the zinc vaporises and is recovered as zinc oxide, after which the copper concentrate can be processed further in the desired way.
  • This kind of method is described in e.g. patent CN 1288966. If the further processing of the concentrate takes place pyrometallurgically, the method requires the construction of two furnace units. Additionally, one disadvantage is the formation of sulphur dioxide, which necessitates its own processing equipment.
  • US patent publication 4,260,588 describes a way to handle the upgrading of a complex copper sulphide concentrate.
  • the concentrate is leached with a copper-containing chloride solution at an elevated temperature and pressure at a pH value of about 3.
  • a sulphidic concentrate containing copper and iron is obtained and the other non-ferrous metals contained in the complex concentrate such as zinc, nickel and cobalt are recovered from the leach.
  • the method appears fairly complicated and costly.
  • Another fact that could be regarded as a drawback is that the chlorides need to be removed from the concentrate meticulously, so that they do not cause problems in further processing of the concentrate.
  • the purpose of the invention is to achieve a method for upgrading copper sulphide concentrate containing zinc by removing the zinc from the concentrate, so that the concentrate is suitable for the pyrometallurgical recovery of copper.
  • the invention relates to a method for upgrading copper sulphide concentrate containing zinc by removing the zinc from the concentrate, so that the concentrate is suitable for the pyrometallurgical recovery of copper. It is typical of the method that zinc is removed from the concentrate by leaching the concentrate with a solution containing sulphuric acid at atmospheric pressure and temperature, firstly in oxidising conditions and that before the end of the leach, a reducing agent is fed into the leaching stage to precipitate out the dissolved copper. It is typical of the method accordant with the invention that the sulphuric acid concentration at the end of the leaching stage is regulated to the region of 0- 100 g/l, preferably 5 - 25 g/l.
  • the oxidising agent used is a gas, which is at least one of the following: air, oxygen-enriched air and oxygen.
  • the oxidising agent used is at least one of the following: hydrogen peroxide, manganese dioxide and potassium permanganate.
  • the redox potential is adjusted so that there is a minimum of 10 mg/l of copper at the start of the leach and that at the end of the leach there is no copper in the solution.
  • the reducing agent to be fed into the end of the leaching stage is a reducing gas.
  • the gas is typically hydrogen sulphide.
  • the reducing agent to be fed into the end of the leaching stage is sodium hydrosulphide or sodium sulphide.
  • the reducing agent to be fed into the end of the leaching stage is copper sulphide concentrate. It is typical of the method accordant with the invention that there is a minimum of 0.1 g/l of iron and at least 10 mg/l of copper in the solution at the start of the leach.
  • a copper sulphide concentrate containing zinc is routed to leaching, with the aim of leaching such an amount of zinc from the concentrate that the concentrate is suitable for pyrometallurgical processing.
  • Leaching is sulphate-based and occurs in atmospheric conditions. Atmospheric conditions means leaching that takes place in unpressurised reactors and at a temperature that is at the most 105 0 C.
  • the copper sulphide concentrate is mainly a primary copper sulphide such as chalcopyrite and does not substantially contain secondary sulphides. Chalcopyrite does not dissolve substantially in conditions where zinc is leached from the concentrate.
  • Zinc-containing copper sulphide concentrate is fed into a solution containing sulphuric acid, in which the acid concentration is regulated to be in the range of 0 - 100 g/l at the end of the leach and preferably 5 - 25 g/l.
  • an oxidising agent is fed into the solution, said agent being for example an oxidising gas such as air, oxygen-enriched air or oxygen.
  • the oxidising agent may also be something other than gas, such as hydrogen peroxide, potassium permanganate or manganese oxide.
  • the acid-containing solution contains a small amount of dissolved iron and copper.
  • a sufficient amount of iron allows the zinc to dissolve at a sufficient rate i.e. it improves the dissolution kinetics.
  • the copper in the solution catalyses the oxidation of the iron.
  • the oxidised iron participates in the dissolution of zinc according to reaction (2) below;
  • the redox potential of the leach is adjusted so that at the beginning of the leach there is at least 10 mg/l of copper in the solution and at the end of the leach there is no copper in the solution.
  • the progress of the leach is monitored so that the acid concentration of the solution is regulated to be within the desired region at the end of the leach.
  • the amount of oxidising agent required to dissolve the zinc is determined, and is fed into the leaching reactor at the start of the leach.
  • the leaching reactor is preferably an agitated reactor. When the required amount of oxidising agent has been fed, the reactions continue further, even though the feed of oxidant has finished.
  • the zinc content of the concentrate has fallen to the desired level, part of the copper may also have dissolved. Dissolved copper is precipitated at the end of the leach by means of some reducing agent.
  • the reducing agent may be solid, liquid or gaseous such as hydrogen sulphide.
  • Other reducing agents are for instance sodium hydrosulphide NaHS, sodium sulphide Na 2 S or copper sulphide concentrate itself, which acts as a slow reductant.
  • the result obtained from leaching is copper concentrate, with a zinc content that is suitably low for the pyrometallurgical processing of concentrate.
  • the zinc sulphate solution is processed in the desired way in order to fabricate a commercial product,
  • the aim is to keep the total time and costs of leaching in process conditions at the most economically viable level.
  • the long leaching time demanded by the slowly-reducing reductant and on the other hand the possibly higher cost of a quick-acting reductant and the reagent consumption are taken into account (i.e. time vs. reagent consumption).
  • the concentrate was composed of the following minerals: CuFeS 2 ,
  • the composition of the concentrate was as follows:
  • Leaching was performed at atmospheric pressure and a temperature of 95 0 C and the leaching time was 9 h.
  • the solution contained 9.6 g/l of ferrous iron and 1 g/l of copper.
  • the solids content of the solution was 200 g/l and at the beginning of the leach the H 2 SO 4 concentration of the solution was 50.8 g/l.
  • the oxygen-containing gas used was oxygen, which was fed into the reactor for 3 h after which time the feed was stopped.
  • Fresh concentrate was used for reduction, and 1.1 kg was fed into the reactor when 6 - 7 hours had passed since the start of the test. As shown in Table 2 below, the zinc content of the concentrate had fallen to a value of 1.4 % and the copper content had risen to 21.4%.
  • the amount of copper lost in leaching was below 10%.
  • the results show that the concentrate acts as a slow reductant, and if leaching had continued, the copper would have gradually been precipitated back. Concentrate is without doubt the most cost-efficient reducing agent, if it is possible to perform reduction for a long period of time.
  • the redox potential was measured with Pt electrodes vs. Ag/AgCI electrode.
  • the composition of the leached concentrate was the same as in example 1 , likewise the leaching reactor, leaching pressure and temperature.
  • Leaching time was 11 h.
  • the solution contained 52.5 g/l of sulphuric acid, 9.8 g/l of ferrous iron and 1.1 g/l of copper. Oxidation of the solution was stopped after 1 h and hydrogen sulphide was fed as the reducing gas between 10 - 11 h.
  • the zinc content of the concentrate had fallen to a value of 1.0% and the copper content had risen to a value of 20.6%.
  • the progress of leaching is shown in Table 3.
  • Table 3 shows that, when oxidation ended, the redox potential fell quickly from a level of 406 mV to a level of 390 mV. Before the feed of reductant the value was 330 mV and fell quickly once the reductant feed began to a value of 86 mV. The final value of 207 mV indicates the probable oxygen introduced with the make-up water. The table also indicates that a smaller feed of reduction gas would have been sufficient, because the dissolved copper was precipitated as soon as the feed of reduction gas was begun.
  • composition of the concentrate leached in the test was as given in Table
  • the leaching reactor, leaching pressure and temperature were the same as in examples 1 and 2.
  • Leaching time was 12 h.
  • the solution contained 51.4 g/l of sulphuric acid, 9.1 g/l of ferrous iron and 0.9 g/l of copper.
  • the oxidation of the solution was stopped after 4h and hydrogen sulphide was fed as the reduction gas between 11.5 - 12 h.
  • the zinc content of the concentrate had fallen to a level of 1.4% and the copper content had risen to a level of 21.7%. Reduction precipitated all of the dissolved copper so no copper losses were generated.
  • the progress of leaching is shown in Table 5:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de préparation d'un concentré de cuivre pouvant être destiné à un traitement pyrométallurgique, à partir d'un concentré dans lequel du zinc est présent sous forme d'impureté. Selon ce procédé, le zinc est lixivié à partir du concentré avec une solution contenant de l'acide sulfurique dans des conditions d'oxydation à température et pression atmosphériques. À la fin de la lixiviation, les conditions sont régulées de façon que le cuivre dissous soit précipité.
PCT/FI2008/050483 2007-09-07 2008-09-03 Procédé de valorisation d'un concentré de cuivre WO2009030811A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN200880105783.2A CN101796204B (zh) 2007-09-07 2008-09-03 提级铜浓缩物的方法
EA201000293A EA017095B1 (ru) 2007-09-07 2008-09-03 Способ удаления цинка из медно-сульфидного концентрата
CA2697187A CA2697187C (fr) 2007-09-07 2008-09-03 Procede de valorisation d'un concentre de cuivre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20070684A FI119819B (fi) 2007-09-07 2007-09-07 Menetelmä kuparirikasteen laadun parantamiseksi
FI20070684 2007-09-07

Publications (1)

Publication Number Publication Date
WO2009030811A1 true WO2009030811A1 (fr) 2009-03-12

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ID=38572882

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2008/050483 WO2009030811A1 (fr) 2007-09-07 2008-09-03 Procédé de valorisation d'un concentré de cuivre

Country Status (6)

Country Link
CN (2) CN101796204B (fr)
CA (1) CA2697187C (fr)
EA (1) EA017095B1 (fr)
FI (1) FI119819B (fr)
PE (1) PE20090848A1 (fr)
WO (1) WO2009030811A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1435699A (en) * 1919-09-30 1922-11-14 Niels C Christensen Process of treating sulphide ores of zinc
US2609272A (en) * 1946-12-09 1952-09-02 Guaranty Invest Corp Ltd Process for the treatment of matte to recover metallic salts
US4260588A (en) * 1978-09-16 1981-04-07 Duisburger Dupferhutte Production of sulphidic copper concentrates
FI68177C (fi) * 1980-02-08 1985-08-12 Sherritt Gordon Mines Ltd Foerfarande foer utvinning av koppar och zink ur sulfidmalm
WO1996005329A1 (fr) * 1994-08-15 1996-02-22 R & O Mining Processing Ltd. Conversion hydrometallurgique de sulfure de zinc en sulfate a partir de minerais et de concentres contenant du sulfure de zinc
WO1996029439A1 (fr) * 1995-03-22 1996-09-26 M.I.M. Holdings Limited Procede de lessivage de minerais sous une pression atmospherique
WO2006070052A1 (fr) * 2004-12-28 2006-07-06 Outotec Oyj. Methode pour un traitement hydrometallurgique d'un concentrat de sulfure contenant plusieurs metaux precieux

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5344479A (en) * 1992-03-13 1994-09-06 Sherritt Gordon Limited Upgrading copper sulphide residues containing nickel and arsenic
CN1277939C (zh) * 2004-01-12 2006-10-04 张在海 细菌浸出含铜黄铁矿石中的铜的方法
FI118473B (fi) * 2006-02-17 2007-11-30 Outotec Oyj Menetelmä kuparin talteenottamiseksi kuparisulfidimalmista

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1435699A (en) * 1919-09-30 1922-11-14 Niels C Christensen Process of treating sulphide ores of zinc
US2609272A (en) * 1946-12-09 1952-09-02 Guaranty Invest Corp Ltd Process for the treatment of matte to recover metallic salts
US4260588A (en) * 1978-09-16 1981-04-07 Duisburger Dupferhutte Production of sulphidic copper concentrates
FI68177C (fi) * 1980-02-08 1985-08-12 Sherritt Gordon Mines Ltd Foerfarande foer utvinning av koppar och zink ur sulfidmalm
WO1996005329A1 (fr) * 1994-08-15 1996-02-22 R & O Mining Processing Ltd. Conversion hydrometallurgique de sulfure de zinc en sulfate a partir de minerais et de concentres contenant du sulfure de zinc
WO1996029439A1 (fr) * 1995-03-22 1996-09-26 M.I.M. Holdings Limited Procede de lessivage de minerais sous une pression atmospherique
WO2006070052A1 (fr) * 2004-12-28 2006-07-06 Outotec Oyj. Methode pour un traitement hydrometallurgique d'un concentrat de sulfure contenant plusieurs metaux precieux

Also Published As

Publication number Publication date
FI20070684A0 (fi) 2007-09-07
CN101796204A (zh) 2010-08-04
EA201000293A1 (ru) 2010-10-29
PE20090848A1 (es) 2009-07-25
CN101796204B (zh) 2014-06-18
FI119819B (fi) 2009-03-31
CA2697187A1 (fr) 2009-03-12
CN102787245A (zh) 2012-11-21
CA2697187C (fr) 2014-04-15
EA017095B1 (ru) 2012-09-28

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