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WO1997004140A1 - Procede hydrometallurgique pour la recuperation de cuivre contenu dans des materiaux metalliques oxydes - Google Patents

Procede hydrometallurgique pour la recuperation de cuivre contenu dans des materiaux metalliques oxydes Download PDF

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Publication number
WO1997004140A1
WO1997004140A1 PCT/ES1996/000147 ES9600147W WO9704140A1 WO 1997004140 A1 WO1997004140 A1 WO 1997004140A1 ES 9600147 W ES9600147 W ES 9600147W WO 9704140 A1 WO9704140 A1 WO 9704140A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
leaching
solution
recovery
extraction
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/ES1996/000147
Other languages
English (en)
Spanish (es)
Inventor
Francisco José ALGUACIL PRIEGO
Luis Magne Ortega
Aurora Gomez Coedo
Patricio Navarro Donoso
Mª Teresa DORADO LOPEZ
Jaime Simpson Alvarez
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.)
Universidad de Santiago de Chile
Consejo Superior de Investigaciones Cientificas CSIC
Original Assignee
Universidad de Santiago de Chile
Consejo Superior de Investigaciones Cientificas CSIC
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
Priority claimed from ES9501420A external-priority patent/ES2114444B1/es
Priority claimed from ES9501858A external-priority patent/ES2114452B1/es
Priority claimed from ES9600941A external-priority patent/ES2123417B1/es
Application filed by Universidad de Santiago de Chile, Consejo Superior de Investigaciones Cientificas CSIC filed Critical Universidad de Santiago de Chile
Publication of WO1997004140A1 publication Critical patent/WO1997004140A1/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
    • C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • 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 falls within the sectors of chemical technology, material technology and metallurgical technology.
  • a possible route for the benefit of these metallurgical wastes consists of a hydrometallurgical treatment thereof.
  • aqueous solutions containing ammonium as a leaching agent with a high selectivity with respect to the copper present in these metallic materials.
  • the process object of the present invention patent follows this path and consists in subjecting these metallurgical residues to a treatment that includes several essential steps. Although a part of these stages, considered in isolation, are known, when properly joined they constitute a new process, allowing the separation and recovery of the copper contained in these materials.
  • the present invention describes a process for the recovery of copper and possibly other metals of interest, from oxidized metallurgical residues, such as copper smelting powders, by leaching with aqueous solutions of ammonium ion (which is supplied to the system as ammonium hydroxide, ammonium carbonate and / or ammonium chloride), which results in the formation of the corresponding copper ammonia complexes and separation of this metal from the fertile solution obtained by a stage of solvent extraction stage with type extraction agents acid (with or without the ability to form chelate compounds). In this extraction stage the acidity generated in the metal extraction process is neutralized by the ammonia released in the reaction itself and the ammonium ion solution is regenerated. The copper that has passed into the organic phase is re-extracted from it using the sulfuric acid obtained in the electrolysis of the metal.
  • ammonium ion which is supplied to the system as ammonium hydroxide, ammonium carbonate and / or ammonium chloride
  • the hydrometallurgical treatment consists of a set of stages that together form a closed circuit.
  • solubilization of the copper contained in the metallurgical residue is achieved, in the form of ammoniacal complexes.
  • the treatment of the fertile solution is carried out, recovering the copper dissolved and the leaching solution regenerated, so the circuit is closed
  • the copper is separated from the fertile solution by solvent extraction.
  • acid-type reactive extraction agents are used as extraction agents.
  • the copper extraction reaction would be:
  • the neutralizer is the ammonia of the copper ammonia complex itself, formed according to the reactions [2] and [3].
  • the leaching agent is regenerated in the extraction reaction [S] so that it can be used again.
  • HR represents the acid extraction agent, also in reaction [S] and to facilitate adjustment thereof the reaction has been written as if the predominant copper ammonia complex was the
  • the leaching stage (stage I) of the metallurgical waste (S 1) can be carried out in a single stage at temperatures between 15 and 100 ° C, preferably 25 ° C, atmospheric pressure or a pressure lower than S atmospheres, preferably atmospheric pressure, and with a residence time between half an hour and four hours, preferably one hour.
  • Leaching is carried out with an aqueous solution of ammonium ion (DI) (which is supplied to the system as ammonium hydroxide, ammonium carbonate and / or ammonium chloride) and preferably containing a concentration of the attack reagent between 1 and 260 grams thereof per 1000 cm 3 of solution.
  • DI ammonium ion
  • the pulp ratio or the concentration of the leaching agent in the attack solution must be adequate to ensure the formation of at least the diaminopropy (II) complex and thus not have an ammonia deficit to neutralize the protons produced in the process of metal extraction (equation [5]). On the other hand, this situation can also be avoided if sulfates are precipitated before the extraction operation, since this precipitation produces ammonia as shown in the reaction [6].
  • Iron which is usually the most important impurity, when attacked immediately passes to the solid residue. If it is present as iron (II), it dissolves very partially to form the Fe (NH3) n2 + ammoniacal complexes, although they also tend to decompose to form insoluble iron (III) compounds and pass to the solid residue.
  • the treatment of the leaching solution for the separation and recovery of copper, removal of impurities and regeneration of the attack ammonia solution is carried out in a series of successive stages, in which conventional techniques such as extraction with solvents
  • the order and use of these stages is not essential and can be varied both as to adapt to the nature, composition and laws of the material to be treated.
  • the present invention process is characterized in that it uses ammonia in some of these stages, facilitating the separation of copper and other impurities by neutralizing the acid that is generated in any of these stages.
  • stages II, III, IV and V represent one of the possible sequences of separation and recovery of copper, removal of impurities and regeneration of the attack solution.
  • This sequence corresponds to one of the preferred variants for the type of starting material considered in this illustrated description of the process.
  • the solution obtained in the leaching stage is treated to remove the sulfates thereof, recover the copper, remove other possible impurities and regenerate the leaching solution.
  • stage II The sulfate removal stage (stage II) is done by precipitating as
  • CaSCy2H 2 0 S6 by the addition of calcium oxide (II), calcium hydroxide (II) or other precipitating agent (D3) of this anion.
  • This stage also compensates for the possible ammonia deficit that may exist in the process and regenerate the leaching solution. From this stage an aqueous solution (D4) would be obtained which would be carried out to a solvent extraction operation.
  • the solution (D4) resulting from the previous stage (stage II) is treated in a solvent extraction circuit using acid-like extraction agents.
  • an acid concentration equivalent to that of the extracted metal is generated, the neutralization of this acid by the ammonia of the metal complex completely displaces the extraction equilibrium, which favors the reaction.
  • the copper extraction stage (stage III) can be carried out preferably using acidic extraction agents such as oximes (for example the commercial products LIX 860, Acorga PT5050 and MOC-45), oxines (for example the commercial product Kelex 100 ), B-diketones (for example the commercial product LIX
  • acidic extraction agents such as oximes (for example the commercial products LIX 860, Acorga PT5050 and MOC-45), oxines (for example the commercial product Kelex 100 ), B-diketones (for example the commercial product LIX
  • alkylphosphoric acids for example the commercial product DP-8R
  • alkylphosphonic acids such as the commercial product PC-88A
  • alkylphosphinic acids for example the commercial product Cyanex 272
  • mono and dithioalkyl phosphic acids such as commercial products Cyanex 302 and Cyanex 301
  • LIX is a registered trademark of Henkel Corp.
  • Acorga is a registered trademark of ICI
  • MOC is a registered trademark of Allied Signal
  • Kelex is a registered trademark of Sherex
  • Cyanex is a registered trademark of American Cyanamid, and DP-8R and PC-88A are registered trade products of Daihachi Chemical.
  • the extraction of copper with these extraction agents is carried out at a temperature between 15 and 45 ° C, a residence time between 5 and 20 minutes and dissolving the extraction agent in an aliphatic and / or aromatic organic diluent, for example the n-dean.
  • the organic phase charged with copper would pass to the re-extraction stage (stage IV) where the copper would be recovered using an acid solution, preferably return electrolyte, although another re-extraction technique could be used.
  • the regenerated organic phase corresponds to (D7), the organic phase charged with copper to (D6), the acid re-extraction solution to (D8) and the charged aqueous solution that goes to recovery of the metal by electrolysis to (D9).
  • stage V The refining (D5) obtained from the extraction operation, practically free of copper, would be taken to a stage (stage V) where the impurities would be removed and / or other metals of interest would be recovered and the leaching solution (DI) would be regenerated.
  • stage V The number of these stages and their sequence is not essential and would be adapted to the composition of the solution.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (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)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Procédé hydrométallurgique pour la récupération de cuivre contenu dans des matériaux métalliques oxydés par lixiviation à l'aide d'une solution aqueuse qui contient des ions ammonium (que l'on apporte au système sous la forme d'hydroxyde d'ammonium, de carbonate d'ammonium et/ou de chlorure d'ammonium), et qui permet de former des complexes ammoniacaux de cuivre (II), et une séparation du cuivre de la solution fertile obtenue par extraction à l'aide de solvants (agents acides d'extraction), la solution de lixiviation étant régénérée par neutralisation de l'acide produit lors de l'extraction du cuivre avec l'ammoniaque du complexe métallique.
PCT/ES1996/000147 1995-07-14 1996-07-12 Procede hydrometallurgique pour la recuperation de cuivre contenu dans des materiaux metalliques oxydes Ceased WO1997004140A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
ESP9501420 1995-07-14
ES9501420A ES2114444B1 (es) 1995-07-14 1995-07-14 Procedimiento hidrometalurgico para la recuperacion de cobre de residuos metalurgicos oxidados.
ESP9501858 1995-09-26
ES9501858A ES2114452B1 (es) 1995-09-26 1995-09-26 Procedimiento para la recuperacion de cobre de materiales metalicos con base oxidos-sulfatos.
ES9600941A ES2123417B1 (es) 1996-04-25 1996-04-25 Procedimiento hidrometalurgico para la recuperacion de cobre de minerales sulfurados.
ESP9600941 1996-04-25

Publications (1)

Publication Number Publication Date
WO1997004140A1 true WO1997004140A1 (fr) 1997-02-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES1996/000147 Ceased WO1997004140A1 (fr) 1995-07-14 1996-07-12 Procede hydrometallurgique pour la recuperation de cuivre contenu dans des materiaux metalliques oxydes

Country Status (1)

Country Link
WO (1) WO1997004140A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015713A1 (fr) * 1991-03-05 1992-09-17 Environchip Technologies Ltd. Procede de recuperation de metal
EP0524782A2 (fr) * 1991-07-19 1993-01-27 Minera Escondida Limitada Traitement des concentrés de sulfure de cuivre
WO1993004208A1 (fr) * 1991-08-14 1993-03-04 Henkel Corporation Procede de recuperation de cuivre
EP0551155A1 (fr) * 1992-01-10 1993-07-14 B.U.S. ENGITEC SERVIZI AMBIENTALI S.r.l. Procédé pour récupérer le zinc et le plomb des poussières provenant d'aciéries électriques et pour recycler ces métaux purifiés vers le four, et installation pour la mise en oeuvre de ce procédé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992015713A1 (fr) * 1991-03-05 1992-09-17 Environchip Technologies Ltd. Procede de recuperation de metal
EP0524782A2 (fr) * 1991-07-19 1993-01-27 Minera Escondida Limitada Traitement des concentrés de sulfure de cuivre
WO1993004208A1 (fr) * 1991-08-14 1993-03-04 Henkel Corporation Procede de recuperation de cuivre
EP0551155A1 (fr) * 1992-01-10 1993-07-14 B.U.S. ENGITEC SERVIZI AMBIENTALI S.r.l. Procédé pour récupérer le zinc et le plomb des poussières provenant d'aciéries électriques et pour recycler ces métaux purifiés vers le four, et installation pour la mise en oeuvre de ce procédé

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MENA A.: "Leaching of Chrysocolla with ammonia-ammonium carbonate solutions", METALLURGICAL AND MATERIALS TRANSACTIONS B: PROCESS METALLURGY AN D MATERIALS PROCESSING SCIENCE, vol. 16b, no. 2, 1 March 1985 (1985-03-01), MATERIALS INFORMATION SOCIETY US, pages 441 - 448, XP002015487 *
OUDENNE P. D.: "Leaching kinetics of malachite in ammonium carbonate solutions", METALLURGICAL AND MATERIALS TRANSACTIONS B: PROCESS METALLURGY AN D MATERIALS PROCESSING SCIENCE, vol. 14b, no. 1, 1 March 1983 (1983-03-01), MATERIALS INFORMATION SOCIETY US, pages 33 - 40, XP002015486 *

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