WO2008103873A1 - Processus pour la récupération de valeurs contenant du métal depuis des minéraux et des minerais - Google Patents

Processus pour la récupération de valeurs contenant du métal depuis des minéraux et des minerais Download PDF

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Publication number
WO2008103873A1
WO2008103873A1 PCT/US2008/054661 US2008054661W WO2008103873A1 WO 2008103873 A1 WO2008103873 A1 WO 2008103873A1 US 2008054661 W US2008054661 W US 2008054661W WO 2008103873 A1 WO2008103873 A1 WO 2008103873A1
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WO
WIPO (PCT)
Prior art keywords
process according
minerals
ore
metal
chalcopyrite
Prior art date
Application number
PCT/US2008/054661
Other languages
English (en)
Inventor
Gretchen T. Lapidus-Lavine
Fiona M. Doyle
Original Assignee
The Regents Of The University Of California
Universidad Autonoma Metropolitana-Iztapalapa
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 The Regents Of The University Of California, Universidad Autonoma Metropolitana-Iztapalapa filed Critical The Regents Of The University Of California
Priority to US12/528,166 priority Critical patent/US20100012502A1/en
Priority to MX2009000956A priority patent/MX2009000956A/es
Publication of WO2008103873A1 publication Critical patent/WO2008103873A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This invention relates to the recovery of metal-containing values from minerals and/or ores containing the same, and more particularly to the recovery of metal-containing values from minerals and/or ores by a process of reduction.
  • metal-containing values is meant metals and/or metal compounds.
  • this invention relates to the recovery of values containing copper, i.e. metallic copper and/or copper compounds, from chalcopyrite and other ores containing copper and also preferably containing sulfur.
  • the present invention proves a novel method to reduce chalcopyrite (CuFeS 2 ) and other minerals that are susceptible to reduction, to a less refractory mineral phase (for example, Cu x S) that can be conducted at near ambient temperatures and pressures, without the production of toxic gases.
  • the invention comprises a process for the recovery of metal-containing values from an ore, or from one or more minerals, that are not readily oxidizable and that are susceptible to reduction, comprising:
  • the present invention builds on the concept, as shown for instance by Dreisinger et al. supra, of first reducing chalcopyrite to resulting mineral phases (chalcocite (Cu 2 S) or djurleite (Cuj. 96 S) that are more easily oxidized to produce copper.
  • chalcocite Cu 2 S
  • Cuj. 96 S djurleite
  • the inefficiencies of the previous techniques are overcome by the process of this invention, in which the reduction of chalcopyrite, as well as of other ores mentioned below, is carried out using a cathode comprising a material that promotes the generation of monatomic hydrogen (e.g., via the H.E.R., or Hydrogen Evolution Reaction) and in which the reduction is carried out in an electrolysis chamber having a single undivided acidic electrolytic medium.
  • the soluble hydrogen sulfide and ferrous ions are then transported to the anode, where they are oxidized: the sulfide to sulfur and the ferrous ion to ferric, virtually eliminating the problem of toxic gas production.
  • H.E.R. Hydrogen Evolution Reaction
  • the discharge step involves adsorption of hydrogen atoms at available sites on the cathode surface and is represented in Shrier as: H 3 O + + M + e ⁇ M - H + H 2 O This is described as being followed by a transfer of adsorbed hydrogen across the interface into interstitial sites within the metal, represented as:
  • Electrochemical desorption is said to be more complex, involving reaction between an adsorbed hydrogen atom, a hydrated proton and an electron, in which for desorption to occur the proton must discharge onto a hydrogen atom adsorbed onto the metal surface.
  • This is generally represented in Shrier as:
  • the preferred materials for the cathode in this invention comprise those metals that promote a relatively fast discharge step but that also promote a relatively slow chemical or electrochemical desorption step, and are described more specifically below.
  • a sulfur-containing ore or mineral such as chalcopyrite
  • excess hydrogen must be produced at the cathode.
  • the overall reaction of the process in the reactor, with respect to chalcopyrite, is:
  • the off-gases could be used as a source of energy to offset the electrical costs of the process.
  • the solid product may be treated with an additional oxidant, such as, but not limited to, hydrogen peroxide, or it may be simply heated, allowing the ferric ion to oxidize the chalcocite, dissolving the copper.
  • the ores and minerals for which the process may be used are those that contain one or more reducible phases but are not easily oxidizable.
  • the term "mineral” as used in the art means a (single) mineral phase (chalcopyrite or zinc ferrite) and the term “ore” is used to mean a mixture or aggregate of minerals.
  • the process of this invention can be used with an ore, a mineral, or a mixture of minerals as the treated material.
  • Metals whose values may be recovered by this process include copper, zinc, manganese, silver, and nickel.
  • the ores and/or minerals may include sulfides. Some examples are chalcopyrite, bornite, pentlandite, pyrargyrite, zinc ferrites and manganese oxides.
  • the cathode electrode is comprised of materials that enhance the HER (hydrogen evolution reaction) at the cathode, preferably those metals that promote a relatively fast discharge step but that also promote a relatively slow chemical or electrochemical desorption step.
  • metals include, for example, titanium, nickel, tantalum, molybdenum, aluminum, platinum, palladium, and iridium, including alloys, composites, and the like thereof.
  • Such materials are described, for instance, in Shrier, Table 9.3, p. 9:48.
  • the electrode materials must be resistant to sulfate ion or other anions that may be included in the acid media, and when treating sulfide ores such as chalcopyrite, promote sulfide oxidation at the anode.
  • aluminum foam was used for the cathode and graphite [reticulated glassy carbon (RVC) or Dimensionally StableTM Anodes] was used for the anode.
  • RVC reticulated glassy carbon
  • the invention extends to the use of different materials that serve the same purpose, and the anode may comprise any suitable material that meets the above requirements. The same is the case for the material of the reactor. In the examples, a cylindrical glass reactor was employed; however the actual material need only be resistant to the medium and should be physically designed to maximize solid-liquid mixing.
  • the process is conducted in an acidic medium.
  • This medium preferably comprises sulfuric acid or hydrochloric acid; however other acids such as glacial acetic acid may be used as long as they do not attack the electrodes or the reactor materials.
  • High acid and sulfate concentrations (> 1 M) may be needed to attain high reaction velocities in the reduction of chalcopyrite; however, the process may be generally conducted at lower acid concentrations.
  • the process is operated so as to maximize the contact between the solution and the ore or mineral particles as well as between the solution and the electrodes.
  • the process may be operated at ambient temperature and pressure.
  • the process of this invention produces excellent results under such conditions.
  • higher or lower temperature and/or pressure are not precluded and their use may increase the velocity of the process, as long as the aqueous solution remains a liquid. Evaporation is not prohibited, although fumes can be corrosive and thus should be controlled.
  • the product of the process of the invention comprises a reduced form of the metal contained in the ore and/or mineral fed to the process, and from that form the final metal values may be readily recovered.
  • chalcopyrite CuFeS 2
  • chalcocite Cu 2 S
  • Djurleite Cui .9 ⁇ S
  • the reduced- form product of the process of the invention will be metallic ions (e.g., Mn +2 ); in the case of others such as silver-containing materials the product may be the metal itself.
  • Example 5 2.5 grams of the -150+300 mesh fraction of a chalcopyrite concentrate (17% Cu, 22% Fe, and 30%S) was placed in a glass reactor containing 250 ml of 0.5 M H 2 SO 4 in water at room temperature (22 0 C). Current was passed through the stirred solution using an aluminum foam cathode (20 ppi) and a Dimensionally Stable Anode® at a rate of 0.7 Amps for a period of 6 hours (a total of 15,120 coulombs). After this time, the solution contained 1950 ppm Fe and negligible Cu with an unqualified but sizeable amount of sulfur floating on the surface. The solid residue, containing 5.9% Fe and 33% Cu, was identified principally as chalcocite, copper and unreacted pyrite. From reconstructive head calculations, the conversion of chalcopyrite to chalcocite and copper was at least 90%.
  • Example 7 [0024] 10 grams of manganese nodule DH-2 (18% Mn, 10% Fe, 0.15% Cu, 0.77% Ni and 0.1 1% Co) was placed in a glass reactor containing 250 ml of 1 M H 2 SO 4 in water at room temperature. Current was passed through the stirred solution using an aluminum foam cathode (20 ppi) and a reticulated vitreous carbon (RVC) anode at a rate of 0.4 Amps for a period of 5Vi hours (a total of 7,920 coulombs). After this time, the solution contained 7180 ppm Mn, 3880 ppm Fe, 34 ppm Cu, 303 ppm Ni and 41 ppm Co.
  • RVC reticulated vitreous carbon
  • the solid residue contained 0.04% Mn, 0.52% Fe, 0.06% Cu, 0.01% Ni and 0.004% Co. From reconstructive head calculations, the dissolution of the different oxides was at least 99% for Mn, 95% for Fe, 58% for Cu, 99% for Ni and 96% for Co.
  • the solid phase was filtered and placed in contact at room temperature (22°C) with a 250 ml of a solution containing 0.2M thiourea of which 12% had previously been converted to formamidine disulfide. After constant stirring, the silver extraction was estimated at 54, 60 and 89% after 1, 5 and 21 hours of contact, respectively.
  • the untreated concentrate showed a silver extraction of only 8, 20 and 81% after 1, 5 and 21 hours, respectively under the same conditions.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un processus destiné à la récupération de valeurs contenant du métal depuis un minerai et/ou depuis un ou plusieurs minéraux, qui ne sont pas facilement oxydables et qui sont susceptibles d'être réduites. Le processus comprend l'étape consistant à : soumettre ledit minerai ou le ou les minéraux à une réduction dans une chambre d'électrolyse ayant un seul support électrolytique acide non divisé ; la réduction étant exécutée par de l'hydrogène en utilisant une cathode comprenant un matériau qui facilite la génération d'hydrogène monoatomique, qui produit une ou plusieurs valeurs contenant du métal sous une forme réduite.
PCT/US2008/054661 2007-02-22 2008-02-22 Processus pour la récupération de valeurs contenant du métal depuis des minéraux et des minerais WO2008103873A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/528,166 US20100012502A1 (en) 2007-02-22 2008-02-22 Process for recovery of metal-containing values from minerals and ores
MX2009000956A MX2009000956A (es) 2007-02-22 2008-02-22 Proceso para la recuperacion de valores que contienen metales a partir de minerales y menas.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US90319507P 2007-02-22 2007-02-22
US60/903,195 2007-02-22

Publications (1)

Publication Number Publication Date
WO2008103873A1 true WO2008103873A1 (fr) 2008-08-28

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US (1) US20100012502A1 (fr)
MX (1) MX2009000956A (fr)
WO (1) WO2008103873A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012078020A2 (fr) * 2010-12-09 2012-06-14 Universidad Autónoma Metropolitana Procédé de lixiviation du cuivre et de l'argent à partir de minerais à phases minérales réfractaires qui contiennent du fer et du soufre

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220033985A1 (en) * 2020-07-30 2022-02-03 The Trustees Of Columbia University In The City Of New York Systems and methods for the electrochemical conversion of chalcopyrite to enable hydrometallurgical extraction of copper

Citations (5)

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US3103474A (en) * 1963-09-10 Electrowinning of metals from electrolytes
US4515672A (en) * 1981-11-09 1985-05-07 Eltech Systems Corporation Reticulate electrode and cell for recovery of metal ions
US4551213A (en) * 1984-05-07 1985-11-05 Duval Corporation Recovery of gold
US5620585A (en) * 1988-03-07 1997-04-15 Great Lakes Chemical Corporation Inorganic perbromide compositions and methods of use thereof
US5650057A (en) * 1993-07-29 1997-07-22 Cominco Engineering Services Ltd. Chloride assisted hydrometallurgical extraction of metal

Family Cites Families (4)

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US3764490A (en) * 1972-04-20 1973-10-09 W Chambers Method of recovering metals
US3736238A (en) * 1972-04-21 1973-05-29 Cyprus Metallurg Process Process for the recovery of metals from sulfide ores through electrolytic dissociation of the sulfides
US3806434A (en) * 1973-09-13 1974-04-23 Herrett W Apparatus and method for electrolytic recovery of metals
GB8926853D0 (en) * 1989-11-28 1990-01-17 Gillham Robert W Cleaning halogenated contaminants from water

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3103474A (en) * 1963-09-10 Electrowinning of metals from electrolytes
US4515672A (en) * 1981-11-09 1985-05-07 Eltech Systems Corporation Reticulate electrode and cell for recovery of metal ions
US4551213A (en) * 1984-05-07 1985-11-05 Duval Corporation Recovery of gold
US5620585A (en) * 1988-03-07 1997-04-15 Great Lakes Chemical Corporation Inorganic perbromide compositions and methods of use thereof
US5650057A (en) * 1993-07-29 1997-07-22 Cominco Engineering Services Ltd. Chloride assisted hydrometallurgical extraction of metal

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012078020A2 (fr) * 2010-12-09 2012-06-14 Universidad Autónoma Metropolitana Procédé de lixiviation du cuivre et de l'argent à partir de minerais à phases minérales réfractaires qui contiennent du fer et du soufre
WO2012078020A3 (fr) * 2010-12-09 2012-08-02 Universidad Autónoma Metropolitana Procédé de lixiviation du cuivre et de l'argent à partir de minerais à phases minérales réfractaires qui contiennent du fer et du soufre

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Publication number Publication date
MX2009000956A (es) 2009-03-09
US20100012502A1 (en) 2010-01-21

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