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WO2025222254A1 - Procédé hydrométallurgique pour cuivre - Google Patents

Procédé hydrométallurgique pour cuivre

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Publication number
WO2025222254A1
WO2025222254A1 PCT/AU2025/050405 AU2025050405W WO2025222254A1 WO 2025222254 A1 WO2025222254 A1 WO 2025222254A1 AU 2025050405 W AU2025050405 W AU 2025050405W WO 2025222254 A1 WO2025222254 A1 WO 2025222254A1
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WO
WIPO (PCT)
Prior art keywords
electrode
copper
solution
ions
cell
Prior art date
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Pending
Application number
PCT/AU2025/050405
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English (en)
Inventor
James William VAUGHAN
David Andrew Mann
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University of Queensland UQ
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University of Queensland UQ
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Publication date
Priority claimed from AU2024901144A external-priority patent/AU2024901144A0/en
Application filed by University of Queensland UQ filed Critical University of Queensland UQ
Publication of WO2025222254A1 publication Critical patent/WO2025222254A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode
    • 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
    • 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
    • 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
    • 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
    • C22B3/10—Hydrochloric acid, other halogenated 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
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells

Definitions

  • the present disclosure relates to hydrometallurgical processes for obtaining copper metal from a copper-containing feedstock.
  • the present disclosure further relates to electrolytic cells for obtaining copper metal from a copper-containing feedstock.
  • Background [0002] Primary copper production starts with the mining of copper-bearing ores, with the great majority of copper ores being sulfides. Copper is typically produced from these ores by one of two process routes: pyrometallurgical (dry) or hydrometallurgical (wet).
  • Pyrometallurgical processes which account for approximately 80% of primary copper production, typically involve grinding sulfide ore, floating the sulfide minerals to create a copper concentrate, smelting the concentrate to make a copper matte, converting the matte to blister copper, casting anodes and electrorefining the anodes to high purity metallic copper.
  • the process steps to convert copper concentrate to anode quality copper metal consume about 8.9 GJ/t-Cu, with total energy for copper production being about 33 GJ/t-Cu.
  • Hydrometallurgical processes account for the remaining 20% of copper production and the typical process involves leaching, solvent extraction and electrowinning. The hydrometallurgical approach requires about 14.7 GJ/t-Cu, largely for the electrowinning step.
  • the relatively high energy consumption of the hydrometallurgical electrowinning step is related to the copper being present in cupric form such that two electrons are required per copper ion in order to form metallic copper at the cathode.
  • conventional electrowinning involves evolving oxygen gas at the anode which requires a high electrowinning cell potential, about 2 V.
  • electrowinning of such materials leads to a copper deposit having undesirable physical properties, such as the copper deposit growing in a dendritic form which increases the complexity of the equipment required and results in additional materials handling steps.
  • a hydrometallurgical process for obtaining copper metal from a copper-containing feedstock comprising: - solubilising copper in the feedstock in an aqueous media comprising a stoichiometric excess of halide complexing agent and an oxidative lixiviant to obtain a solution and a solid residue, the solution comprising cuprous ions; - electrolytically reducing cuprous ions in the solution as catholyte to obtain a copper deposit at a first electrode as a cathode coupled with a second electrode as an anode; - electrolytically stripping the copper deposit from the first electrode as an anode coupled with a third electrode as a cathode and obtaining copper metal at the third electrode.
  • a hydrometallurgical process to obtain copper from a copper-containing feedstock comprising: - solubilising copper in the feedstock in an aqueous media comprising a stoichiometric excess of halide complexing agent and an oxidative lixiviant to obtain a solution and a solid residue, the solution comprising cuprous ions; and - electrolytically reducing cuprous ions in the solution as a catholyte to obtain the copper as a deposit at a first electrode as a cathode of an electrolytic cell and coupled with a second electrode as an anode of the electrolytic cell, the first electrode comprising a cylindrical shell defining a cell volume configured to receive the second electrode comprising an anodic cylinder therein.
  • an electrolytic cell for obtaining copper metal from a chloride solution comprising cuprous ions, the electrolytic cell comprising: - a first electrode comprising a cylindrical shell and defining a cell volume, the cell volume configured to receive, respectively: - a second electrode as an anodic cylinder; and - a third electrode as a cathodic cylinder, wherein the first electrode coupled with the second electrode electrolytically reduce cuprous ions in the solution to obtain a copper deposit at the first electrode as a cathode and the third electrode coupled with the first electrode electrolytically strips the copper deposit from the first electrode as an anode to obtain copper metal at the third electrode.
  • Figure 1 shows a cutaway side view of a cylindrical electrolytic cell in an electrowinning configuration in accordance with an embodiment of the present disclosure
  • Figure 2 shows a cutaway side view of a cylindrical electrolytic cell in an electrorefining configuration in accordance with an embodiment of the present disclosure
  • Figure 3 shows a picture of copper electrodeposited onto the first cylindrical cathode.
  • the process comprises the steps of leaching, electrowinning (100A), and electrorefining (100B).
  • the copper-containing feedstock may comprise a copper sulfide compound, with the solid residue comprising elemental sulfur.
  • the copper sulfide compound may comprise iron, with the solid residue comprising an iron precipitate.
  • the iron is precipitated from a homogenous solution and recovered from the process in a separate stream from the elemental sulfur.
  • the copper-containing feedstock comprises chalcopyrite and/or chalcocite and/or bornite and/or covellite.
  • the copper-containing feedstock may comprise copper in combination with precious metals and/or other base metals.
  • the base metals may comprise iron, tin, aluminium, nickel, cobalt, lead, zinc, selenium, indium, gallium, and combinations thereof.
  • the precious metals may include gold, silver, and/or platinum group metals (ruthenium, rhodium, palladium, osmium, iridium).
  • the copper-containing feedstock comprises waste electrical and electronic equipment (WEEE), also referred to herein as e-waste.
  • WEEE waste electrical and electronic equipment
  • the pH of the aqueous media may be controlled in a particular pH range during the solubilisation of copper in the feedstock. In parts of the process, the pH range may be selected to reduce solubility of certain impurities of the feedstock. For example, the pH range may be adjusted to promote precipitation of impurities from solution such as iron, arsenic, aluminium and sulfate.
  • the pH of the aqueous media may be controlled in a range of 1 to 3 during the solubilisation of copper in the feedstock.
  • the pH of the aqueous media is controlled in a range of 1.5 to 2.5.
  • the pH of the aqueous media may be controlled by any suitable material.
  • the pH of the aqueous media may controlled by the addition of hydrochloric acid, sulfuric acid, sodium hydroxide, sodium carbonate, copper hydroxide, calcium oxide, calcium carbonate, magnesium oxide, and/or magnesium carbonate.
  • Solubilisation may be conducted at a temperature of up to the boiling temperature of the aqueous media. It will be appreciated that higher temperatures lead to improved leaching kinetics, however also increase energy requirements and may require more expensive equipment that is suitable for use with such higher temperatures.
  • an operating temperature is controlled in a range of 45°C to 107°C during the solubilisation of copper in the feedstock.
  • the copper may be solubilised in any suitable manner.
  • the copper may be solubilised in an agitated reactor.
  • the agitated reactors are operated in a counter-current fashion with respect to the feedstock and the aqueous media with solid-liquid separation in between stages.
  • the oxidative lixiviant may comprise cupric ions.
  • the oxidative lixiviant may comprise cupric ions of cupric halides.
  • the oxidative lixiviant may comprise cupric ions of cupric chloride, cupric bromide, and/or cupric iodide. In certain embodiments, the oxidative lixiviant comprises cupric ions of cupric chloride or other halide. [0044]
  • the oxidative lixiviant may comprise ferric ions.
  • the oxidative lixiviant may comprise ferric ions of ferric halides.
  • the oxidative lixiviant may comprise ferric ions of ferric chloride, ferric bromide, and/or ferric iodide. In certain embodiments, the oxidative lixiviant comprises ferric ions of ferric chloride.
  • solubilisation may include introducing to the aqueous media sodium hypochlorite (NaOCl), sodium perchlorate (NaClO4), hypochlorous acid (HOCl), calcium peroxide (CaO2), sodium persulfate (Na2S2O8), peroxymonosulfuric acid (H2SO5), peroxydisulfuric acid (H2S2O8), hydrogen peroxide (H2O2), air, oxygen (O2), ozone (O3), or chlorine gas (Cl2).
  • the stoichiometric excess of halide complexing agent may comprise halides derived from the cupric halide and/or ferric halide in combination with one or more halide salts.
  • the halide salts may comprise chloride salts, bromide salts, iodide salts, or combinations thereof.
  • the halide salts may comprise sodium halides, potassium halides, calcium halides, magnesium halides, lithium halides, or combinations thereof.
  • the stoichiometric excess of halide complexing agent comprises chloride derived from cupric chloride and/or ferric chloride in combination with one or any combination of sodium chloride, potassium chloride, calcium chloride and magnesium chloride.
  • Cupric ions may be formed from the oxidation of cuprous ions in the solution as anolyte (220) at the second electrode (120) as the anode, the anolyte (220) comprising cupric ions returned to the aqueous media.
  • the method further comprises electrolytically reducing cuprous ions in the solution (210) as catholyte (230) to obtain a copper deposit at a first electrode (110) as a cathode coupled with a second electrode (120) as an anode.
  • aqueous solution streams (220) and (230) are combined. This step may broadly be referred to herein as “electrowinning” (100A), an embodiment of which is shown in Figure 1.
  • the process may further comprise physical and/or chemical treatment of the process solution (210) and solid residue.
  • the physical and/or chemical treatment may be selected to recover sulfur or other metals such as gold, cobalt, nickel, zinc and lead as by-products. Physical treatments may be used on the residue to recover unreacted copper sulfides for recycling back to the leach, and to remove gangue materials and impurity precipitates prior to electrowinning.
  • the process may further comprise solid-liquid separation of the solution and solid residue prior to electrolytically reducing (100A) the cuprous ions in the solution (210).
  • An operating temperature may be controlled up to the boiling temperature for the solution (210) during the electrolytic reduction (100A) of cuprous ions in the solution. In some embodiments, an operating temperature may be controlled in a range of 45°C to 107°C during the electrolytic reduction of cuprous ions in the solution.
  • the process may further comprise returning catholyte (230) at least partially depleted of cuprous ions to the aqueous media.
  • the method further comprises electrolytically stripping the copper deposit from the first electrode (110) as an anode coupled with a third electrode (130). This step may broadly be referred to herein as “electrorefining” (100B), an embodiment of which is shown in Figure 2.
  • the conditions for electrorefining (100B) may be such that other metals or metal compounds present on the first electrode (110) from the electrowinning step (100A) are insoluble and therefore remain as solid deposits on the first electrode (110) as copper is stripped from the first electrode (110). After electrorefining (100B), these metals may then be harvested and, optionally, undergo further separation and processing steps.
  • an operating temperature may be controlled in a range of 45°C to 75°C during the electrolytic stripping (100B) of the copper deposit from the first electrode (110).
  • copper metal deposits on the third electrode (130).
  • the copper may be harvested from the third electrode (130).
  • the copper may be harvested by mechanical action or melting of the copper.
  • the copper is harvested by selective melting from a reusable third electrode (130).
  • the copper is harvested by mechanical separation from a reusable third electrode (130).
  • the copper metal may be obtained at the third electrode (130) as electrolytic copper.
  • a first electrolytic cell may comprise the first electrode (110) and the second electrode (120) during the electrolytic reduction (100A) of cuprous ions in the solution (210) at the first electrode (110).
  • the first electrode (110) and the second electrode (120) may be partitioned by a diaphragm (140) to form a cathode compartment and an anode compartment.
  • the diaphragm (140) can minimise the mixing between the catholyte (230) and anolyte (220) such that oxidant generated at the anode (120) is not consumed at the cathode (110).
  • the solution (210) is separately introduced into the cathode compartment as catholyte (230) via inlet (160) and into the anode compartment as anolyte (220) via inlet (170).
  • the catholyte (230) exiting 100A is separately introduced into the cathode compartment of a subsequent cell in series and anolyte (220) is separately introduced to the anode compartment of a subsequent cell.
  • electrolytically stripping (100B) the copper deposit is undertaken with the same cylindrical electrode as in electrowinning (100A) cuprous ions in the solution (210) or (220). That is, in some embodiments, for example as shown in Figure 2, the cell configuration for electrorefining (100B) comprises the first electrode (110) and the third electrode (130) where the reduction of cuprous or cupric ions at the third electrode occurs during the electrolytic stripping (100B) of the copper deposit from the first electrode (110).
  • Electrolyte (240) may be introduced to the cell via either one or both of inlets (160, 170), with any unused inlet closed.
  • electrolyte (240) is introduced to the cell via inlet (160) and inlet (170) is closed.
  • the first electrode (110) and/or the third electrode (130) may be formed of a material comprising one of titanium, stainless steel, inconel, hastelloy, monel, carbon and copper.
  • the second electrode (120) is an inert anode and may comprise one of titanium, carbon, titanium coated with mixed metal oxide, titanium coated with carbon, porous carbon or titanium coated with carbon felt.
  • the first electrode (110) may be in the form of a cylindrical shell that defines a cell volume. In such embodiments, the cell volume defined by the first electrode (110) is configured to receive the second electrode (120).
  • the second electrode (120) may comprise an anodic cylinder.
  • the cell volume defined by the first electrode (110) is further configured to receive the third electrode (130).
  • the third electrode (130) may comprise a cathodic cylinder. Preferably, the third electrode (130) has a greater surface area than the second electrode.
  • the described cylindrical first electrode (110) arrangement allows for a second electrode (120) that is relatively smaller than the first electrode (110). As the second electrode (120) is typically relatively more expensive, this can reduce the capital cost of the equipment during initial set-up. Moreover, the relatively smaller second electrode (120) provides that the rate limiting step during electrowinning (100A) is the anode reaction, which helps to promote a dense and non-dendritic copper deposit. [0066] Although the present disclosure will be primarily described with regard to the above described cylindrical geometry, it will be appreciated that other arrangements and geometries may be utilised.
  • the electrolytic cell may be defined by an alternating pair of first electrode (110) and second electrode (120), in the form of flat plates that are positioned in a spaced, parallel configuration.
  • first electrode (110) and the second electrode (120) are co-axially positioned and spaced apart, defining an annular volume between the respective surfaces.
  • the first electrode (110) and second electrode (120) are preferably sufficiently spaced to allow for a suitable amount of copper on the surface of the first electrode (110) while keeping the power requirements due to the resistance in the solutions (210, 220, 230) at a reasonable level.
  • the first electrode (110) and the second electrode (120) are spaced from 0.5 cm to 4 cm.
  • the ratio of first electrode:second electrode (110:120) surface area is from 1.05:1 to 6.0:1, for example from 1.2:1 to 6.0:1, or from 2.0:1 to 6.0:1. In one embodiment, the ratio of first electrode:second electrode (110:120) surface area is 5.62:1. In another embodiment, the ratio of first electrode:second electrode (110:120) surface area is 2.54:1. [0069] During electrorefining (100B), the first electrode (110) and the third electrode (130) are co-axially positioned and spaced apart, defining an annular volume between the respective surfaces.
  • the first electrode (110) and third electrode (130) are preferably sufficiently spaced to allow for a suitable amount of copper on the surface of the third electrode (130) while keeping the power requirements due to the resistance in the electrolyte (240) at a reasonable level.
  • the first electrode (110) and the third electrode (130) are spaced from 0.5 cm to 4 cm.
  • the ratio of first electrode:third electrode (110:130) surface area is from 1.05:1 to 6.0:1.
  • the second and third electrodes (120, 130) may be interchangeable within the cell volume defined by the first electrode (110) such that the steps of electrowinning (100A) and electrorefining (100B) may be undertaken in the same electrolytic cell.
  • catholyte (230) and anolyte (220) may be discharged from the cell volume, for example via drain (150), and an electrolyte (240) introduced into the cell volume.
  • the electrolyte (240) may be any suitable electrolyte (240) for electrorefining (100B).
  • the electrolyte (240) may comprise sulfuric acid and copper sulfate.
  • the electrolytic cell may undergo various treatment steps in between alternating electrowinning (100A) and electrorefining cycles (100B).
  • the cell volume may be flushed at various points in the process.
  • the flushing may assist in removing contaminants and recovering precious metal containing materials such as insoluble slime from the electrolytic cell.
  • precious metal containing materials such as insoluble slime from the electrolytic cell.
  • the slimes may fall to the bottom of the electrolytic cell during electrorefining (100B) or during the flushing cycle following electrorefining.
  • the recovered insoluble slime may undergo further processing to recover any precious elements present within the slime.
  • other metals present in the copper-containing feedstock may be recovered at many points during the process, including from pre-processing, during leaching, and from the electrolytic steps (100A, 100B) as described above.
  • precious metals such as silver, gold, platinum and palladium may be separated from the leach solution prior to electrowinning (100A) by adsorption onto activated carbon, by electrochemical reduction onto a relatively reactive metal such as zinc, iron, aluminium, titanium, magnesium or copper, and/or by selective precipitation techniques.
  • Flushing the electrolytic cell may be undertaken during and/or after discharge of catholyte (230), anolyte (220), and/or electrolyte (240) from the cell. Additionally or alternatively, flushing may be undertaken after obtaining copper metal at the third electrode (130).
  • the flushing may be conducted using a cell flush solution comprising weak acid, and/or weak acid in halide brine, and/or water.
  • the flushing may further comprise high pressure washing of the cell. Additionally or alternatively, the flushing may comprise chemically cleaning of the cell, for example with nitric acid.
  • the electrolytic cell may undergo pretreatment prior to electrowinning (100A).
  • a solution comprising copper sulfate may be used prior to electrowinning (100A) to precoat the first electrode (110) with a layer of copper thereby reducing the hydrogen generation potential that can occur in the initial stages of electrowinning (100A).
  • Such pre- coating of the first electrode (110) may further assist in improving current efficiency, improving copper electrodeposit morphology, and reducing acid consumption.
  • the carbon may first undergo a pre- treatment to apply a conductive polymeric coating to improve deposit adherence and/or deposit morphology.
  • a number of electrolytic cells may be provided in series. The process may then comprise electrolytically reducing cuprous ions in catholyte partially depleted of cuprous ions by the first electrolytic cell in one or more additional electrolytic cells to obtain a copper deposit at a first electrode (110) as a cathode coupled with a second electrode (120) as an anode of each of the one or more additional electrolytic cells.
  • the fluid in the cell will be oscillated up and down via a repetitive pulsing action on the fluid by a mechanical device or using compressed gas, to provide enhanced mass transfer during the electrochemical reactions. This will enable efficient operation of the cells in a batch mode of operation or when the continuous solution flow is slow.
  • the first electrode (110) may be subjected to nitric acid prior in between alternating electrowinning (100A) and electrorefining (100B) cycles, that is prior to introduction of the second electrode (120) or third electrode (130) into the cell volume.
  • processes in accordance with the present disclosure can allow for the electrochemical production of high-quality copper with significant reductions in the energy required to produce the copper.
  • the electrolyte used had a composition of 175 g/L NaCl, 1g/L HCl and 30 g/L Cu(I)Cl made up with deionised water (DI).
  • DI deionised water
  • the electrolyte was filtered and reused for each of the experiments.
  • An overhead stirrer was used in conjunction with a Teflon impeller in the liquor holding tank.
  • a TPS WP-80D pH meter was used to measure the pH and ORP in the holding tank.
  • the vessel was heated using an IKA C-MAG HS10 hotplate.
  • a nitrogen sparger was used for the holding tank along with plastic wrap to minimise exposure to the atmosphere.
  • the contents of the holding tank were recirculated through the electrowinning cell using a peristaltic pump.
  • the cell unit was a stainless-steel tubular cathode ( ⁇ 800 mL volume) that uses a conductive graphite rod anode; the cathode surface area was 459 cm 2 and the anode surface area was 81.5 cm 2 with a 3 cm cathode-anode spacing.
  • a DC Teledyne power supply unit of 12 V and 30 A was used to provide power to the electrowinning cell.
  • Experimental procedures (1) [0094] The feed tank was placed onto a hotplate and the stirring unit, the pH probe, ORP probe, hotplate thermocouple, stirring rod, sparger, and inlet and outlet tubes were lowered into the vessel.
  • the inlet tube was placed close to the liquid surface in the feed tank to minimise solids intake.
  • the inlet tube feeds to the bottom of the electrowinning cell via the peristaltic pump.
  • the holding tank and cell unit were insulated to minimise heat losses.
  • the electrolyte solution was then gradually poured into the holding tank with the solids, and the overhead stirrer started. Once the liquor was at the desired temperature, the pump was started. This was left to run until the air in the cell unit was displaced.
  • the pH was adjusted using concentrated 32% HCl to a desired level. An initial sample was taken for ICP analysis. The electrodes were connected and the power supply then turned on, with the voltage being controlled and the current being allowed to drift.
  • the cylindrical cathode in the previous series of experiments was a stainless-steel tubular cathode ( ⁇ 800 mL volume). However, the stainless steel cathode failed due to excessive corrosion and was replaced with a carbon tubular cathode ( ⁇ 200 ml volume) that uses a conductive graphite rod anode.
  • the cathode surface area in this experimental set-up was 242 cm 2 and the anode surface area was 87.8 cm 2 with a 1.015 cm cathode-anode spacing.
  • a jacketed comproportionation reactor was added between the feed tank and the electrowinning cell. This reactor was packed with copper wire and copper shavings and heated to 60°C with a recirculating water bath.
  • the reactor was fed from the feed tank via a peristaltic pump to the base of the reactor.
  • the reactor discharge from the top of the reactor gravity fed the electrowinning cell to the base of the cell.
  • the liquor being recirculated did not contain any solids.
  • the liquor used was the same liquor used for all of the experiments which was filtered through a 0.45 ⁇ m membrane filter and the pH adjusted to ⁇ 1.5 prior to beginning the first experiment with the carbon (graphite) cathode cell.
  • Results (2) [0110] In a first experiment with the graphite anode and graphite cathode cell, the cell voltage was maintained between 0.8 and 1.2 V for a total of 75 hours total run time.
  • the electrorefined copper was deposited onto a titanium cathode and the purity of the copper was measured to be 99.94 weight % copper, based on partial dissolution in nitric acid and solution assay.

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Abstract

La présente divulgation concerne des procédés hydrométallurgiques pour obtenir du cuivre métallique à partir d'une charge d'alimentation contenant du cuivre. Les procédés comprennent la solubilisation du cuivre dans la charge d'alimentation pour obtenir une solution comprenant des ions cuivreux et la réduction des ions cuivreux pour obtenir un dépôt de cuivre au niveau d'une cathode à partir de laquelle le dépôt de cuivre est ensuite retiré. La présente divulgation concerne en outre des cellules électrolytiques pour obtenir du cuivre métallique à partir d'une charge d'alimentation contenant du cuivre.
PCT/AU2025/050405 2024-04-23 2025-04-23 Procédé hydrométallurgique pour cuivre Pending WO2025222254A1 (fr)

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AU2024901144A AU2024901144A0 (en) 2024-04-23 Hydrometallurgical process for copper

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061552A (en) * 1975-02-14 1977-12-06 Dextec Metallurgical Proprietary Limited Electrolytic production of copper from ores and concentrates
US20040144208A1 (en) * 2002-11-18 2004-07-29 Koji Ando Process for refining raw copper material containing copper sulfide mineral
US20060151326A1 (en) * 2003-08-06 2006-07-13 Kenji Koizumi Electrolytic apparatus for use in oxide electrowinning method
US20160298248A1 (en) * 2015-04-13 2016-10-13 The Doe Run Resources Corporation Recovery of Copper from Copper-Containing Sulfide Ores

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061552A (en) * 1975-02-14 1977-12-06 Dextec Metallurgical Proprietary Limited Electrolytic production of copper from ores and concentrates
US20040144208A1 (en) * 2002-11-18 2004-07-29 Koji Ando Process for refining raw copper material containing copper sulfide mineral
US20060151326A1 (en) * 2003-08-06 2006-07-13 Kenji Koizumi Electrolytic apparatus for use in oxide electrowinning method
US20160298248A1 (en) * 2015-04-13 2016-10-13 The Doe Run Resources Corporation Recovery of Copper from Copper-Containing Sulfide Ores

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