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WO2002070758A1 - Lessivage ameliore et a haut rendement de tas biologiques de minerais de cuivre chalcopyrite - Google Patents

Lessivage ameliore et a haut rendement de tas biologiques de minerais de cuivre chalcopyrite Download PDF

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Publication number
WO2002070758A1
WO2002070758A1 PCT/AU2002/000250 AU0200250W WO02070758A1 WO 2002070758 A1 WO2002070758 A1 WO 2002070758A1 AU 0200250 W AU0200250 W AU 0200250W WO 02070758 A1 WO02070758 A1 WO 02070758A1
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WO
WIPO (PCT)
Prior art keywords
bioheap
leaching
ore
copper
maintained
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/AU2002/000250
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English (en)
Inventor
Manuel R. Lastra
Julia Rose Budden
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BHP Innovation Pty Ltd
Original Assignee
BHP Billiton Innovation Pty Ltd
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 BHP Billiton Innovation Pty Ltd filed Critical BHP Billiton Innovation Pty Ltd
Publication of WO2002070758A1 publication Critical patent/WO2002070758A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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

  • This invention relates to the extraction of precious metals, and particularly to the extraction of copper from chalcopyrite ore using biohydrometallurgical processes.
  • Chalcopyrite (CuFeS 2 ) or copper iron sulfide is a fairly common mineral and one of the chief ores of copper. It's existence in large quantities and in many locations (eg. Chile, Peru, Mexico, Europe, South Africa, USA) makes it a leading source of copper.
  • the insoluble copper sulfide mineral is oxidised by the microorganisms to sulfate which is soluble in the aqueous leach media.
  • Any iron present in the copper sulfide substrate is oxidized by the microorganisms to ferric ion (known as an oxidizing agent) and it contributes to the sulfide oxidation step.
  • Oxidation of chalcopyrite can be represented as follows:
  • the ferric sulfate produced in the above reaction oxidizes metal sulfides (eg. sphalerite) ZnS + 2 Fe 2 (SOJ 3 + 2H 2 O + O 2 ⁇ ZnSO 4 + FeSO 4 + 2H 2 SO 4 as the ferric ion is reduced during oxidation of zinc sulphides, it is reoxidized by A.ferrooxidans and in this way the iron redox cycle is closed.
  • metal sulfides eg. sphalerite
  • ZnS + 2 Fe 2 SOJ 3 + 2H 2 O + O 2 ⁇ ZnSO 4 + FeSO 4 + 2H 2 SO 4
  • this chemolithotrophic bacteria derives its energy from oxidation of ferrous ion and reduced valence inorganic sulfur compounds and utilizes carbon dioxide for growth when cultured on chalcopyrite.
  • U.S. Patent Number 06168766 to NIPPON MINING & METALS CO. LTD discloses a process for leaching copper from copper sulfide using bacteria, which ensures that the rate of leaching of copper increases to reduce the leaching time period and that the rate of leaching of primary copper sulfide contained in ores is increased.
  • the process comprises using an acid leaching solution that includes both or any one of iron oxidizing bacteria and sulfur oxidizing bacteria in a concentration of 10 6 microbes/mL, the acid leaching solution having a redox potential of from 550 to 750 mV and 5g/L or more of iron, the ratio of trivalent iron ions to bivalent iron ions (Fe 3+ /Fe 2+ ) in the acid leaching solution being 50 or more.
  • an acid leaching solution that includes both or any one of iron oxidizing bacteria and sulfur oxidizing bacteria in a concentration of 10 6 microbes/mL, the acid leaching solution having a redox potential of from 550 to 750 mV and 5g/L or more of iron, the ratio of trivalent iron ions to bivalent iron ions (Fe 3+ /Fe 2+ ) in the acid leaching solution being 50 or more.
  • a heap preferably having dimensions of at least 2.5 m high and 5 m wide is constructed with chalcopyrite bearing ore.
  • the constructed heap includes exposed sulfide mineral particles at least 25 weight % of which are chalcopyrite.
  • the concentration of the exposed sulfide mineral particles in the heap is such that the heap includes at least 10 Kg of exposed sulfide sulfur per tonne of solids in the heap.
  • at least 50% of the total copper in the heap is in the form of chalcopyrite. A substantial portion of the heap is then heated to a temperature of at least 50°C.
  • the heap is inoculated, with a culture including at least one strain of thermophilic microorganisms capable of bioleaching sulfide minerals at a temperature above 50°C.
  • a process leach solution that includes sulfuric acid and ferric iron is applied to the heap.
  • Bioleaching is carried out so that sufficient sulfide mineral particles in the heap are biooxidized to oxidize at least 10 Kg of sulfide sulfur per tonne of solids in the heap and to cause the dissolution of at least 50% of the copper in the heap into the process leach solution in a period of 210 days or less from completion of the heap.
  • the difficulty with bacterial leaching appears to be at least twofold.
  • the first problem appears to be that in both chemical and biological leaching of chalcopyrite, the rate of dissolution of the ore is uneconomically slow.
  • the other, and perhaps related difficulty appears to be the formation of a physical coating around the copper particle during dissolution, known as a passivating layer, causing the rate of dissolution to plateau. This effect occurs because diffusion of ions to and from the mineral surface is prevented physically by the layer. It is now thought that this precipitate is either iron oxide or Jarosite in nature.
  • a conventional bioheap leaching process may be described as follows.
  • Mined copper ores are crushed to an optimum particle size.
  • the crushed ore is mixed with sulfuric acid in an agglomerating device to consolidate the fines with the coarser ore particles and precondition the ore for bacterial development.
  • Water or raffinate (effluent from the solvent extraction-electrowinning circuit) is added to optimize the moisture content for good agglomerate formation. If the ore is not too acid consuming, the acid requirement to precondition the ore can be met by agglomerating with raffinate.
  • Raffinate usually contains a small population of bacteria, which inoculate the ore.
  • the agglomerated and preconditioned copper ore is conveyed to the leach area where it is stacked 6 to 10 m high on a lined pad or on top of previously leached ore.
  • Plastic piping with ventilation holes is placed on the pad or lift to supply air to the bacteria during leaching. Aeration of the bioheap is initiated soon after stacking the agglomerated ore. Low pressure fans supply air to the ventilation system under the ore.
  • the bioheap is irrigated with raffinate at an application rate that does not cause saturation.
  • PLS Pregnant leach solution
  • ILS intermediate leach solution
  • SX/EW solvent extraction/electro-winning circuit for copper recovery.
  • the raffinate barren solution from the SX/EW circuit
  • Leach times vary among the operations, but is typically in the 200-day range for secondary copper ores. Copper recoveries also vary with 75% to 85% recoveries achieved at most operations.
  • the bacteria may be selected from the group of thermophilic or mesophilic and acidophilic bacteria including for example, Acidithiobacillus Ferrooxidans. Thiobacillus Thiooxidans Leptospirrilurn Ferrooxidans, Thiobacillum Caldus. Sulphobus Acidocaldarius & Acidianus brierleyi. It is known for example, that these microorganisms will variously having optimum efficiency at different temperatures (A. ferrooxidans at temperatures above 35°C and A.brierleyi at temperatures in excess of 60°C and as high as 80°C).
  • the bacteria will be present in the heap or will be inoculated into the heap via the leaching solution or raffinate.
  • the bacteria In an “indirect leaching” process, the bacteria will be contained in a reaction unit separated from the heap.
  • the invention in a process for bioheap leaching such as that described hereinabove which is directed at the extraction of copper from chalcopyrite, provides the improvement of maintaining the reduction potential at below or around Eh ⁇ 550mV.
  • the relative concentration of Fe 2+ / Fe 3+ with a particular emphasis on maintaining high levels of Fe 2+ in the process. This may be achieved for example, in the situation that the heap contains the organisms, ie. in a direct leaching process, by maintaining very limited levels of oxygen in the heap. It is anticipated that in this case the temperature of the heap would need to be maintained at around or above 55°C.
  • the invention is predicated on the discovery that the chalcopyrite dissolution rate is strongly dependent on the reduction potential (Eh) in solution.
  • the invention is further predicated on the discovery that high concentrations of ferric ions suppress the leaching of copper from chalcopyrite and that conversely, high levels of ferrous ions have an enhancing effect on the chalcopyrite extraction process. It is also postulated that copper extraction from chalcopyrite ores is most efficient at high temperatures, for example, in excess of 50°C.

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

Abstract

L'invention concerne un procédé amélioré de lessivage de tas biologiques de minerais de cuivre. Selon ce procédé, le lessivage de tas biologiques est effectué à moins de ou environ Eh &lt ; 550mV. La teneur en Fe?2+ et Fe3+¿, générés pendant le lessivage, est maintenue de préférence à un niveau tel que la teneur en Fe2+ soit supérieure à Fe3+. Ce procédé s'avère particulièrement utile dans le domaine des minerais de chalcopyrite.
PCT/AU2002/000250 2001-03-06 2002-03-06 Lessivage ameliore et a haut rendement de tas biologiques de minerais de cuivre chalcopyrite Ceased WO2002070758A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPR3547 2001-03-06
AUPR3547A AUPR354701A0 (en) 2001-03-06 2001-03-06 Improved, high yield bioheap leaching of chalcopyrite copper ores

Publications (1)

Publication Number Publication Date
WO2002070758A1 true WO2002070758A1 (fr) 2002-09-12

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PCT/AU2002/000250 Ceased WO2002070758A1 (fr) 2001-03-06 2002-03-06 Lessivage ameliore et a haut rendement de tas biologiques de minerais de cuivre chalcopyrite

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AU (1) AUPR354701A0 (fr)
WO (1) WO2002070758A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308468C (zh) * 2003-12-23 2007-04-04 Bhp比尔顿有限公司 用于模拟生物堆沥滤过程的方法和装置
CN100460532C (zh) * 2007-04-16 2009-02-11 中南大学 一种原生硫化矿细菌浸出制备高纯铜的方法
EP1866447A4 (fr) * 2005-03-21 2010-01-20 Bioheap Ltd Lixiviation en tas de minerais de sulfure
CN102094127A (zh) * 2011-01-30 2011-06-15 北京科技大学 一种从高镁型低品位硫化镍矿中回收镍和镁元素的方法
CN101736154B (zh) * 2008-11-26 2011-09-07 北京有色金属研究总院 保持生物堆浸过程生物活性、提高浸出效率的方法
EP3184657A4 (fr) * 2014-08-22 2018-03-14 Compañía Minera Zaldivar Limitada Lixiviation de sulfures de cuivre en milieu de chlorure ferreux avec des bactéries
WO2018202691A1 (fr) * 2017-05-02 2018-11-08 Linnaeus University Procédé de conduite d'un processus de biolixiviation de chalcopyrite
CN115595438A (zh) * 2022-10-13 2023-01-13 中国科学院过程工程研究所（Cn） 一种低硫矿石生物堆浸的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4571387A (en) * 1983-01-26 1986-02-18 British Columbia Research Council Biological-acid leach process
US5676733A (en) * 1993-12-03 1997-10-14 Geobiotics, Inc. Method for recovering metal values from concentrates of sulfide minerals
US5779762A (en) * 1994-10-25 1998-07-14 Geobiotics, Inc. Method for improving the heap biooxidation rate of refractory sulfide ore particles that are biooxidized using recycled bioleachate solution
JPH10265864A (ja) * 1997-03-27 1998-10-06 Nikko Kinzoku Kk バクテリアを用いた硫化銅鉱からの銅浸出方法
US5873927A (en) * 1997-05-16 1999-02-23 Echo Bay Mines, Limited Integrated, tank/heap biooxidation process
US6107065A (en) * 1995-06-02 2000-08-22 Geobiotics, Inc. Nonstirred bioreactor for processing refractory sulfide concentrates and method for operating same
WO2001031072A1 (fr) * 1999-10-28 2001-05-03 Mintek Technique permettant de proceder a une lixiviation biologique avec maitrise du potentiel d'oxydo-reduction

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4571387A (en) * 1983-01-26 1986-02-18 British Columbia Research Council Biological-acid leach process
US5676733A (en) * 1993-12-03 1997-10-14 Geobiotics, Inc. Method for recovering metal values from concentrates of sulfide minerals
US6146444A (en) * 1993-12-03 2000-11-14 Geobiotics, Inc. Method for recovering metal value from concentrates of sulfide minerals
US5779762A (en) * 1994-10-25 1998-07-14 Geobiotics, Inc. Method for improving the heap biooxidation rate of refractory sulfide ore particles that are biooxidized using recycled bioleachate solution
US6086656A (en) * 1994-10-25 2000-07-11 Geobiotics, Inc. Method for improving the heap biooxidation rate of refractory sulfide ore particles that are biooxidized using recycled bioleachate solution
US6107065A (en) * 1995-06-02 2000-08-22 Geobiotics, Inc. Nonstirred bioreactor for processing refractory sulfide concentrates and method for operating same
JPH10265864A (ja) * 1997-03-27 1998-10-06 Nikko Kinzoku Kk バクテリアを用いた硫化銅鉱からの銅浸出方法
US5873927A (en) * 1997-05-16 1999-02-23 Echo Bay Mines, Limited Integrated, tank/heap biooxidation process
WO2001031072A1 (fr) * 1999-10-28 2001-05-03 Mintek Technique permettant de proceder a une lixiviation biologique avec maitrise du potentiel d'oxydo-reduction

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AHONEN ET AL.: "Redox potential- controlled bacterial leaching of chalcopyrite ores", 1993, MINERALS, METALS & MATERIALS SOCIETY *
DATABASE WPI Derwent World Patents Index; Class D16, AN 1998-018951/02 *
DATABASE WPI Derwent World Patents Index; Class D16, AN 1998-590026/50 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308468C (zh) * 2003-12-23 2007-04-04 Bhp比尔顿有限公司 用于模拟生物堆沥滤过程的方法和装置
EP1866447A4 (fr) * 2005-03-21 2010-01-20 Bioheap Ltd Lixiviation en tas de minerais de sulfure
AU2006227594B2 (en) * 2005-03-21 2010-11-11 Bioheap Limited Heap leaching of sulphide ores
CN100460532C (zh) * 2007-04-16 2009-02-11 中南大学 一种原生硫化矿细菌浸出制备高纯铜的方法
CN101736154B (zh) * 2008-11-26 2011-09-07 北京有色金属研究总院 保持生物堆浸过程生物活性、提高浸出效率的方法
CN102094127A (zh) * 2011-01-30 2011-06-15 北京科技大学 一种从高镁型低品位硫化镍矿中回收镍和镁元素的方法
EP3184657A4 (fr) * 2014-08-22 2018-03-14 Compañía Minera Zaldivar Limitada Lixiviation de sulfures de cuivre en milieu de chlorure ferreux avec des bactéries
WO2018202691A1 (fr) * 2017-05-02 2018-11-08 Linnaeus University Procédé de conduite d'un processus de biolixiviation de chalcopyrite
CN115595438A (zh) * 2022-10-13 2023-01-13 中国科学院过程工程研究所（Cn） 一种低硫矿石生物堆浸的方法

Also Published As

Publication number Publication date
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