WO2002027072A1 - Procedes hydro-metallurgiques employant des solutions contenant des sels ferrique et/ou ferreux dissouts - Google Patents

Procedes hydro-metallurgiques employant des solutions contenant des sels ferrique et/ou ferreux dissouts Download PDF

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Publication number
WO2002027072A1
WO2002027072A1 PCT/AU2001/001234 AU0101234W WO0227072A1 WO 2002027072 A1 WO2002027072 A1 WO 2002027072A1 AU 0101234 W AU0101234 W AU 0101234W WO 0227072 A1 WO0227072 A1 WO 0227072A1
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Prior art keywords
ferric
accordance
sulphide
oxidation
iron
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PCT/AU2001/001234
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English (en)
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Stewart Lloyd Shipard
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Stewart Lloyd Shipard
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Priority to AU2001291506A priority Critical patent/AU2001291506A1/en
Publication of WO2002027072A1 publication Critical patent/WO2002027072A1/fr

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    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to hydrometallurgical processes utilising solutions containing dissolved ferric and/or ferrous salts.
  • Iron is a ubiquitous component of virtually all ore bodies, including concentrates. Leaching processes, especially acidic operations, invariably dissolve both the valuable metal and the Iron. Therefore, separation from the Iron, and recovery of the valuable metal from the leach liquor generated is generally a significant component cost for a hydrometallurgical operation.
  • the preferred method of Iron separation depends on the array of mineralogy present in the feed, along with the respective leaching rates and solubilities of the valuable metal and the Iron.
  • Examples of methods applied for the separation of Iron from mineral leach liquors include, direct electrorefining, precipitation or crystallisation, volatilisation, solvent extraction, and ion exchange.
  • Electroplating involves the formation of a metal coating with the required metal being dissolved from the anode.
  • electrorefining involves dissolution of a metal anode with ideally an equal mass recovered at the cathode.
  • electrowinning involves the metal being supplied to the electrolysis operation in dissolved form.
  • Alkali minerals are quite abundant and include oxides, carbonates, silicates and hydroxides. Oxides of Iron are associated with most alkali mineral deposits.
  • An example of a process with critical Iron separation requirement may be the leaching of Nickel from a low grade oxide ore that is associated with abundant Iron, for example, a Nickel Laterite ore.
  • This mineral can be acid leached at high temperatures and pressures, generating a relatively low acid liquor containing essentially Iron and Nickel.
  • Autoclaves are generally applied to increase the rate of mineral dissolution.
  • the dissolved Iron is separated either, by formation of an acid insoluble Ferric oxide species, or by addition of chemicals that, increase the alkalinity. Increased alkalinity is usually achieved by addition of lime or caustic soda. This leaves Nickel in an Iron free solution. if the concentration of Nickel is low, its electrode activity will also be low and the concentration will need to be increased before economic electrorefining can be conducted.
  • Generating a suitable Nickel concentration may involve application of Solvent extraction.
  • the concentration can be increased by immediate evaporation of the liquor after digestion, followed by Iron precipitation.
  • Copper is similarly acid extracted from a range of oxide, carbonate and hydroxide minerals. Copper dissolution generally requires much lower levels of acid, temperature and pressure, than for Nickel laterite dissolution.
  • a somewhat dilute solution containing Copper and Iron is produced.
  • the general process for separating the two dissolved metals involves solvent extraction, as it is difficult to fully separate Iron from Copper by precipitating the Iron as Ferric, as Copper will co-precipitate when lime is applied above pH 3.
  • specialty chemicals are added to the solvent phase, which have a high specific affinity for Copper in preference to the Ferrous or Ferric. Thus, a separation is obtained, with the Copper being back extracted into a strong acid solution.
  • Metallic Copper is recovered by electrowinning from the strong acid liquor.
  • Sulphide minerals from Oxide concentrates such as mineral sands or Tantalum Oxide is an important process operation. Separation of the Sulphide minerals is generally by either gravity or chemical flotation means.
  • contaminant Sulphide minerals are currently removed from coal by means of gravity and flotation means.
  • the process disclosed in this document can be applied to sulphidic coal feed stock material for the purpose of separating the Sulphide to recover a purified coal product.
  • sulphide minerals Numerous valuable metals are associated with sulphide minerals. Some examples are gold, silver, platinum group metals, uranium, nickel, copper, tin, tellurium, tantalum, lead, zinc, iron and cobalt. Complex or alloy Sulphide minerals that combine Iron and another metal also exist.
  • the valuable metal may or may not enter the leach liquor, as this depends on its unique solubility under the chemical environment and temperature conditions applied.
  • Suiphide minerals display a wide range of reactive character.
  • the "primary sulphides” such as Galena (PbS), Acanthite (Ag 2 S) (also called Agenthite), Millerite (NiS), Chalcocite (Cu 2 S), Covellite (CuS) and Sphalerite (ZnS) are the most reactive.
  • second sulphides that is Sulphides that also contain iron, such as Pentlandite ([NiFe] 9 S 8 ) Arsenopy te (AsFeS) and Chalcopy te ([CuFe] ⁇ - x S 2 -x) are less reactive, with sulphides that contain Iron and elemental Sulphur, such as Pyrite (FeS 2 ) type sulphides, including "high Sulphur” Arsenopyrite (AsFeS 2 ) are generally the least reactive. These least reactive minerals are termed “refractory”. However, reactivity can not be assessed solely by chemical formula, as crystal structure, particle size and other properties are critical interacting factors.
  • the valuable metal component associated with any Sulphide mineral can be recovered by either pyrometallurgical or hydrometallurgical means, and some processes combine both.
  • a process that will leach a refractory mineral will also leach a primary Sulphide, whilst a process suitable for leaching a primary Sulphide may not be capable of leaching a refractory mineral.
  • the present invention provides processes that can be applied to suit any Sulphide mineral.
  • Pyrometallurgical processes can be divided into either roasting or smelting techniques. The later, incorporates controlled or limited Oxygen conditions, thereby oxidising Sulphide to Sulphur whilst the metal is simultaneously reduced to the metallic form. The metal then separates from the molten Sulphur. Whilst roasting processes fully oxidise the Sulphur to Sulphur dioxide, and the metal to oxides.
  • Hydrometallurgical sulphide processes do not produce Sulphur Dioxide, and are associated with less environmental pollution concerns. Therefore, such processes can be advantageous if they are associated with affordable capital expenditure at acceptable operating costs.
  • Hydrometallurgical processes can be divided into two categories, “pressure systems” and “atmospheric systems”.
  • Pressure techniques generally rely on the use of Oxygen at pressures above atmospheric. These processes require plant and equipment to extract Oxygen from the atmosphere for this purpose, though direct air is applicable for the more reactive sulphides. Pressure techniques' use agitated autoclave vessels, usually operated on a continuous mode with fresh feed and water entering a series of agitated chambers from one end, with reaction products being discharged at the other. The possible shortcomings associated with such techniques include large capital costs and risks associated with operating a heated and pressurised vessel.
  • reaction rate is inversely related to the particle size. That is, particle size reduction increases the reaction kinetics. The increased rate can enable better economics to be attained.
  • Another group of pressure leach techniques involves the use of oxides of nitrogen as the oxidant species.
  • the oxidant can be autogenously regenerated in the headspace of the pressurised Sulphide reaction vessel.
  • the oxidant to be applied to the Sulphide mineral can be regenerated in a separate purpose built vessel.
  • pressure techniques involve a higher capital cost than atmospheric hydro processes. However, they provide faster reaction rates and thus economics that better suite medium to large projects.
  • the present invention does not involve a poisonous gas, and may operate at atmospheric pressure.
  • Atmospheric techniques involving direct application of air to the mineral slurry suspension are readily applicable to the more reactive primary sulphide minerals.
  • International Patent Publication WO 006784A1 which is titled "Processing of Copper Sulphide Ores", is an example of a process with application restricted to primary minerals.
  • the more refractory minerals require techniques that generate a greater degree of oxidation potential in the slurry.
  • One such process involves application of bacteria to catalyse the sulphide mineral oxidation, with air or more specifically Oxygen being used as the primary oxidant, whilst the bacteria act as a catalyst.
  • Bacterial techniques are commonly applied in heap leach operations and in smaller mineral processing plants. Acid liquors generally in the pH 1.0 to 3.0 region are applied, or self generated from Sulphur oxidation for bacterial processes. Whilst bacterial techniques have been successfully applied to the most refractory type Pyrite minerals, as explained below, the technology does not present a universal option for all sulphide mineral processing' projects. A suitable reference of the state of this art is provided by US patent 6110253.
  • bacteria are not particularly resistant to fluctuations in the chemical and thermal environment. Therefore, a particular bacteria strain may require purified low chloride water. Supplying this water can be an additional and significant cost burden at some mining locations.
  • bacterial oxidation techniques have not proven commercially successful when applied to medium and large projects, with continuous production objectives. Bacterial oxidation involves an inherently slow reaction rate, even when optimised, and therefore incurs relatively huge tank requirements.
  • Halide processes including chloride, bromide, or iodide, or combinations of these halides have been created. To maximise the usefulness of a halide oxidant, with regard to solubility and electrochemical oxidising potential, these processes need to operate at higher pH levels, when conducted at atmospheric pressure.
  • oxidising agent could be, hypochlorite or dissolved chlorine gas, similarly hypo-bromide or bromine gas and likewise with Iodine, or a combination mixed halide species.
  • References include US Patent 4557759, Australian Patents Application 48578/85, 55722/90 and 25022/84.
  • halide processes have proven applicable for reactive and moderately refractory sulphides such as Chalcopyrite, yet have not been proven for Pyrite based minerals.
  • the straight halide processes' involving direct application of an oxidant halide species to the mineral surface generally operate in the pH range of 6.0 to 9.0, thereby maximising the oxidants chemical potential.
  • limitations associated with the solubility of the metal species are prevalent, resulting with the need for low solids concentrations during the sulphide oxidation.
  • solubility can be enhanced, and economic reaction rates achieved by operating at close to saturation level for chloride ions and near boiling point temperature.
  • the limited application of this process type may be indicative that there is scope for technical improvement in comparison to the reaction rates attained with the previously mentioned pressure and bacteria processes.
  • the Cupric method is able to operate at a lower pH of 4.0, that is a higher acid level. Due to the greater solubility of oxidised metals in the increased acid conditions, higher slurry concentrations can be applied. However, significantly higher solubilities can still be attained in stronger acid conditions.
  • the present invention enables application of stronger acid solutions and therefore enables even higher concentrations to be attained.
  • Halide oxidant species have a propensity to exit the process through natural evaporation of the gas.
  • Iodine or bromine processes, with lower gasification losses are an option, however these are associated with additional chemical cost requirements and environmental risks.
  • the present invention does not generate a volatile substance. Therefore, the entire anode oxidising potential created is transferable to the sulphide mineral.
  • halide ions provide a beneficial catalyst role to all hydrometallurgical sulphide oxidation techniques, irrespective of the operating pressure or oxidising agent being applied. See Australian Patent Application 12701/95 as an example.
  • the atmospheric hydrometallurgical processes referred to above provide alternatives with generally lower capital costs than pyrometallurgical routes.
  • these known alternative processes have inherent shortcomings such as, slow reaction rate, low pulp concentration and inefficient transfer of the anode oxidising energy to the Sulphide mineral.
  • pressure techniques or pyrometallurgical processes being largely the preferred economic option, especially for larger projects, with a Sulphide mineral that displays refractory behaviour.
  • a suitable example is the simple process disclosed by the recent patent Application PCT/AU00/00568 (WO006784A1 ).
  • a process that combines Ferric with application of pressurised autoclave equipment a minimum Oxygen level above atmospheric conditions is maintained through the mineral leaching and it is therefore different to the leaching concept disclosed in this patent.
  • the application of Oxygen rather than Ferric only during the mineral digestion requires solvent extraction prior to electrowinning for the Copper recovery.
  • the methods of the present invention have as one object thereof to overcome the above mentioned, problems associated with the prior art.
  • a straight forward, laboratory digestion technique will not be an appropriate method for assessing the potential of a Ferric leach solution.
  • a straight forward, leaching process would be one in which the solids and reactant liquor are first mixed, then heated to increase the reaction rate.
  • Gold can be leached into a cyanide solution during grinding with addition of appropriate chemicals to the mill liquor feed.
  • Oxygen itself is an expensive requirement.
  • the method of the present invention provides a lower cost means of providing a satisfactory oxidant.
  • the application of a Ferric oxidant liquor means that grinding media containing Iron can not be applied.
  • Patent Application 50067/90 discloses that iron and or ceramic grinding media can be applied. However, when ferric is applied Iron is rapidly dissolved. Clearly the disclosure of this prior art specification does not contemplate the application of ferric as an oxidant, as is a feature of the present invention.
  • This patent discloses an electrolytic concept whereby, when correctly applied, the valuable components dissolved with the Iron can be recovered, whilst also allowing for the recovery of Iron in metallic form, if desirable.
  • This electrolytic process discloses a novel method that enables the direct generation of Ferric ions at an anode in the presence of Chloride ions, without the formation of Chlorine gas.
  • Ferric ions can be intum applied as oxidants to assist in the leaching of valuable metals from minerals, such as Sulphides.
  • Discussion of the present invention introduces various hydrometallurgical process concepts applicable to the extraction of valuable metals from sulphide minerals at atmospheric pressure, with the ability to apply relatively high levels of ferric ions, and thus high oxidant potential and power. Thereafter application of Ferric as the oxidant enables several alternative methods for recovering the valuable components from the Sulphide material, of which, one particular method also claimed as an invention, involves the direct electrowinning of the valuable metal components directly from the leach digest liquor.
  • the word "comprise”, or variations such as “comprises” or “comprising” will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
  • metallurgical processes are commonly divided into two groups. Hydrometallurgical operations are conducted in water and or solvents, whilst pyrometallurgical processes apply thermal energy to create temperature driven reactions that are not otherwise possible in water.
  • a hydrometallurgical process characterised at least in part by an electrolytic method enabling the direct generation of ferric ions at an anode, whilst enabling the suitable recovery of valuable metals dissolved with the iron.
  • the process is not restricted to any particular counter anion to the ferric cation.
  • a distinct advantage of the discovery is that one hundred percent Ferric levels can be regenerated in the presence of chloride ions, without the formation of chlorine gas.
  • the Iron may also be recovered in metallic form.
  • the ferric ions may be in turn applied as oxidants to assist in the leaching of valuable metals from minerals.
  • the mineral may be a sulphide mineral.
  • a process for the recovery of valuable metals from sulphide minerals at atmospheric pressure the process characterised by the application of high levels of ferric ions, thereby achieving high oxidant potential and power, and the subsequent application of ferric as an oxidant in a leaching process in the recovery of the valuable metals from the sulphide minerals.
  • the process further provides the direct electrowinning of the valuable metal components directly from the leach digest liquor.
  • the process comprises the electrolytic recovery of the valuable metal components at a cathode, from solutions that contain considerably high levels of iron.
  • the process further comprises the use of appropriate anode materials for the chemical conditions and temperature, and a suitably concentrated ferrous or ferric liquor, such that chlorine gas will not be evolved at the anode if the solution concentration is above a critical minimum.
  • This dissolved iron level is preferably at or above about 25 grams per litre. Further preferably, the dissolved iron level is at or above about 100 grams per litre.
  • the process involves the formation of a negatively charged complex in a solution containing ferrous and/or ferric.
  • the process is preferably characterised by the selective concentrating of dissolved metals by electrowinning, and the simultaneous production of highly concentrated ferric solutions, without the formation of undesirable toxic species such as chlorine gas.
  • the process further preferably comprises the migration of a negatively charged ferrous complex toward an anode surface, including through the micro pores of a membrane under the influence of an electric field.
  • the process is characterised by a membrane cell holding a solution containing two metals, one of which is dissolved iron, the cathode activity of the iron being significantly and effectively reduced by formation of a negatively charged iron complex.
  • a solution containing ferric can be processed, under suitably concentrated conditions, in a continuous manner with it entering either the anode or the cathode compartment of a membrane cell.
  • This direct electrowinning is preferably performed in a single compartment, electrolysis operation, without a membrane.
  • the technology can be applied to a membrane electrolysis operation.
  • the process is characterised by the separation of metals with higher cathode reduction potential than Iron, such as Zinc.
  • the anode preferably has an oxide coating.
  • the oxide coating being insoluble in the anolyte solution.
  • the oxide coating can be formed naturally on the material, with or without an electric current being supplied, or can be applied by other coating means, and can be of a completely different chemistry to the substrate of the anode.
  • the anode is preferably formed of ruthenium and iridium oxides on a titanium substrate.
  • the anode oxide coating may be formed of one or more ceramic oxide materials.
  • the ceramic oxide materials include oxides of alumina, zirconia and tantalum silicates.
  • the process steps of solvent extraction or crystallisation are incorporated into the process.
  • the process of the present invention When applied for the dissolution of Sulphide minerals containing iron, the process of the present invention generates ferrous in solution, from the feed mineral. This Ferrous must be removed as a product from the process to maintain a process mass balance. Though numerous advantages of electrolysis techniques have been discovered, this oxidation of the ferrous can be achieved by means other than electrolysis methods. An example is the oxidation by air or purified oxygen, which generates ferric hydroxide that precipitates from a low acid solution. Another is the formation of the insoluble ferric arsenate compound.
  • the solution contains cations which have a higher cathodic reduction potential than ferrous then these are preferably reduced and separated from the iron under conditions in which they are in sufficient concentration in respect to the ferrous and above critical concentrations with respect to the water.
  • Lower current density on the cathode and higher concentrations of the target metal in solution are preferable for better selectivity of separation during electrowinning.
  • Copper ion leached by ferric ion oxidation is preferably recycled as an oxidant suitable for oxidising sulphide minerals containing copper, such as chalcopyrite.
  • a process for the dissolution at atmospheric pressure of sulphide minerals comprising the oxidation of the sulphide minerals by ferric ions to form ferrous ions during the leaching operation, the ferrous ions thus formed are thereafter oxidised in a separate process to regenerate ferric ions, the regenerated ferric ions being reintroduced to the oxidation of the sulphide minerals.
  • the process may utilise the deliberate application of saline process water, thereby enabling appropriate boiling points to be attained at relatively lower oxidising potential.
  • Highly concentrated liquor levels that provide an increased boiling point at atmospheric pressure can be utilised, and may provide significant benefits.
  • Oxidation potential with respect to the liquor used for the sulphide oxidation and mineral leaching may be altered by varying, either, the ferric to ferrous ratio, the total ferric concentration or other chemicals dissolved in the sulphide oxidation liquor. Thereby a selective oxidation and leaching of one sulphide mineral in preference to another can be attained.
  • the size classification process may preferably be incorporated in situ with the leaching, or as an adjunct to the reaction vessel.
  • inorganic chemicals are able to catalyse the hydrometallurgical oxidation of the Sulphur.
  • These inorganic process catalysts may include one or more of the group arsenic, phosphorus, vanadium, uranium and tellurium, being able to form stable oxide or hydroxide species that are soluble in the liquor phase during the sulphide mineral oxidation.
  • the process may also comprise a method step in which the ferric liquor and sulphide mineral slurry is almost evaporated, whereby as the liquor evaporates, the boiling point increases along with the ferric concentration, such that the oxidation potential increases to a point sufficient to fully oxidise elemental sulphur.
  • Figure 1 represents a flow sheet for a process to dissolve a Pyrite type mineral in accordance with a first embodiment of the present invention, with the primary commercial purpose to extract and recover Gold;
  • Figure 2 represents a flow sheet for an Arsenopyrite process in accordance with a second embodiment of the present invention with the primary commercial purpose to extract and recover Gold;
  • Figure 3 represents a flow sheet for a process that involves extraction and recovery of a metal that is of low solubility, such as the extraction of Lead from Galena, in accordance with a third embodiment of the present invention
  • Figure 4 represents a flow sheet describing a process for separating Iron
  • Figure 5 represents a flow sheet for a process that involves oxidation of a Sulphide feed stock containing Iron, Copper and Nickel, in accordance with a fifth embodiment of the present invention
  • Figure 6 represents a flow sheet for a process whereby an alkali mineral is acid leached with recovery of the metals and acid regeneration by electrolytic means in accordance with a sixth embodiment of the present invention.
  • Copper is chosen as a general example;
  • Figure 7 is a flow sheet for a method in accordance with the present invention as applied to the removal of sulphides from acid insoluble minerals, in accordance with a seventh embodiment of the present invention.
  • the reaction at the anode may involve the oxidation of water if it has a greater anode activity than the anion.
  • the reaction at a cathode may involve reduction of water. Therefore, an acid can be generated at the anode, or a hydroxide at the cathode, if these are desirable, or inadvertent.
  • the ability to selectively reduce a metal in preference to Iron, in a dilute solution is a function of the respective reduction potential. For example, the reduction potential of Copper (+0.35 volts) is significantly higher than Nickel (-0.23 volts), which is higher than that of Iron (-0.41 volts). The selective recovery of Copper from a dilute solution containing Iron can therefore tolerate a much higher amount of Iron than a comparative Nickel process.
  • Chloride is a ubiquitous anion. It will therefore infiltrate into almost all known mineral processing and electrolytic processes.
  • Chlorine gas will not be evolved at the anode if the solution concentration is above a critical minimum. Whilst Chlorine atoms may form at the anode as an intermediate they do not combine to form a volatile substance.
  • Cuprous chloride If a dilute solution is made Cuprous chloride it will precipitate on cooling, as indicated by the (s) subscript. If Ferrous Chloride is combined and the concentration of each species increased then the soluble Cuprous-Ferrous Chloride complex forms. Whereupon, in the presence of an electric field, the Cuprous being positively charged is attracted toward the cathode, and the Ferrous complex anion is attracted to the anode only.
  • the non-Ferrous metal can be recovered and separated from the Iron, whilst both are dissolved in the aqueous solution.
  • a solution containing Ferric can be processed, under suitably concentrated conditions, in a continuous manner with it entering either the anode or the cathode compartment of the membrane cell.
  • the direct electrowinning can also be performed in a single compartment, electrolysis operation. That is, without a membrane.
  • Chloride If excess complex forming anions are present, such as Chloride, free Chloride anions will be available to migrate to the anode surface and the resultant reaction will cause Chlorine gas to form. If the feed liquor has a shortage of Chloride or other suitable anions then negatively charged complexes can simply not form. If strong complexing agents that are charge neutral, such as amine (NH 2 ) are present these will exclude the Chloride from the Ferrous and or Ferric complexes, reducing the ability to form negatively charged complexes, and reducing the ability of an electric field to transport such species in the desired direction.
  • amine amine
  • Increasing the concentration of the solution, by thermal evaporation, is perhaps the simplest method of increasing the stability of both Ferrous and Ferric complexes.
  • Other concentration techniques such as vacuum assisted evaporation or electrodialysis may be equally applicable.
  • the preferred arrangement, such as the selection and shape of cathode and anode materials, for the electrolytic method will vary from project to project. It is expected that those skilled in the refining of metals by electrolytic means would be able to identify optimum conditions for particular case examples.
  • this section has disclosed a method by which the concentration of a solution, that may or may not contain Chloride anions, is increased to cause formation of stable complex structures.
  • Application of such solutions can result in benefits for the electrowinning of metals from a solution containing Ferrous and/or Ferric, without the formation of Chlorine gas, or other halide oxidant species, if Chloride is present in that solution.
  • a simple process is hereby disclosed that can even be applied for the electrolytic manufacture of metallic Iron from solutions that contain Iron. With an electrolytic process that is highly suitable for application to a low acid, Chloride solution, conducted in vessels open to the atmosphere.
  • This aspect of the present invention can be equally applied to enhance the separation of metals with higher cathode reduction potential than Iron, such as Zinc.
  • the propensity to enable Chlorine gas formation at the anode is reduced by preformation of an oxide coating that is insoluble in the anolyte solution. How or when the coating is formed does not appear to be critical. It can either form naturally on the material, with or without an electric current being supplied, or be applied by other means to a completely different substrate.
  • coatings of precious metal oxides such as Ruthenium and Iridium on a Titanium substrate, can eliminate the formation of Chlorine gas whereas under the same conditions the gas will readily form on exposed Titanium. It is envisaged that other oxide coatings on metal substrates will provide similar advantages.
  • ceramic oxide materials provide a similar resistance to the formation of Chlorine gas. These materials include Alumina, Zirconia and Tantalum Silicates, and can be composite mixtures.
  • Ferric solutions can be applied for many purposes.
  • a ferric solution is applied to the processing of Sulphide minerals.
  • the product solution contains three moles of Iron, in relation to every two moles in the reactant solution. Therefore, when conducted at appropriate chemical conditions such that Ferric Hydroxide will separate from the process liquor, oxidation of the product solution with Oxygen regenerates a balanced requirement of Ferric.
  • Direct electrowinning of these solutions can readily produce a Copper metal with above 90% purity, which is highly suitable for further electrorefining to pure Copper metal, if desired.
  • the present invention further discloses a process in which copper ion leached by the ferric ion oxidation is also able to be recycled and provide a potential oxidant agent suitable for oxidising sulphide minerals containing copper, such as chalcopyrite.
  • the concentration of Ferric, Ferrous and Nickel effect the equilibrium. Increasing the Ferric increases the reaction rate, whilst increasing the Ferrous and or Nickel decreases the reaction rate.
  • the benefits of this disclosure are not only a product solution with higher Nickel concentrations, but leaching conditions with higher solids concentrations can also be applied during the Sulphide mineral oxidation. Both of these mean reduced tank volumes for the same tonnage of material processed and thus reduced capital cost opportunity relative to other process technologies.
  • a process for the atmospheric dissolution of sulphide minerals is essentially a "closed loop liquor” operation, comprising the oxidation of the sulphide minerals by ferric ions to form ferrous (plus other) ions during the leaching operation.
  • the ferrous ions thus formed are thereafter oxidised in a separate process to regenerate ferric ions, the regenerated ferric ions being reintroduced to the oxidation of the sulphide minerals.
  • a bleed stream may be extracted from the closed loop for control and removal of minor contaminants dissolved into the liquor.
  • the Sulphide component of the mineral is oxidised to form Sulphur.
  • This Sulphur maybe inturn oxidise to form an anion of Sulphur.
  • the valuable metal associated with the Sulphide mineral may dissolve or remain insoluble.
  • the process of the present invention can be applied to all known sulphide minerals, including the most refractory of sulphides, such as arsenopyrite and pyrite.
  • sulphide minerals including the most refractory of sulphides, such as arsenopyrite and pyrite.
  • the optimum chemical environment and critical iron level being adjusted to best suit each particular mineral source and economic objective.
  • the feed mineral(s) can be prepared by particle size reduction, or a chemical leaching process to expose a fresh Sulphide mineral surface.
  • These mineral preparation processes can be achieved with any type of equipment or time frame and need not be restricted to known methods.
  • ore preparation techniques is not seen as critical to the present invention, other than where they can be applied simultaneously.
  • particle size reduction and Ferric leaching of a Sulphide mineral may be conducted simultaneously, in the same equipment and or unit operation.
  • Ferric ions can be applied as an oxidant of Sulphide over a wide range of chemical conditions and temperatures. Each specific application will have its own set of possibly unique optimum conditions, thus the process of the present invention is not restricted to any precise set of chemical and physical conditions.
  • suitable chemical conditions applicable for Ferric as an oxidant are found in weak acid solutions between pH zero and 4.5, with reaction temperatures above 50 degrees Celsius. Ferric can be suitably applied in higher or lower acid strengths if required. As long as the chemical environment is such that the Ferric can maintain sufficient oxidising potential, or contribute as a catalyst to the leaching or overall processing of the Sulphide mineral.
  • the processes of the present invention may utilise the deliberate application of saline process water.
  • the additives for this increased boiling point purpose need not be restricted solely to salts of Iron and Sodium. Increased boiling points can be obtained by the addition of "spectator chemicals” such as Hydrochloric acid or Sulphuric acid, or a combination of chemicals. These chemicals may or may not be a natural component of the raw process water being applied. Similarly, water miscible solvents or organic chemicals may also be applied for this purpose.
  • spectator chemicals such as Hydrochloric acid or Sulphuric acid, or a combination of chemicals.
  • the process can further be applied with varied oxidation potential, with respect to the liquor used for the sulphide oxidation and mineral leaching. This being achieved by varying, either, the ferric to ferrous ratio, the total ferric concentration or other chemicals dissolved in the sulphide oxidation liquor. Thereby, a selective oxidation and leaching of one sulphide mineral in preference to another may be attained. Temperature control is another means of selectively leaching a more reactive sulphide from a more refractory mineral.
  • the leach operation can be conducted in any leach vessel design.
  • the vessel could be as simple as an earth lined dam or a heap leach type' process with an impermeable lining. It could be a percolation column, a vat leach, an agitated tank reactor even an autoclave, though pressure is not a prerequisite to assist the process when Sulphur is the preferred product state.
  • the preferred leach process design will depend on the interaction of many variables and include the mineral and gangue type.
  • the leaching mode of operation can be performed in batch, counter current of plug flow processing. Again, many known project specific variables will impact on the preferable equipment design and operating procedures.
  • the leaching process of the present invention may be operated in a continuous mode or in a series of batch operations, or a combination of the two.
  • the sulphide oxidation reaction- can be operated such that the solids progress in a regime counter current to the leaching liquor.
  • the process may work equally well or better in some circumstances with a plug flow approach with both solids and liquor progressing in the same direction, as seen in a tube reactor.
  • the mineral particle should be introduced to the reactant liquor, when the reactant liquor has been preheated to the desired initial reaction point.
  • Agitation of the slurry during the sulphide digestion should be designed such that the potential for air entrainment is minimised. That is, agitation itself can be minimised.
  • Steps should be taken to minimise the amount of dissolved Oxygen gas in the reactant Liquor, prior to its addition to the Sulphide leaching vessel.
  • the process is assisted by the reduction of oxygen gas in the digestion liquor during the sulphide oxidation process, resulting in faster reaction rates and most significantly a greater degree of sulphide mineral oxidation. Boiling the liquor immediately prior to sulphide oxidation and or maintaining the boiling point during the oxidation can adequately attain this reduced oxygen content.
  • the reduced oxygen content can be produced by any of a number of other means.
  • a fresh particle surface needs to be exposed, either prior to, or during the Sulphide leaching, especially if the particle has a high degree of oxide coating and a propensity to display refractory behaviour.
  • Full implementation of these rules is not always possible, but adherence to the doctrine provides better results.
  • the leach equipment costs and performance can be significantly improved if the application of floccule forming additives is conducted.
  • high molecule weight flocculant polymers such as Acrylamide polymers
  • improved leaching rate and particle handling are observed.
  • the sulphide oxidation reaction and mineral leaching may require heat to be applied to initiate and maintain the reaction process at suitably economic rates.
  • This heating energy can be supplied by any means of heat energy delivery, such as heat exchangers, submerged electrical elements, injected steam, or from an infra red or microwave light source.
  • the sulphide oxidation reaction and mineral leaching may be thermally self sufficient when operating at a desirable process rate in reaction vessels of suitable size to limit energy losses.
  • the heat energy released can be utilised to supply heat to other chemical or physical reactions.
  • the sulphide oxidation process of the present invention may be made to preferentially provide the larger particles with a longer residence time by incorporating a particle size' classification operation during the sulphide mineral oxidation stage. Thereby the residence time by which the larger particles are in the presence of the ferric liquor at its highest oxidation potential is increased.
  • the size classification process can be incorporated in situation with the leaching, or as an adjunct to the reaction vessel.
  • the Ferric leaching of the present invention may be applied in a percolation column.
  • the ferric rich feed liquor entering from the bottom is deliberately pulsated such that the reacted finer solids are preferentially transported by viscous means to the top. A preferential reaction of the larger particles is thereby automatically attained.
  • the sulphide mineral oxidation process can be conducted in water of any salinity, and it can be assisted by the application of hard water at appropriate points of the process liquor circuit. Calcium and Magnesium will precipitate anions generated by the oxidation of Sulphur, such as Sulphate, thereby assisting their removal from the process liquor. In addition, Calcium will assist in the precipitation of Arsenate anion, if it is leached from a mineral bearing Arsenic.
  • the operation of the sulphide mineral oxidation can be applied at temperatures, which form saturated solutions of the valuable metal when cooled.
  • temperatures which form saturated solutions of the valuable metal when cooled.
  • the Sulphur be separated from the residue material after oxidation of the Sulphide mineral, then it can be recovered as a product or as will be explained, further oxidised.
  • the product slurry from the mineral digestion is simply cooled below the melting point of Sulphur, prior to solid liquid separation.
  • Solidified Sulphur can also be separated from the residue after filtration by otherwise known dissolution techniques, as it is soluble in Chlorinated Hydrocarbons. It can also be separated by direct filtration of the residue at temperatures at which the Sulphur melts. Sulphur product
  • Sulphur can be separated from the residue during the leaching, in any of the methods described below.
  • Arsenic is such an example.
  • Phosphorus, Vanadium, Uranium and Tellurium are other possible catalysts.
  • Another method hereby disclosed for Sulphur oxidation is to almost evaporate the Ferric liquor and Sulphide mineral slurry. As the liquor evaporates, the boiling point increases along with the Ferric concentration, thus the oxidation potential increases to a point sufficient to fully oxidise elemental Sulphur. The evaporated solids can then be redissolved and the valuable metals recovered by appropriate means.
  • Figure 1 there is shown a process for obtaining gold product from a pyrite containing flotation concentrate, a gravity concentrate or run of mine material.
  • the method of preparation if any, is not considered important.
  • the operation of particle size reduction (1 ) is displayed, since it is most likely that the feed material will be a flotation concentrate, as this particular unit operation is generally appropriate for such feed material.
  • This operation is also possible to incorporate this operation with the Sulphide mineral oxidation leaching reaction (2). That is, an oxidative Ferric liquor is placed into the grinding mill and a simultaneous grinding leach operation is performed.
  • the simultaneous grinding leach ensures that the highest possible degree of Ferric reaction is generated.
  • a high degree of Ferric reaction is always desirable as this enables equipment size reductions at the leaching stage and operating electrical efficiency when the Ferric is regenerated by the electrolytic process (5).
  • the mill design for the simultaneous leaching is not critical, though the preferred operating technique is to have the solids clearly submerged at all times. It appears that vertical mills with or without rotating impeller are a better design conception to deliver grinding with minimum air entrainment.
  • Gold dissolved in the clarified liquor is adsorbed onto activated carbon, ion exchange resins or Zeolite type materials. It is recovered from the adsorbent by appropriate and otherwise well known methods.
  • Equation (g) explains the reaction, which occurs during operation of the Sulphide oxidation process, with respect to Pyrite mineral.
  • the preferred method for operating the electrolytic membrane cell depends on the ratio of Ferric to Ferrous and the concentration of Ferrous in the liquor after digestion. If Iron is to be plated at the cathode then a minimum concentration of Ferrous must be maintained. This is invariably above 100 grams of Ferrous cation per litre.
  • the Iron product may or may not remain attached to the cathode. If it remains attached it may be simply scratched or scraped from the cathode surface, or both cathode plus fresh metallic Iron are further processed to recover the product Iron.
  • the metallic Iron is dislodged from the cathode surface during the electrolysis operation, it can be easily separated from the liquor by some physical means, such as gravity thickening and or filtering (6).
  • the clarified catholyte is then transferred to the anode compartment of the membrane cell whereupon the remaining Ferrous is oxidised to Ferric.
  • the liquor When the liquor is sufficiently oxidised it is reheated (7) to the desired process temperature and reapplied to digest further Pyrite.
  • the Sulphur contained in the residue is separated by some means, well known (8). Such as filtration at temperatures above the melting point of Sulphur or Solvent extraction.
  • the gold is then extracted and recovered by application of an alkaline cyanide process (9).
  • Figure 2 there is shown a process similar to that of Figure 1 but directed to arsenopyrite and the presence of Arsenic catalyses the oxidation of Sulphur.
  • Ferric oxidation generates the Arsenous cation, As 3+ .
  • This species is able to be simultaneously oxidised by even very low levels of Oxygen to form the As 5+ Arsenic cation, as per equation (i) (Ferric may or may not also cause this reaction.)
  • Equation (j) attempts to explain the overall reaction.
  • Arsenopyrite incorporates the application of a membrane cell, similar to that disclosed in the previously detailed Pyrite example. This is applied to ensure maximum regeneration of the Ferric, in a desirable time. It has been discovered that Arsenic can be removed in the metallic form from the cathode cell, if the presence of Ferric is virtually zero. In this application, Arsenic can be separated from the Ferric liquor that enters the anode compartment as it is transported by electrical phenomenon into the cathode compartment. Arsenic can be plated in preference to Ferrous by operating with a limited Ferrous concentration in the cathode cell.
  • cathode material can assist the process, as a material that enables Hydrogen Gas to be evolved with hydroxide ions being generated can be applied.
  • the formation of hydroxide ions provides potential benefit by reducing the need to add other alkali chemicals.
  • a recommended point of application for this particular electrolytic operation is post Ferric Arsenate separation.
  • Arsenopyrite concentrates experienced to date are suitable examples, then it is most likely that an Arsenopyrite gold feed stock will also contain some Pyrite mineral hosting additional Gold, or vice versa. It is thus most likely for a process that is a hybrid of the two process diagrams disclosed above, to be required.
  • FIG 3 there is shown a process in accordance with the present invention for use with low solubility metals.
  • the extraction and recovery of Lead from Galena is used as an example.
  • a Chloride anion system is provided though the overall process concept, works equally well with Sulphate or acetate, in theory other anions.
  • the elemental Sulphur is then separated with the residue solids (3) and can be recovered with methods similar to the means discussed above.
  • the liquor is then further cooled such that Lead Chloride precipitates out (4). This insoluble Lead is separated from the Ferrous process liquor (5).
  • the Ferrous needs to be oxidised and is transferred to the electrolytic membrane cell (6), whilst the Lead precipitate is placed into the cathode cell.
  • the ferrous liquor can be placed into either the cathode compartment solely or into both compartments. Ferrous is required in the cathode compartment acts to assist the transfer of electric charges into the anode compartment.
  • the process may also be achieved by combining, operations (4), (5) and (6) into a single unit operation conducted entirely in the electrolytic cell.
  • a potential problem is foreseen with the possible formation of precipitate in the pores of membrane cell primarily during periods of plant shutdown.
  • a Ferric Acetate process may be applied to Galena as it has been discovered that Acetate anions are suitable for this purpose of maximising the solubility of the Lead.
  • Chloride or Sulphate precipitation route it is critical that only a small amount of acetate, will optimise the process. If too much Acetate is added to either process, acetic acid evaporates from the process. It must be noted that Acetate anions bond strongly with the Ferric and lower its oxidation potential.
  • Galena it is common for Galena to be associated with other Sulphide minerals. As is explained in the following example, the separation of Lead by precipitation can be incorporated as a component of a more complex overall process.
  • FIG 4 there is shown a process in accordance with the present invention for use in respect of sulphides containing a combination of copper, lead, zinc, silver and gold.
  • the Sulphide mineral is oxidised in hot ferric liquor as indicated by item (1 ).
  • the oxidation of such ores is able to generate virtually one hundred percent consumption of the applied Ferric, that is the output liquor is virtually free of Ferric.
  • Iron is associated with the Copper, in a mineral such as Chalcopyrite, though there may also be a separate reactive Iron Sulphide mineral in the feed.
  • the feed stock contains Gold
  • this component can report with the residue solids and be recovered by alkaline cyanide processing.
  • An alternative if the Gold is associated with a less reactive mineral such as Pyrite is to limit the oxidising potential applied and treat the Gold bearing mineral separately.
  • the recovery of Silver is hereby disclosed. Its' recovery relies on the application of the high solubility of Silver Chloride complexes in strong Chloride solutions. If the process liquor is operated in a slight excess of hydrochloric acid, say as little as 0.01 gram Hydrochloric per litre, then the Silver will remain in solution when cooled. If the chloride level is low, Silver will co-precipitate with the Lead. The critical Chloride level required to maintain the Silver in solution whilst the lead precipitates is a direct function of the Silver concentration.
  • the Silver Chloride anion can be removed from the process.
  • Adsorption onto activated carbon or ion exchange resin or solvent extraction, are alternative separation and concentration procedures.
  • the diagram indicates Silver extraction by adsorption (5).
  • a method hereby claimed that enables the Ferric potential to be generated after a salt has been separated from the process liquor is by addition of an acid prior to an electrolysis process.
  • the free acid proton is reduced to Hydrogen gas at the cathode, whilst the required Ferric is generated at the anode.
  • the acid addition point can be located at any position along the flow chart, and selected to best suit a particular operation.
  • the solution should contain Ferrous, Cuprous, Zinc and possibly small quantities of Lead and Silver.
  • the solution is transferred into the first of a series of membrane cells designed to electrowin firstly the Copper (6), then the Iron and Zinc (7), simultaneously.
  • the design or volume of cathode and anode cells need not be identical.
  • the cell has to be designed such that the anode has a sufficient potential to enable oxidation of the desired Ferrous and removal of the metal products produced from the cathode.
  • Process control of the electrolytic aspects of the above process is quite critical for high process efficiency to be attained. For example, migration of the Ferrous ion into the anode compartment, through the membrane can occur at a rate faster than desirable. Especially as electrode inefficiencies occur.
  • Iron is associated with the Copper, in a mineral such as Chalcopyrite, though there may also be a reactive Iron Sulphide.
  • the Sulphur (3) is separated from the residue after clarification of the discharge liquor from Sulphide oxidation (2).
  • the clarification can be attained by any known means.
  • Each operation is conducted in a membrane cell, thereby enabling Ferric to be generated in the anode compartments.
  • the liquor is recycled through the anode compartments.
  • the precise order or path through the anode compartments is not critical.
  • a preferred route can be identified to suite any particular equipment and desired production rate.
  • the diagram indicates three cells, though one cell can be adequate if the applied electrical conditions are increased to respectively generate the Copper, Nickel and Iron, and fresh cathode material is applied for each metal product.
  • a method of reducing the possibility of Iron contamination is to operate the Copper and Nickel electrowinning with Ferrous concentrations below the minimum Ferrous level for electroplating Iron.
  • FIG 6 there is shown a method in accordance with the present invention for use in respect of copper oxides. Copper is used as an example, though the process can be performed with respect to any metal that is, able to be separated with the electrowinning concept disclosed in this document and provides an acid soluble valuable metal.
  • the ore may be prepared by any known technique (1 ).
  • the leaching (2) can be conducted in any known equipment including heap leach and in situ leaching operations.
  • the addition of acid will be required, especially to initiate the process, as the ore is likely to have other components of no value, such as limestone, that will consume acid.
  • the acid (3) can be any commercial type, such as hydrochloric or sulphuric acids.
  • Sulphuric will provide Sulphate and cause the precipitation of Gypsum. This may be an advantage that limits the build up of Calcium in the recirculating liquor, but it may be disadvantageous if undesirable co-precipitation occurs.
  • the electrolytic operations consist of a series of electrolytic membrane cells through which the acid passes.
  • the Copper is reduced to the metal form in the cathode compartment of the first cell (5).
  • Ferrous is reduced to the metallic Iron in a secondary, cathode compartment (6).
  • the third objective of the electrolytic process is to regenerate the acid. This is achieved by oxidising water at the anodes, whereby Oxygen gas is generated.
  • Oxygen gas is generated.
  • To form oxygen at the anode in preference to Chlorine gas at the anode requires minimisation of the free Chloride at the electrode surface. It has been discovered that factors that optimise this, include a high current density and minimum agitation.
  • FIG. 7 there is shown a process in accordance with the present invention for use is respect of the removal of sulphides from acid insoluble minerals.
  • Sulphide mineral content can be dissolved from materials that have low acid solubility. Common examples are mineral sands, certain Iron ores, Tantalum oxides, coal, clay and talc.
  • Particle size reduction (1 ) is an optional step. With the oxide concentrates studied, the Sulphide contamination appears quite reactive, which probably indicates that it is associated with discrete particles rather than occluded within the oxide mineral.
  • the preferred reactor for the sulphide leach reaction (2) is a percolation column, or vat leach operation. Though as per all previous examples, the process is not restricted to any particular equipment design for the Sulphide mineral digestion.

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Abstract

L'invention concerne un procédé hydro-métallurgique caractérisé, au moins en partie, par une méthode électrolytique destiné à produire directement des ions ferriques à une anode, en présence d'ions chlorure, sans formation de chlore gazeux, ledit procédé permettant de récupérer des métaux de valeur dissouts dans le fer. Le procédé est également caractérisé par la formation d'un complexe à charge négative dans une solution contenant un élément ferreux et/ou ferrique. Le procédé peut aussi être caractérisé par la concentration sélective de métaux dissouts pendant l'électro-extraction, et par la production simultanée de solutions ferriques hautement concentrées, sans formation d'espèces toxiques indésirables, telles que le chlore gazeux. L'invention concerne un procédé de dissolution atmosphérique de minéraux sulfurés, qui consiste à oxyder les minéraux sulfurés par des ions ferriques pour former des ions ferreux au cours de l'opération de lixiviation. Les ions ferriques ainsi formés sont ensuite oxydés lors d'un traitement séparé destiné à régénérer les ions ferriques, lesquels sont réintroduits pendant l'oxydation des minéraux sulfurés.
PCT/AU2001/001234 2000-09-28 2001-09-28 Procedes hydro-metallurgiques employant des solutions contenant des sels ferrique et/ou ferreux dissouts WO2002027072A1 (fr)

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WO2015000002A1 (fr) 2013-07-04 2015-01-08 Pureox Industrieanlagenbau Gmbh Procédé d'oxydation électrochimique de solutions de chlorure de fe2+
US8936770B2 (en) 2010-01-22 2015-01-20 Molycorp Minerals, Llc Hydrometallurgical process and method for recovering metals
US10400306B2 (en) 2014-05-12 2019-09-03 Summit Mining International Inc. Brine leaching process for recovering valuable metals from oxide materials
CN111094602A (zh) * 2017-07-07 2020-05-01 9203-5468 魁北克公司 Dba Nmr360 氧化和水热解离金属氯化物以分离金属和盐酸的方法
CN115212897A (zh) * 2022-07-26 2022-10-21 河北工业大学 一种自立式纳米多孔铜负载五硫化九铜纳米片复合材料及其制备方法与应用
WO2024045447A1 (fr) * 2022-09-02 2024-03-07 昆明理工大学 Procédé de métallurgie électrochimique pour l'extraction de métal et de soufre à partir de sulfure métallique

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CN114247569B (zh) * 2021-12-10 2023-09-22 郑州大学 一种滑石与硫化铜的浮选分离的方法

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EP0362157A2 (fr) * 1988-09-22 1990-04-04 Tanaka Kikinzoku Kogyo K.K. Procédé pour convertir une valence ionique et appareil à cet effet
WO1993006261A1 (fr) * 1991-09-23 1993-04-01 Spunboa Pty Ltd Extraction electrolytique de metaux a partir de solutions

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US3986943A (en) * 1975-05-27 1976-10-19 Duval Corporation Hydrometallurgical process for the production of antimony
EP0362157A2 (fr) * 1988-09-22 1990-04-04 Tanaka Kikinzoku Kogyo K.K. Procédé pour convertir une valence ionique et appareil à cet effet
WO1993006261A1 (fr) * 1991-09-23 1993-04-01 Spunboa Pty Ltd Extraction electrolytique de metaux a partir de solutions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8936770B2 (en) 2010-01-22 2015-01-20 Molycorp Minerals, Llc Hydrometallurgical process and method for recovering metals
US10179942B2 (en) 2010-01-22 2019-01-15 Secure Natural Resources Llc Hydrometallurgical process and method for recovering metals
WO2015000002A1 (fr) 2013-07-04 2015-01-08 Pureox Industrieanlagenbau Gmbh Procédé d'oxydation électrochimique de solutions de chlorure de fe2+
US10400306B2 (en) 2014-05-12 2019-09-03 Summit Mining International Inc. Brine leaching process for recovering valuable metals from oxide materials
CN111094602A (zh) * 2017-07-07 2020-05-01 9203-5468 魁北克公司 Dba Nmr360 氧化和水热解离金属氯化物以分离金属和盐酸的方法
CN115212897A (zh) * 2022-07-26 2022-10-21 河北工业大学 一种自立式纳米多孔铜负载五硫化九铜纳米片复合材料及其制备方法与应用
CN115212897B (zh) * 2022-07-26 2023-07-14 河北工业大学 一种自立式纳米多孔铜负载五硫化九铜纳米片复合材料及其制备方法与应用
WO2024045447A1 (fr) * 2022-09-02 2024-03-07 昆明理工大学 Procédé de métallurgie électrochimique pour l'extraction de métal et de soufre à partir de sulfure métallique

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