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WO1999066085A1 - Traitement des pyrites et des ferrites metalliques grillees par lessivage a l'acide peroxysulfurique - Google Patents

Traitement des pyrites et des ferrites metalliques grillees par lessivage a l'acide peroxysulfurique Download PDF

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Publication number
WO1999066085A1
WO1999066085A1 PCT/CA1999/000536 CA9900536W WO9966085A1 WO 1999066085 A1 WO1999066085 A1 WO 1999066085A1 CA 9900536 W CA9900536 W CA 9900536W WO 9966085 A1 WO9966085 A1 WO 9966085A1
Authority
WO
WIPO (PCT)
Prior art keywords
ferrite
ore
metal
roasted
acid
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/CA1999/000536
Other languages
English (en)
Inventor
Michael Mourad Hanna
Vaikuntam Iyer Lashmanan
Marc Murray Rishea
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.)
PROTIUM METALS Inc
Original Assignee
PROTIUM METALS Inc
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 PROTIUM METALS Inc filed Critical PROTIUM METALS Inc
Priority to EP19990924624 priority Critical patent/EP1086256A1/fr
Priority to CA002334511A priority patent/CA2334511A1/fr
Priority to AU41273/99A priority patent/AU4127399A/en
Priority to BR9911113A priority patent/BR9911113A/pt
Priority to MXPA00012343A priority patent/MXPA00012343A/es
Publication of WO1999066085A1 publication Critical patent/WO1999066085A1/fr
Priority to US09/734,478 priority patent/US20020001552A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting 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
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • 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
    • C22B3/04—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 present invention relates to a process for the treatment of roasted metal sulphide ores, and especially to a process for the treatment of roasted ores containing copper and zinc sulphides for the separation of copper, zinc and other metal values therefrom.
  • the present invention also relates to a process for the treatment of ferrites (as defined herein) in roasted metal sulphide ores and from other sources for separation of metals (metal values) therefrom.
  • Extraction and refining of base metals from sulphide ores may be carried out by smelting, a pyrometallurgical process, which is usually followed by metal electrowinning and metal refining.
  • Base metal sulphides are generally calcined i.e. roasted in air, to produce a metal oxide that is smelted to produce crude metal, for example blister nickel. The crude metal is subsequently re-melted, and cast into anodes which are used as feed material for metal electrowinning processes.
  • Precious and rare metals, e.g. selenium and tellurium do not dissolve in the electrolyte that is used and fall to the bottom of the electrolyte cell as anode slimes.
  • the slimes may be digested with sulphuric acid to remove the residual base metals.
  • the liquor obtained is then added to a stage for recovery of secondary base metals.
  • Arsenic usually remains in the electrolyte and causes environmental problems in the aqueous state. Residual slimes are smelted to produce a precious metal (dore) bar which may contain a residue of base metals plus antimony, bismuth, tellurium and some rare earth metals.
  • the dore bar usually contains between 10-50 percent by weight of gold, and is usually shipped to the mint for gold extraction and refining. The refining of such dore bars is usually expensive, using for example the chloride and cyanidation processes that are used in many precious metal refineries for the separation of metals from gold.
  • a process for the recovery of, in particular, copper and zinc from metal sulphide ores that does not involve the smelting of the ores would be useful, especially to eliminate the resulting environmental hazards associated with smelting and other processes.
  • ferrites and ferrates complex multiple oxides of ferric oxide are formed, which may be referred to as ferrites and ferrates; as used herein, all such complex multiple oxides of ferric oxide are referred to as ferrites, with further complexes or compounds with other metals being referred to as metal ferrites.
  • processes involving dead or sulphation roasting followed by treatment with sulphuric acid to recover e.g. zinc as soluble sulphates generally result in failure to recover metal values from ferrites in the absence of additional subsequent severe leach conditions with high acid concentrations and elevated temperature.
  • typical weak acid leaching to recover zinc values from zinc oxide formed during roasting does not recover zinc values from zinc ferrites.
  • the latter zinc values must be recovered under more severe leaching conditions, with higher acid concentration and higher temperatures.
  • iron values are not only recovered from zinc ferrite but also from other iron oxides in the roasted ore. Consequently, solutions containing zinc contain higher concentrations of iron, which affects subsequent steps to recover zinc and other dissolved metal values.
  • the higher acid concentrations must be neutralized, thereby requiring use of greater quantities of lime or other bases, which affects steps to recover metal values from tails and in other downstream processes.
  • one aspect of the present invention provides a process for the treatment of a roasted metal sulphide ore, for the separation of metals therefrom, comprising : (a) leaching said roasted ore with peroxysulphuric acid; and
  • Another aspect of the present invention provides a process for the treatment of a metal sulphide ore, for the separation of metals therefrom, comprising: (a) subjecting said metal sulphide ore to a roasting step;
  • the ore has been subjected to a dead roast or to a sulphation roast .
  • the roasted ore contains ferrite .
  • a ferrite is added to the ore, before or after roasting.
  • a solution containing copper and zinc is obtained.
  • Another aspect of the present invention provides a process for the treatment of a ferrite comprising: leaching said ferrite with peroxysulphuric acid.
  • the ferrite is subject to the process for recovery of metals therein.
  • the ferrite is being recovered from ceramic ferrites or from the electronics industry.
  • leaching or treatment is carried out with peroxysulphuric acid (Caro's acid) in the presence of gaseous chlorine .
  • peroxysulphuric acid Caro's acid
  • the present invention relates to a process for the treatment of metal sulphide ores, and in particular to a process for the treatment of metal sulphide ores that contain substantial proportions of copper and zinc sulphides.
  • the ores will likely also contain iron sulphides, and may also contain at least minor amounts of a large variety of other metallic compounds especially in the form of sulphides.
  • the ore could contain aluminum, arsenic, bismuth, barium, calcium, cadmium, potassium, magnesium, manganese, sodium, nickel, phosphorous, lead, titanium, tellurium and vanadium, as well as other metals. Many such ores also contain gold.
  • the leaching process is operable on ore or ore concentrate formed from an ore, which has previously been subjected to a roasting process.
  • the roasted ore or concentrate should be in a particulate form, especially particles of a size suitable for use in a fluidized bed, rotary kiln or torbed process for treatment of turbulent masses of material, as is known.
  • the ore or concentrate may have been subjected to a grinding process .
  • Methods for roasting of ores are known.
  • dead roasting the particulate ore is roasted in the presence of air, with sufficient air being present for oxidation of the sulphide to the corresponding oxide and formation of sulphur dioxide.
  • Good circulation of air through the particulate during the roasting process is believed to be important, both to expedite the roasting of the sulphide to the oxide and to prevent the formation of local hot spots within the ore during the roasting process.
  • a fluidized bed or other techniques may be used for the roasting of the ore as is known .
  • the roasting of the ore is conducted at a temperature to effect oxidation of the metal sulphide to the corresponding metal oxide, particularly copper sulphide and zinc sulphide to the corresponding oxides, without agglomeration of the particulate.
  • oxides are be formed at relatively low roasting temperatures e.g. 700°C or higher, but that ferrite is also formed, if iron is present as is normally the case, at similar temperatures.
  • sulphur dioxide may be introduced into the roasting chamber to cause the formation of metal sulphates during the roasting process.
  • Metal sulphates are water soluble and therefore the roasting material should require less quantity of acid in order to solubilize metal species i.e. solubilize metal oxides, during the leaching step.
  • the use of sulphation roasting will result in a lower operating temperature than required for an oxidation roasting.
  • the roasting may be carried out in the presence of both oxygen and sulphur dioxide, as such a mixture of gases will result in conversion of metal oxides to the corresponding sulphate by reaction with sulphur trioxide, and the conversion of metal sulphides to the corresponding metal sulphates by reaction with oxygen.
  • the first reaction tends to be endothermic and the second reaction exothermic, thereby permitting control of the temperature in the process.
  • roasted ore is subjected to leaching with peroxysulphuric acid.
  • Caro's acid is peroxysulphuric acid, also known as persulphuric acid, which has the formula H 2 S0 5 or HOS0 2 OOH.
  • peroxysulphuric acid also known as persulphuric acid, which has the formula H 2 S0 5 or HOS0 2 OOH.
  • Such an acid is both highly acidic and a strong oxidizing agent.
  • the leaching is carried out in multiple steps, with the acid concentration in the first step being relatively dilute compared to the concentration in a subsequent step.
  • the process provides a leach solution, which is a solution of leached metals.
  • the metals are in a soluble form, which would normally be in the form of a sulphate of the metal .
  • the peroxysulphuric acid is converted to sulphuric acid during the leaching process, and many metal sulphates especially those of copper and zinc are soluble in the solution.
  • Leach solutions may be diluted, if necessary or desirable, and then be treated for recovery of metal values therein. In particular, the leach solutions are treated for recovery of copper and zinc . Techniques for the recovery of copper and zinc from acid solutions, especially sulphuric acid solutions, are known.
  • the leach solutions will contain relatively high concentrations of one or more metals, and that such metals would normally be the first to be recovered from the leach solution. The leach solution subsequently remaining would normally then be further treated for recovery of other metal values. Techniques for the recovery of such other metal values from such solutions are known.
  • ferrites are also known. However, ferrites are leachable in the process of the present invention. In particular, embodiments of the invention, ferrites may be added to roasted ore or treated separately according to the invention.
  • Ferrites are multiple oxides of ferric oxide with another oxide.
  • a variety of techniques are known for the formation of ferrites, including heating metal oxides with ferric oxide. This occurs naturally in roasting of ores as roasting tends to form metal oxides e.g. metal sulphides are converted to the corresponding oxides. Many ores contain significant quantities of iron, which tends to be converted to iron oxide, especially ferric oxide, during roasting. Thus, ferrites tend to be formed during roasting even under controlled temperature conditions. As noted above, temperatures used in roasting are similar to those for formation of ferrites. Other sources of ferrites are known. For instance, ceramic ferrites are obtained by sintering or firing mixtures of the oxides. Ferrites are used in rectifiers, recording tapes, permanent magnets, semiconductors, insulating materials and dielectrics, e.g. in the computer, television, radio, radar and other industries, especially electronics industries.
  • Fe +6 oxidation states
  • it is believed that it oxidizes ferrites to effect separation of the metal value from the iron, thereby facilitating recovery of the metal value.
  • formation and use of Fe +6 is believed to be important in the leaching of ferrites from a variety of sources, it is believed to be particularly so in leaching of metal values from roasted sulphide ores.
  • leaching or treatment is carried out using both Caro's acid and gaseous chlorine.
  • Caro's acid and gaseous chlorine can provide further improvements in the degree of extraction.
  • Arsenic oxides tend to vaporize and be removed from the roasting chamber. It is believed to be advantageous to remove arsenic during roasting, and prevent arsenic from entering the aqueous phase during the leaching step. There may be difficulty in controlling the presence of arsenic in aqueous solutions, with the consequent environmental hazard.
  • Tails obtained from the leach solution may be treated for separation of gold and other metals from the tails.
  • a preferred method for the leaching of gold from the tails is to subject the tails to treatment with Caro's acid, as is described in WO 97/05294 of Protium Metals Inc., published February 13, 1997.
  • the process of the present invention provides a method of recovery of a variety of metal values, including copper and zinc, from roasted sulphide ores without requiring the smelting of the ore. This has substantial advantages in reducing environmental hazards associated with smelting processes.
  • the present invention also provides a versatile process for recovering copper, zinc and other metals, including precious metals, from roasted metal sulphide ores and concentrates.
  • the present invention provides for the recovery of metals from ferrites obtained from a number of sources including roasted ores and recycled ferrites used in other industries .
  • EXAMPLE I A metal sulphide ore concentrate containing copper, zinc and iron was subjected to a roasting step at a temperature of about 950°C. Samples of the calcined ore obtained were subjected to leaching with aqueous solutions of sulphuric acid or Caro's acid at temperatures of 25°C or 90°C. Details of the calcined ore and leaching conditions are given in Table 1. Other leaching conditions, especially leaching time, were the same for all leaching steps.
  • Run A Leach with H 2 S0 4 at pH 1.5, 25 °C
  • Run B Leach with H 2 S0 4 at pH 1.0, 90 °C
  • Run C Leach with Caro's acid, 90 °C
  • Run D Leach with Caro's acid plus chlorine, 90 °C

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

Abstract

L'invention concerne un procédé de traitement d'une pyrite métallique grillée permettant de séparer les métaux qu'elle contient. Ledit procédé consiste à lessiver le minerai grillé avec de l'acide peroxysulfurique, éventuellement en présence de chlore, et à en séparer une solution métallifère. Le procédé de l'invention est particulièrement utile pour séparer le cuivre et le zinc des pyrites de ces métaux, notamment lorsque le minerai a été soumis à un grillage à mort ou à un grillage sulfateur et lorsque le minerai grillé contient des ferrites métalliques nécessitant, en temps normal, des concentrations d'acide et des températures de lessivage élevées pour l'extraction de ces métaux.
PCT/CA1999/000536 1998-06-12 1999-06-09 Traitement des pyrites et des ferrites metalliques grillees par lessivage a l'acide peroxysulfurique Ceased WO1999066085A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP19990924624 EP1086256A1 (fr) 1998-06-12 1999-06-09 Traitement des pyrites et des ferrites metalliques grillees par lessivage a l'acide peroxysulfurique
CA002334511A CA2334511A1 (fr) 1998-06-12 1999-06-09 Traitement des pyrites et des ferrites metalliques grillees par lessivage a l'acide peroxysulfurique
AU41273/99A AU4127399A (en) 1998-06-12 1999-06-09 Treatment of roasted metal sulphide ores and ferrites by leaching with peroxysulphuric acid
BR9911113A BR9911113A (pt) 1998-06-12 1999-06-09 Tratamento de minérios de sulfetos metálicos ustulados e de ferritas por lixiviação com o ácido peroxisulfúrico
MXPA00012343A MXPA00012343A (es) 1998-06-12 1999-06-09 Tratamiento de minerales de sulfuro de metales calcinados y ferritas mediante lixiviacion con acido peroxisulfurico.
US09/734,478 US20020001552A1 (en) 1998-06-12 2000-12-11 Treatment of roasted metal sulphide ores and ferrites by leaching with peroxysulphuric acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA 2240450 CA2240450A1 (fr) 1998-06-12 1998-06-12 Procede pour le traitement de ferrites et de minerais sulfures metalliques grilles
CA2,240,450 1998-06-12

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/734,478 Continuation US20020001552A1 (en) 1998-06-12 2000-12-11 Treatment of roasted metal sulphide ores and ferrites by leaching with peroxysulphuric acid

Publications (1)

Publication Number Publication Date
WO1999066085A1 true WO1999066085A1 (fr) 1999-12-23

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PCT/CA1999/000536 Ceased WO1999066085A1 (fr) 1998-06-12 1999-06-09 Traitement des pyrites et des ferrites metalliques grillees par lessivage a l'acide peroxysulfurique

Country Status (8)

Country Link
US (1) US20020001552A1 (fr)
EP (1) EP1086256A1 (fr)
AU (1) AU4127399A (fr)
BR (1) BR9911113A (fr)
CA (1) CA2240450A1 (fr)
MX (1) MXPA00012343A (fr)
WO (1) WO1999066085A1 (fr)
ZA (1) ZA200007369B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2245380C1 (ru) * 2003-10-21 2005-01-27 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) Способ переработки продуктов, содержащих сульфиды металлов
RU2265068C1 (ru) * 2004-10-07 2005-11-27 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) (МИСиС) Способ переработки упорного минерального сырья, содержащего металлы
WO2008061231A1 (fr) * 2006-11-16 2008-05-22 Albemarle Netherlands B.V Purification de l'oxyde de molybdène technique
RU2336341C1 (ru) * 2007-04-16 2008-10-20 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) Способ кучного бактериального выщелачивания сульфидсодержащих продуктов
RU2384633C1 (ru) * 2008-08-19 2010-03-20 Федеральное государственное унитарное предприятие "Государственный научно-исследовательский, проектный и конструкторский институт горного дела и металлургии цветных металлов" (ФГУП "Гипроцветмет") Способ переработки упорного медного сырья, содержащего благородные металлы
US7824633B2 (en) 2006-11-21 2010-11-02 Freeport-Mcmoran Corporation System and method for conversion of molybdenite to one or more molybdenum oxides

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RU2336340C1 (ru) * 2007-04-16 2008-10-20 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) Способ выщелачивания сульфидсодержащих продуктов
RU2337154C1 (ru) * 2007-04-16 2008-10-27 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) Способ извлечения металлов из сульфидсодержащих руд
CN102959104A (zh) * 2010-11-08 2013-03-06 阿尔贝特·伊万诺维奇·彼甘诺夫 用镁将三氯化铝进行金属热还原生产铝的方法及其实施装置
CN112143896A (zh) * 2020-08-26 2020-12-29 昆明理工大学 一种碲化铋废料回收碲、铋的方法
CN119506584B (zh) * 2024-11-26 2025-08-12 山东国大黄金股份有限公司 一种利用湿法浸锑高盐废液提高银铜回收率的方法

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JPH10140257A (ja) * 1996-11-07 1998-05-26 Sumitomo Metal Mining Co Ltd 塩素浸出電解採取法によるニッケルの湿式精錬方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2245380C1 (ru) * 2003-10-21 2005-01-27 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) Способ переработки продуктов, содержащих сульфиды металлов
RU2265068C1 (ru) * 2004-10-07 2005-11-27 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) (МИСиС) Способ переработки упорного минерального сырья, содержащего металлы
WO2008061231A1 (fr) * 2006-11-16 2008-05-22 Albemarle Netherlands B.V Purification de l'oxyde de molybdène technique
US7824633B2 (en) 2006-11-21 2010-11-02 Freeport-Mcmoran Corporation System and method for conversion of molybdenite to one or more molybdenum oxides
RU2336341C1 (ru) * 2007-04-16 2008-10-20 Государственное образовательное учреждение высшего профессионального образования "Московский государственный институт стали и сплавов" (технологический университет) Способ кучного бактериального выщелачивания сульфидсодержащих продуктов
RU2384633C1 (ru) * 2008-08-19 2010-03-20 Федеральное государственное унитарное предприятие "Государственный научно-исследовательский, проектный и конструкторский институт горного дела и металлургии цветных металлов" (ФГУП "Гипроцветмет") Способ переработки упорного медного сырья, содержащего благородные металлы

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EP1086256A1 (fr) 2001-03-28
US20020001552A1 (en) 2002-01-03
BR9911113A (pt) 2002-01-29
AU4127399A (en) 2000-01-05
ZA200007369B (en) 2002-03-11
CA2240450A1 (fr) 1999-12-12

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