[go: up one dir, main page]

WO2009007792A1 - Production de cuivre - Google Patents

Production de cuivre Download PDF

Info

Publication number
WO2009007792A1
WO2009007792A1 PCT/IB2007/052782 IB2007052782W WO2009007792A1 WO 2009007792 A1 WO2009007792 A1 WO 2009007792A1 IB 2007052782 W IB2007052782 W IB 2007052782W WO 2009007792 A1 WO2009007792 A1 WO 2009007792A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
reducing
reduction step
reduction
salt
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/IB2007/052782
Other languages
English (en)
Inventor
Gerard Pretorius
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.)
CUPRACHEM TECHNOLOGY Pty Ltd
Original Assignee
CUPRACHEM TECHNOLOGY 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 CUPRACHEM TECHNOLOGY Pty Ltd filed Critical CUPRACHEM TECHNOLOGY Pty Ltd
Priority to PCT/IB2007/052782 priority Critical patent/WO2009007792A1/fr
Priority to AP2010005138A priority patent/AP2636A/xx
Publication of WO2009007792A1 publication Critical patent/WO2009007792A1/fr
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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • 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
    • C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
    • 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
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • 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
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • 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 production of copper.
  • the invention relates to a method of producing copper and to a method of recovering copper from a copper-containing substrate.
  • Copper is usually recovered from copper-containing ores either pyrometallurgically, by electrolytic reduction of a copper-containing solution or by reduction of a copper-containing solution with a suitable reducing agent.
  • the reduction processes are generally carried out on solutions of copper (II).
  • a problem associated with the reduction of copper (II) solutions is that the metal which plates out from such solutions during reduction traps impurities.
  • the copper which is produced by electrolytic or chemical reduction usually requires further purification in order to produce a metal having a purity of greater than 99%.
  • a method of producing copper from a solution containing a copper (II) salt including the steps of reducing at least some of the copper (II) salt to a copper (I) salt in a first reduction step; solubilising the copper (I) salt to produce a soluble copper (I) complex; and reducing the soluble copper (I) complex to copper in a second reduction step.
  • Most copper (I) salts are insoluble and the solubilising step is necessary to obtain a dissolved copper (I) complex for the second reduction step.
  • the copper (II) salt may be essentially any water-soluble copper salt excluding copper nitrate or any other oxidative salts.
  • the copper (II) salt will be copper sulphate or copper chloride.
  • the solubilising step may be achieved by conducting the first reduction step in the presence of a soluble halide, e.g. a chloride as a solubilising agent, or by adding a soluble halide, e.g. a chloride, subsequent to or during the first reduction step.
  • solubilising the copper (I) salt may be achieved by using copper (II) chloride as the copper (II) salt. The reduction of the copper (II) salt and the solubilising of the copper (I) salt may thus take place essentially simultaneously.
  • the soluble halide will be used in excess.
  • the soluble copper (I) complex will be a sodium chloride- copper chloride complex.
  • Any water-soluble chloride salt of which the metal cation doesn't have an oxidative reaction with copper (I) e.g. ferric cations can, in principle, be used as the solubilising agent. Examples include AICI3, CaCI 2 , FeCI 2 or the like (but not FeCb). Without being bound thereby, the Applicant believes that the soluble copper (I) complex when a soluble chloride is used is probably a CuCI 4 3" species, e.g. with an Al 3+ or 3Na + to balance the charge.
  • the reducing agent When a reducing agent is used in the first reduction step for the reduction of copper (II) to copper (I), the reducing agent will preferably be a mild reducing agent such as sulphur dioxide or copper metal. Sodium sulphite or sodium thiosulphate may also be used. Preferably, only a catalytic amount, i.e. less than a stoichiometric amount of a reducing agent will be used in the first reduction step to initiate reduction of the copper (II) to copper (I) so that further reduction of the copper (II) to copper (I) will result from the copper metal produced in the second reduction step. For example, if copper powder is used in the first reduction step, it may be used in an amount of about 5%-25% of the stoichiometric amount required to reduce all the copper (II).
  • the addition of a small amount of copper metal powder to the copper (II) solution in the presence of an excess of sodium chloride will initially result in the reduction of part of the copper (II) to produce some insoluble CuCI.
  • the insoluble CuCI will then be solubilised by the sodium chloride and the solubilised CuCI will be reduced to copper in the second reduction step, e.g. by using a reducing agent.
  • the copper produced in the second reduction step will, in turn, reduce more copper (II) to copper (I) whilst itself being oxidised to copper (I). This process will then continue until all of the copper (II) has been consumed.
  • the remaining copper (I) will then be reduced by the reducing agent to copper metal.
  • a reducing agent is thus used in the second reduction step.
  • the reducing agent used in the second reduction step is a reducing metal.
  • the reducing metal may be iron, aluminium or zinc. Instead, the reducing metal may be nickel, cobalt, manganese or magnesium.
  • the reducing agent used in the second reduction step may be iron if copper crystals are sought after.
  • the reducing agent used in the second reduction step may be aluminium if copper powder is sought after. It was found that reduction with aluminium was highly exothermic and that the addition of aluminium to the reaction mixture needed to be controlled to prevent overheating. Zinc was found to be less exothermic than aluminium and iron less exothermic than zinc. The Applicant believes that the mild reaction of iron with copper (I) resulted in copper crystal formation while an exothermic reaction like aluminium with copper (I) resulted in copper powder formation. It is therefore the Applicant's conclusion that nickel and cobalt as reducing agents with copper (I) will also result in the formation of copper crystals while other reducing agents like manganese and magnesium with copper (I) will result in the formation of copper powder.
  • the preferential reduction of copper (I) to copper in the presence of copper (II) in the second reduction step is a reflection of the difference in the redox potentials for the reduction of copper (I) and copper (II) to copper as can be seen below
  • a further advantages of the reduction mechanism via the copper (I) intermediate is it selectivity over other metal impurities except gold and silver that will plate before copper (I).
  • the high nobility of copper (I) ensures that only copper will be reduced in preference to any other soluble metals.
  • the second reduction step is an electrolytic reduction.
  • a membrane may be used to separate the chlorides from the anode because of the formation of chlorine gas during the electrolysis process.
  • chlorine is a corrosive and usually undesirable oxidising agent and the Applicant has found that there is a drop in the chloride concentration of the reaction mixture as chlorine gas is produced. This embodiment would therefore probably not be a preferred embodiment.
  • the solution containing the copper (II) salt may be produced from a copper-containing ore, preferably a basic copper-containing ore, such as malachite, C11CO3. Cu(OH) 2 , azurite, 2C11CO3. Cu(OH) 2 or cuprite, Cu 2 O.
  • Sulphide ores such as CuFeS 2 , CUsFeS 4 , Cu 2 S, CuS, may also be used after roasting or oxidation.
  • an excess of sodium chloride is added to a copper (II) sulphate solution followed by a catalytic amount of copper powder as a reducing agent.
  • copper (I) forms, it precipitates as a white insoluble precipitate.
  • the high chloride concentration then causes dissolution of the copper (I) chloride and the solution turns from blue to green.
  • the reactions which take place are:
  • the catalytic amount of the mild reducing agent needed to initiate the reaction depended on the surface area of the strong reducing agent used. Generally, 0.2 mole of copper powder or Na 2 S ⁇ 3 per 1 mole of copper (II) produced a satisfactory result.
  • a method of recovering copper from a copper-containing substrate including the steps of converting the copper-containing substrate to a copper (II) containing solution; reducing at least some of the copper (II) in the copper (II) containing solution to produce an insoluble form of copper (I) in a first reduction step using a less than stoichiometric amount of a first reducing agent; solubilising the insoluble form of copper (I) with a solubilising agent to produce a soluble form of copper (I) by adding the solubilising agent prior to, during or subsequent to the first reduction step; and reducing the solubilised form of copper (I) to copper in a second reduction step using a second reducing agent.
  • the copper-containing substrate may be a copper-containing ore, e.g. malachite or copper oxides.
  • the copper-containing ore may thus be as hereinbefore described.
  • the first reducing agent may be selected from sodium sulphite and copper powder.
  • the second reducing agent may be selected from iron, zinc and aluminium.
  • the invention extends to a method of producing copper, the method including the step of reducing a soluble form of Cu (I) in solution with a reducing metal.
  • the reducing metal may be iron, aluminium or zinc.
  • the dissolved Cu(I) is reduced in the presence of dissolved Cu(II).
  • Finely milled malachite (30Og; -250 ⁇ m) with a copper content of 50 % (2,36 mol Cu) was added to water (1 ,2t) in a 21 polypropylene beaker.
  • the suspension was stirred vigorously and sulphuric acid (20Og; 98%; approximately 2 mol) was slowly added over a period of 20 minutes to control foaming resulting from this production of carbon dioxide.
  • the reaction was exothermic and the temperature rose from 20 0 C to AA 0 C.
  • the resulting suspension was filtered producing a filter cake which was washed with water (2x1 OOmt).
  • Aluminium buttons (4Og; 1 ,48 mol) in a perforated plastic container were then added to the green solution with vigorous stirring over a period of two hours whilst maintaining the temperature at 70 0 C. It is important that the aluminium is static relative to the solution during agitation. The green colour disappeared and successively became grey, pink, maroon and then reddish when the reaction was complete.
  • the copper suspension produced after the aluminium reduction step was filtered and the filtrate was washed with water.
  • the resulting copper filter cake was passed through a 75 ⁇ m screen with a small amount of water. Concentrated hydrochloric acid was added to the resulting powder slurry to reduce the pH to less than
  • the resulting product was a fine copper powder (151 ,5g) having a purity of greater than 99%.
  • the copper recovery was therefore
  • the powder can be stored under acidic water or when dried, under argon.
  • the powder prepared this way typically has a d 50 of 15 ⁇ m.
  • the filtrate which largely contained soluble aluminium and sodium salts, was optionally neutralized and the aluminium precipitated which is a waste or byproduct and sodium chloride reused.
  • the filtrate (approximately 51) mainly contained NaCI and FeSO 4 .
  • the iron (II) must first be electrolytically or chemically (H 2 O 2 ) oxidised to iron (III) while maintaining the pH between 4-6 via alkaline addition (slake lime) to precipitate FeSO 4 OH. This specie filtrates with ease while the NaCI stays in solution which can be recycled for the next run.
  • the mass of the iron plates was reduced to 171 .7g. From the filtrate 636g, 520m ⁇ was evaporated in a mild steel vessel at 100 0 C until 31 OmE. It was then cooled to 15°C where crystallisation took place. 9Og moist FeSO 4 .7H 2 O was filtered from a remaining 32Og, 25OmE filtrate. The filtrate contained mainly FeCI 2 which can be used in a subsequent run while the FeSO 4 .7H 2 O can be converted via known oxidative pressure leaching techniques into Fe 2 Os and H 2 SO 4 .
  • the Applicant has discovered that when soluble copper (I) is reduced with a reducing metal such as iron, copper crystals grow from the surface of the reducing iron and if the metal is aluminium or zinc, a soft copper agglomerate precipitates from the surface of the reducing metal, so that the surface of the reducing metal is left clean and active again. This agglomerate readily disperses into fine ( ⁇ 75 ⁇ m) copper powder.
  • a reducing metal such as iron
  • the copper crystals that form when iron is used as a reducing agent can be as long as 10mm, but typically the bulk of the crystals is between 0.25mm to 4mm. Both the copper crystals or copper powder that form are very selective and do not trap any significant amount of impurities.
  • the method of the invention thus produces a fine, pure copper powder or crystals from essentially any water soluble copper solution.
  • the powder has a purity of over 99% and can be used either in powder metallurgy or powder coating applications.
  • the purity of the copper crystals is greater than 99.9%, and the copper crystals are much less sensitive to air oxidation than the powder and can be melted into any desirable shape.
  • Table 2 is a comparison with prior art electro-winning processes and the crystal growth process of the invention. Table 2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé destiné à produire du cuivre à partir d'une solution contenant un sel (II) de cuivre, incluant les étapes consistant à réduire au moins une partie du sel (II) de cuivre en un sel (I) de cuivre au cours d'une première étape de réduction, solubiliser le sel (I) de cuivre afin de produire un complexe (I) de cuivre soluble, et réduire le complexe (I) de cuivre soluble en cuivre au cours d'une seconde étape de réduction.
PCT/IB2007/052782 2007-07-12 2007-07-12 Production de cuivre Ceased WO2009007792A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/IB2007/052782 WO2009007792A1 (fr) 2007-07-12 2007-07-12 Production de cuivre
AP2010005138A AP2636A (en) 2007-07-12 2007-07-12 The production of copper

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2007/052782 WO2009007792A1 (fr) 2007-07-12 2007-07-12 Production de cuivre

Publications (1)

Publication Number Publication Date
WO2009007792A1 true WO2009007792A1 (fr) 2009-01-15

Family

ID=38704688

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2007/052782 Ceased WO2009007792A1 (fr) 2007-07-12 2007-07-12 Production de cuivre

Country Status (2)

Country Link
AP (1) AP2636A (fr)
WO (1) WO2009007792A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11806789B2 (en) 2021-06-14 2023-11-07 Destiny Copper Inc. Processes for producing granular copper

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3353950A (en) * 1964-08-12 1967-11-21 Duisburger Kupferhuette Process for the production of finely particulate high purity copper powder
US6007600A (en) * 1997-08-29 1999-12-28 Outokumpu Oyj Method for producing copper in hydrometallurgical process
WO2005083132A1 (fr) * 2004-02-26 2005-09-09 Outokumpu Technology Oy Production de cuivre metallique par reduction hydrometallurgique d'oxyde de cuivre (i)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3353950A (en) * 1964-08-12 1967-11-21 Duisburger Kupferhuette Process for the production of finely particulate high purity copper powder
US6007600A (en) * 1997-08-29 1999-12-28 Outokumpu Oyj Method for producing copper in hydrometallurgical process
WO2005083132A1 (fr) * 2004-02-26 2005-09-09 Outokumpu Technology Oy Production de cuivre metallique par reduction hydrometallurgique d'oxyde de cuivre (i)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11806789B2 (en) 2021-06-14 2023-11-07 Destiny Copper Inc. Processes for producing granular copper
EP4355517A4 (fr) * 2021-06-14 2025-11-05 Destiny Copper Inc Procédés de production de cuivre granulaire

Also Published As

Publication number Publication date
AP2636A (en) 2013-04-05
AP2010005138A0 (en) 2010-02-28

Similar Documents

Publication Publication Date Title
KR100426231B1 (ko) 황화물구리광석또는농축물로부터구리를추출하는방법
JP3999805B1 (ja) 砒素含有溶液の処理方法
US4094668A (en) Treatment of copper refinery slimes
US8388730B2 (en) Process of leaching gold
CA2634878C (fr) Methode de production de scorodite et de recyclage de la solution recueillie apres l'etape de synthese de la scorodite
JPWO1998058089A1 (ja) 貴金属製錬方法
CA2618326C (fr) Procede de fabrication de la scorodite
AU2007216890B2 (en) Process for treating electrolytically precipitated copper
JP2007530778A (ja) 酸化金属材料からの金属の回収
GB2415694A (en) Method of separation/purification for high-purity silver chloride and process for producing high-purity silver by the same
JPH02197533A (ja) 有価金属の分離方法
US4127639A (en) Process for recovering silver from residues containing silver and lead
JP4615561B2 (ja) 砒素含有溶液の処理方法
JP4087433B2 (ja) 砒素含有溶液の処理方法
WO2009007792A1 (fr) Production de cuivre
US4671945A (en) Method for separation and leaching of the valuable metals in sulphide materials
RU2744291C1 (ru) Способ выделения оксида меди (I) Cu2O из многокомпонентных сульфатных растворов тяжелых цветных металлов
KR20090051034A (ko) 비산철 분말
US4118221A (en) Copper recovery from sulfate solutions containing nickel and cobalt
GB2081696A (en) Process for the production of an iron-free chromium (iii) compound
CN114269955A (zh) 从冶金残留物浸出有价元素的方法
AU2003264660B2 (en) Method for removal of silver from a copper chloride solution
JP2007314405A (ja) 砒酸鉄粉末
US20240218480A1 (en) Recovery of metals from metallic or metal-bearing materials
WO2004081242A1 (fr) Recuperation de metaux a partir de poussieres industrielles

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07805127

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07805127

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 06/09/2010).

122 Ep: pct application non-entry in european phase

Ref document number: 07805127

Country of ref document: EP

Kind code of ref document: A1