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WO2025153829A1 - Processus - Google Patents

Processus

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Publication number
WO2025153829A1
WO2025153829A1 PCT/GB2025/050085 GB2025050085W WO2025153829A1 WO 2025153829 A1 WO2025153829 A1 WO 2025153829A1 GB 2025050085 W GB2025050085 W GB 2025050085W WO 2025153829 A1 WO2025153829 A1 WO 2025153829A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
halide
acid
salt
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/GB2025/050085
Other languages
English (en)
Inventor
Roger B. Pettman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of WO2025153829A1 publication Critical patent/WO2025153829A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/0423—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
    • C22B3/04—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
    • 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
    • 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 disclosure concerns methods of extracting metal from a metal sulfide containing material, wherein the metal comprises copper, nickel, lead, zinc.
  • Extraction processes for other metals are known in the art.
  • methods of extracting precious metals such as gold or silver
  • methods of extracting precious metals involve extracting precious metal from the precious metal containing material (usually referred to as the “leaching” of precious metal from the precious metal containing material) and then capturing the leached precious metal from the solution.
  • some methods use highly poisonous inorganic cyanides to extract the precious metal from the precious metal containing material.
  • Such processes are associated with considerable environmental concerns (where accidental leakages can result in environmental contamination) as well as considerable health and safety concerns (where inadvertent cyanide exposure can cause notable human health concerns).
  • Other methods for extracting precious metals are disclosed in WO 2017/158561.
  • the aqueous acidic oxidant mixture achieves particularly successful extraction of copper, nickel, lead and/or zinc, from materials that comprise one or more sulfide salts of copper, nickel, lead and/or zinc. It is thought that the combination of water, an acid, an oxidising means, and a halide ion source, overcomes the challenges associated with extraction in the presence of sulfide salts, addresses the challenges associated with any potential passivation layer formation, and provides improved kinetics for metal extraction. Moreover, it was surprisingly found that the improved extraction can be achieved using more environmentally friendly components, rather than resorting to less environmentally friendly components, such as cyanide, pyrotechnic technologies, or ferric oxidants, for example. Furthermore, extracting the copper, nickel, lead and/or zinc as a halide provides significant advantages due to the increased solubility in water of the halide salt, allowing less water to be used, and so further reducing the environmental impact and carbon footprint.
  • the present disclosure concerns a method of extracting metal from a metal sulfide containing material, wherein the metal comprises copper, nickel, lead, zinc, or combinations thereof.
  • the method disclosed herein is a method of extracting copper, nickel, lead, zinc, or combinations thereof, and the metal sulfide containing material includes one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof.
  • the metal comprises copper, nickel and/or zinc
  • the metal sulfide containing material is a copper sulfide, nickel sulfide and/or zinc sulfide containing material (i.e. a material including one or more sulfide salts of copper, nickel and/or zinc).
  • the metal comprises copper and/or zinc
  • the metal sulfide containing material is a copper sulfide and/or zinc sulfide containing material (i.e. a material including one or more sulfide salts of copper and/or zinc).
  • the metal comprises copper
  • the metal sulfide containing material is a copper sulfide containing material (i.e. a material including one or more sulfide salts of copper).
  • the method disclosed herein is concerned with extracting from a metal sulfide containing material, i.e. a material that contains one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof.
  • a metal sulfide containing material i.e. a material that contains one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof.
  • sulfide salts there are various possible sulfide salts that may be present in the metal sulfide containing material, even for a given metal.
  • other components may be present in a given metal sulfide salt, where the metal sulfide salt need not be exclusively composed of sulfide plus copper, nickel, lead and/or zinc.
  • the oxidising means comprises hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromous acid, hypoiodous acid, a hypochlorite salt, a hypobromite salt, a hypoiodite salt, a percarbonate salt, a persulfate salt, a permanganate salt, an anode connected to a power source, or combinations thereof.
  • hypochlorite salt refers to any salt capable of generating the hypochlorite anion (CIO-) in solution.
  • the hypochlorite salt is an alkali metal hypochlorite salt e.g. lithium hypochlorite, potassium hypochlorite, calcium hypochlorite, and/or sodium hypochlorite.
  • the hypochlorite salt is sodium hypochlorite.
  • hypoiodite salt refers to any salt capable of generating the hypoiodite anion (IO-) in solution.
  • the hypoiodite salt is an alkali metal hypoiodite salt e.g. lithium hypoiodite, potassium hypoiodite, and/or sodium hypoiodite.
  • the hypoiodite salt is sodium hypoiodite.
  • the percarbonate salt is sodium percarbonate.
  • persulfate salt refers to any salt capable of generating persulfate anions SO5 2 ’ and/or S2O8 2 ’ in solution and this includes caro’s acid.
  • the persulfate salt is lithium persulfate, potassium persulfate, calcium persulfate and/or sodium persulfate.
  • the persulfate salt is sodium persulfate.
  • permanganate salt refers to any salt capable of generating the permanganate anion (MnC ) in solution.
  • the permanganate salt is an alkali metal permanganate salt e.g. lithium permanganate, potassium permanganate, and/or sodium permanganate.
  • the permanganate salt is potassium permanganate.
  • an anode is an electrode at which oxidation occurs.
  • the anode is at least partially (or, fully) submerged in the aqueous acidic oxidant mixture.
  • the anode is connected to a power source which is capable of applying an electrical current such that the electrons flow away from the anode, thereby allowing oxidation (i.e. loss of electrons) to occur at the anode.
  • oxidation by electrolysis the power source will in turn usually be connected to a cathode.
  • Hydrogen peroxide is available from many companies on a commercial basis and can be supplied at large scale by road or rail. These companies include but are not limited to Evonik, Solvay GmbH, Kemira, Arkema. Some companies offer the concept of on site generation, which may be compatible with the method disclosed herein.
  • the halide ion source can include a variety of different possible halides and still result in successful extraction of copper, nickel, lead and/or zinc.
  • the halide ion source comprises a bromide ion source, a chloride ion source, an iodide ion source, or combinations thereof.
  • the halide ion source comprises a bromide ion source, a chloride ion source, or combinations thereof, as such scenarios result in particularly good extraction.
  • the halide ion source may be at least one bromide ion source.
  • halide ion source may be used to form the aqueous acidic oxidant mixture.
  • the amount of the halide ion source added to form the aqueous acidic oxidant mixture can for example range from 1 to 20 wt.% based on the total weight of the aqueous acidic oxidant mixture.
  • the amount of the halide ion source added to form the aqueous acidic oxidant mixture can be at least 1 wt.%, preferably at least 5 wt.% based on the total weight of the aqueous acidic oxidant mixture.
  • the aqueous acidic oxidant mixture has a pH of less than 7. It will be understood that a pH of less than 7 refers to a pH of ⁇ 7, i.e. an acidic pH. It has been found that the aqueous acidic oxidant mixture can take a variety of different acidic pH values and still provide successful extraction. For example, the aqueous acidic oxidant mixture can have a pH of greater than or equal to 0.1 , greater than or equal to 0.4, or greater than or equal to 0.8. The aqueous acidic oxidant mixture can have a pH of less than or equal to 6.9, less than or equal to 6, less than or equal to 5, or less than or equal to 4.
  • the aqueous acidic oxidant mixture has a pH of less than or equal to 3, more preferably less than or equal to 2.
  • the aqueous acidic oxidant mixture has a pH in the range of 0.1 -1.5, particularly good extraction is achieved.
  • the skilled person will appreciate how to tailor the aqueous acidic oxidant mixture so as to achieve a particular pH.
  • the pH is measured by standard methods known in the art, for example using a standard electronic pH meter or colour coded test strip, across temperatures ranging from 5°C to 75°C.
  • the oxidising means and the halide ion source are not necessarily mutually exclusive terms, and so may be the same or different species.
  • the oxidising means and the source of the halide ion may both be hypobromous acid (thereby providing a direct source of BrOH to the aqueous acidic oxidant mixture), and/or dissolved bromine.
  • the oxidising means and the halide ion source are different species.
  • the acid and the halide ion source are not necessarily mutually exclusive terms, and so may be the same or different species.
  • the source of the halide ion and the acid may both be hypobromous or hypochlorous acid.
  • the halide ion source and the acid are different species.
  • the acid and the oxidising means are not necessarily mutually exclusive terms, and so may be the same or different species.
  • the acid and the oxidising means may both be hypobromous or hypochlorous acid.
  • the acid and the oxidising means are different species.
  • all three of the oxidising means, the halide ion source, and the acid are different species.
  • the amount of metal sulfide containing material that contacts the aqueous acidic oxidant mixture can be tailored depending on e.g. the type of metal sulfide containing material, but can for example be added in amounts of 1 g to 1000 g, preferably 10 g to 800 g, more preferably 30 g to 600 g.
  • the ratio, by weight, of metal sulfide containing material : aqueous acidic oxidant mixture can be tailored depending on e.g. the type of metal sulfide containing material, and the scale at which the method is being conducted, and can for example range from 1 :0.2 to 1 : 10000.
  • the ratio, by weight, of metal sulfide containing material : aqueous acidic oxidant mixture can be at least 1 :0.2, preferably at least 1 :1 , more preferably at least 1 :2.
  • the ratio, by weight, of metal sulfide containing material : aqueous acidic oxidant mixture can be up to 1 :10000, up to 1 :1000, up to 1 :10, preferably up to 1 :8, more preferably up to 1 :7.
  • the aqueous acidic oxidant mixture is stirred for at least 5 minutes before the aqueous acidic oxidant mixture is contacted with the metal sulfide containing material.
  • steps a) and b) occur sequentially. That is, the aqueous acidic oxidant mixture is provided and subsequently contacted with the metal sulfide containing material.
  • steps a) and b) occur simultaneously.
  • the metal sulfide containing material may be contacted with an intermediate mixture with one or more (but not all) of the aqueous acidic oxidant mixture ingredients, then the remaining ingredients of the aqueous acidic oxidant mixture are subsequently added.
  • the aqueous acidic oxidant mixture is immediately in contact with the metal sulfide containing material upon its formation.
  • the provision of the acidic aqueous oxidant mixture of step a), and the contacting of this mixture with the metal sulfide containing material of step b) occurs at the same time.
  • the step contacting the aqueous acidic oxidant mixture with the metal sulfide containing material to extract the metal from the metal sulfide containing material and form a metal halide solution.
  • the same metal sulfide containing material may be separated from the metal halide solution and washed, preferably with a fresh mixture of the aqueous acidic oxidant mixture disclosed herein. In the instance that the metal sulfide containing material is washed with a fresh mixture of the aqueous acidic oxidant mixture disclosed herein, this will form additional metal halide solution.
  • the method herein can be a method of extracting nickel from a nickel sulfide containing material, to extract the nickel from the nickel sulfide containing material and form a nickel halide solution.
  • the method herein can be a method of extracting lead from a lead sulfide containing material, to extract the lead from the lead sulfide containing material and form a lead halide solution.
  • the method herein can be a method of extracting zinc from a zinc sulfide containing material, to extract the zinc from the zinc sulfide containing material and form a zinc halide solution.
  • the method disclosed herein has particular applicability to copper, nickel and/or zinc extraction. Therefore preferably, the method herein is a method of extracting copper, nickel and/or zinc from a copper sulfide, nickel sulfide and/or zinc sulfide containing material, to extract the copper, nickel and/or zinc from the copper sulfide, nickel sulfide and/or zinc sulfide containing material and form a copper halide, nickel halide and/or zinc halide solution.
  • the method disclosed herein has particular applicability to copper and/or zinc extraction. Therefore preferably, the method herein is a method of extracting copper and/or zinc from a copper sulfide and/or zinc sulfide containing material, to extract the copper and/or zinc from the copper sulfide and/or zinc sulfide containing material and form a copper halide and/or zinc halide solution.
  • the step of contacting the aqueous acidic oxidant mixture with the metal sulfide containing material to extract the metal from the metal sulfide containing material and form a metal halide solution is the step of contacting the aqueous acidic oxidant mixture with the metal sulfide containing material to extract the metal from the metal sulfide containing material and form a metal halide solution.
  • the extraction of the metal from the metal sulfide containing material can be referred to as the leaching of the metal from the metal sulfide containing material, and the term “leach” can be used to refer to the mixture/solution used to extract the metal.
  • the metal is extracted from the metal sulfide containing material to form a metal halide, which may then be isolated, or it may be converted into other forms of the metal in question.
  • the metal halide may be converted to another metal salt (such as metal carbonate, and/or metal hydroxide), and/or metal 0 .
  • metal 0 refers to the metal in question in an oxidation state of zero, for example copper 0 , nickel 0 , lead 0 and/or zinc 0 , as opposed to referring to the metal in question in cation or salt form.
  • the method may further comprise the step of converting the metal halide (extracted from the metal sulfide containing material) to another metal salt and/or metal 0 .
  • the step of converting the metal halide to another metal salt and/or metal 0 is denoted herein as step c).
  • step c The skilled person will appreciate that there are various ways in which to convert the metal halide to another metal salt and/or metal 0 and will be familiar with appropriate reagents and conditions.
  • step c) comprises the step of contacting the metal halide solution with carbon dioxide, carbon monoxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid, a reducing means, sodium hydroxide, potassium hydroxide, oxygen, ozone, or a combination thereof.
  • the method comprises the step of converting the metal halide (extracted from the metal sulfide containing material) to another metal salt (such as metal carbonate, and/or metal hydroxide), and/or metal 0 . Doing so allows the halide to effectively be recycled. This therefore allows for an efficient method at least in terms of use of reactants. It will be understood from this that the method disclosed herein encompasses scenarios where recycled leach is present.
  • step c) comprises the step of contacting the metal halide solution with a reducing means, the metal halide is thereby converted to metal 0 .
  • step c) is carried out by electrowinning, thereby converting the metal halide to metal 0 .
  • Electrowinning takes its usual definition in the art, and so refers to passing of an electrical current through the metal halide solution such that the metal is deposited onto a cathode via an electroplating process. Electrowinning is preferred due to reduced biproduct formation.
  • step c) comprises the step of contacting the metal halide solution with sodium hydroxide, potassium hydroxide, oxygen, ozone, or a combination thereof, the metal halide is converted to metal hydroxide.
  • the reducing means is zinc, sodium metabisulfite, hydrogen gas, and/or a cathode connected to a power source.
  • a cathode is an electrode at which reduction occurs.
  • the cathode is at least partially (or, fully) submerged in the metal halide solution.
  • the cathode is connected to a power source which is capable of applying an electrical current such that the electrons flow towards the cathode, thereby allowing reduction (i.e. gain of electrons) to occur at the cathode.
  • reduction by electrolysis and so the skilled person will appreciate that the power source will in turn usually be connected to an anode.
  • the reducing means is zinc, sodium metabisulfite, and/or hydrogen gas.
  • the method herein can be a method of extracting lead from a lead sulfide containing material, to extract the lead from the lead sulfide containing material and form a lead halide solution, optionally further comprising the step of converting the lead halide to lead 0 , lead carbonate, and/or lead hydroxide.
  • the method herein can be a method of extracting zinc from a zinc sulfide containing material, to extract the zinc from the zinc sulfide containing material and form a zinc halide solution, optionally further comprising the step of converting the zinc halide to zinc 0 , zinc carbonate, and/or zinc hydroxide.
  • the method disclosed herein has particular applicability to copper and/or zinc extraction. Therefore preferably, the method herein is a method of extracting copper and/or zinc from a copper sulfide and/or zinc sulfide containing material, to extract the copper and/or zinc from the copper sulfide and/or zinc sulfide containing material and form a copper halide and/or zinc halide solution, optionally further comprising the step of converting the copper halide and/or zinc halide to copper 0 and/or zinc 0 , copper carbonate and/or zinc carbonate, copper hydroxide and/or zinc hydroxide, or combinations thereof.
  • the method herein is a method of extracting copper from a copper sulfide containing material, to extract the copper from the copper sulfide containing material and form a copper halide solution, optionally further comprising the step of converting the copper halide to copper, copper carbonate, and/or copper hydroxide.
  • metal is extracted from the metal sulfide containing material to form a metal halide, which may be recovered and so isolated from the remaining reactants, and/or it may be converted into other forms of metal, which may then in turn be recovered and so isolated from the remaining reactants.
  • the methods disclosed herein may further comprise the step of recovering the metal halide and/or may further comprise the step of recovering the other form(s) of metal to which the metal halide has been converted. It will be understood that by “recovering” it is meant that the metal species in question (i.e. the metal halide, and/or the other form(s) of metal to which the metal halide has been converted) is collected, removed, or isolated, from the reactant mix.
  • metal species in question is solid (such as metal carbonate)
  • solvent extraction process which may or may not contain various chelates, by reverse osmosis, by the use of activated carbon, by electrowinning, or by use of one or more ion exchange resins.
  • other form(s) of metal to which the metal halide has been converted refers to those detailed elsewhere in the present disclosure and so can include another metal salt (such as metal carbonate, and/or metal hydroxide), metal 0 , or a combination thereof, and are subject to the same degrees of preference to those detailed herein.
  • the ion exchange resins are preferably comprised of an organic polymer backbone to which a series of functional groups are attached, said functional groups containing at least one heteroatom.
  • the resins provide improved capture of the metal species compared with capturing using activated carbon. Without wishing to be bound by theory, it is thought that the improved capture of the metal species is due to the at least one heteroatom within the series of functional groups. It is thought that the at least one heteroatom coordinates with the metal species in question, facilitating the formation of a complex between the metal species and the resin. Such resins may therefore be referred to as chelating resins.
  • Step b) may further comprise contacting the aqueous acidic oxidant mixture with a resin, said resin preferably being an ion exchange resin comprised of an organic polymer backbone to which a series of functional groups are attached, said functional groups containing at least one heteroatom.
  • a resin preferably being an ion exchange resin comprised of an organic polymer backbone to which a series of functional groups are attached, said functional groups containing at least one heteroatom.
  • a resin in step b) allows for the formation of a metal halide resin complex.
  • metal halide resin complex refers to the species formed from the interaction between the metal halide (i.e. the metal that has been extracted from the metal sulfide containing material) and the resin. It will be understood from this that the metal halide resin complex refers to the resin with the metal halide complexed thereon or therein.
  • the resin and the metal sulfide containing material may be added simultaneously, or sequentially. “Sequentially” meaning one after the other.
  • the resin and the metal sulfide containing material are added to the aqueous acidic oxidant mixture sequentially, the resin can be added before (i.e. prior to), or after, the addition of the metal sulfide containing material. Accordingly, the resin can be added simultaneously with, prior to, or after, the addition of the metal sulfide containing material.
  • the timing of these steps can be tailored at the convenience of the processing facilities.
  • the resin and the metal sulfide containing material may be added simultaneously to the aqueous acidic oxidant mixture.
  • the resin may be added to the aqueous acidic oxidant mixture prior to the addition of the metal sulfide containing material.
  • the resin may be added to the aqueous acidic oxidant mixture after the addition of the metal sulfide containing material.
  • the amount of resin used in step b) can vary depending on the application in question, but can for example range from 0.1 -100g per 100ml of aqueous acidic oxidant mixture.
  • the amount of resin used in step b) can be at least 0.1g, at least 1 g, at least 2g, preferably at least 5g, per 100ml of aqueous acidic oxidant mixture.
  • the amount of resin used in step b) can be up to 100g, up to 80g, up to 50g, preferably up to 20g, per 100ml of aqueous acidic oxidant mixture.
  • Step c may further comprise contacting the metal halide solution with a resin, said resin preferably being an ion exchange resin comprised of an organic polymer backbone to which a series of functional groups are attached, said functional groups containing at least one heteroatom.
  • a resin preferably being an ion exchange resin comprised of an organic polymer backbone to which a series of functional groups are attached, said functional groups containing at least one heteroatom.
  • a resin in step c) allows for the formation of a complex between the resin and the form(s) of metal to which the metal halide has been converted.
  • such other form(s) of metal can include another metal salt (such as metal carbonate, and/or metal hydroxide), metal 0 , or a combination thereof.
  • metal 0 resin complex a metal carbonate resin complex
  • metal hydroxide resin complex each refer to the species formed from the interaction between the respective metal species in question and the resin.
  • metal 0 resin complex metal carbonate resin complex
  • metal hydroxide resin complex refers to the resin with the respective metal species complexed thereon or therein.
  • the resin may be added prior to, simultaneously with, or after the conversion of the metal halide to other form(s) of metal.
  • such other form(s) of metal can include another metal salt (such as metal carbonate, and/or metal hydroxide), metal 0 , or a combination thereof.
  • the timing of these steps can be tailored at the convenience of the processing facilities.
  • the other form(s) of metal may form and then immediately react to result in the formation of a complex between the resin and the metal species in question (such as, for example, a metal 0 resin complex, a metal carbonate resin complex, and/or metal hydroxide resin complex).
  • a complex between the resin and the metal species in question such as, for example, a metal 0 resin complex, a metal carbonate resin complex, and/or metal hydroxide resin complex.
  • the resin is preferably added simultaneously with, or after, the conversion of the metal halide to other form(s) of metal.
  • other form(s) of metal can include another metal salt (such as metal carbonate, and/or metal hydroxide), metal 0 , or a combination thereof.
  • the amount of resin used in step c) can vary depending on the application in question, but can for example range from 0.1 -100g per 100ml of metal halide solution, or mixture of other form(s) of metal to which the metal halide has been converted.
  • such other form(s) of metal can include another metal salt (such as metal carbonate, and/or metal hydroxide), metal 0 , or a combination thereof.
  • the amount of resin used in step c) can be at least 0.1 g, at least 1 g, at least 2g, preferably at least 5g, per 100ml of metal halide solution, or mixture of other form(s) of metal to which the metal halide has been converted.
  • the amount of resin used in step c) can be up to 100g, up to 80g, up to 50g, preferably up to 20g, per 100ml of metal halide solution, or mixture of other form(s) of metal to which the metal halide has been converted.
  • ion exchange resin takes its usual definition in the art, and so refers to a material that acts as a medium for ion exchange that is generally insoluble in aqueous mediums. It will be understood from this that the ion exchange resin is substantially insoluble in the aqueous solutions and mixtures disclosed herein, e.g. the aqueous acidic oxidant mixture, metal halide solution or mixture of other form(s) of metal to which the metal halide has been converted.
  • substantially insoluble it is meant that less than 0.1 mg/ml of the resin dissolves in the aqueous solutions and mixtures disclosed herein (e.g. the aqueous acidic oxidant mixture, metal halide solution or mixture of other form(s) of metal to which the metal halide has been converted) at 25 °C.
  • definitions relating to the ion exchange resin generally refer to the features of the ion exchange resin per se, i.e. prior to its addition to the aqueous solutions and mixtures disclosed herein. After its addition, it will be understood that, depending on the pH of the medium in question, protonation or deprotonation of certain groups of the ion exchange resin may occur.
  • the ion exchange resin is preferably a porous material.
  • the porosity of the ion exchange resin increases the surface area available for ion exchange.
  • the ion exchange resin when used in the method disclosed herein, is comprised of a polymer backbone (sometimes referred to as a polymer matrix), to which a series of functional groups are attached.
  • the ion exchange resin when used, is comprised of an organic polymer backbone to which a series of functional groups are attached.
  • the ion exchange resin may essentially consist of an organic polymer backbone to which a series of functional groups are attached.
  • ion exchange resins when used in the method disclosed herein, are commercially available from a variety of sources, with commercially available resins including but not limited to the following, which are all ion exchange resins with polystyrene backbones functionalised with the following groups:
  • SEPLITE® LSC660 functionalised with guanidine groups
  • SEPLITE® LSC740 functionalised with thiol groups
  • SEPLITE® LSC710 functionalised with iminodiacetic acid groups - AMBERSEP® 21 K XLT Mesh Anion Exchange Resin (CI-): functionalised with quaternary ammonium groups
  • polymer takes its usual definition the art and so refers to a homopolymer or copolymer formed from the polymerisation of one or more monomers. As such, this term covers e.g. linear polymers, branched polymers, and cyclic polymers.
  • the term “homopolymer” takes its usual definition in the art, and so refers to a polymer whose polymer chains comprise one type of monomer.
  • the term “co-polymer” takes its usual definition in the art, and so refers to a polymer whose polymer chains comprise two or more different types of monomers.
  • the skilled person will appreciate therefore that the term “co-polymer” encompasses polymers that include three different types of monomers (which can at times be referred to in the art specifically as “terpolymers”).
  • the term “block co-polymer” takes its usual definition in the art and so refers to a copolymer whose polymer chains include two or more blocks of monomers.
  • Each block is comprised of a particular monomer type, where at least two of the blocks present comprise a different monomer type to one another.
  • a diblock co-polymer, a tri-block copolymer, and a tetra-block copolymer each refer to copolymers with two, three, and four monomer blocks respectively.
  • the term “monomer” takes its usual definition in the art and so refers to a molecular compound that may chemically bind to another monomer to form a polymer. Unless expressly stated to the contrary, any monomer referred to herein should be understood to include all enantiomers, diastereomers, racemates and mixtures thereof of the monomers in question.
  • polymer backbone refers to the series of covalently bonded atoms that create a continuous molecular chain which acts as a scaffold to which the functional groups are attached. In line with the usual definition in the art, the polymer backbone is generally the longest continuous molecular chain, to which other chains and functional groups may be regarded as being pendant.
  • the organic polymer backbone can be polystyrene, polyvinyl toluene, poly(vinylbenzyl chloride), polyvinyl acetate, polyvinyl butyral and polyvinyl ether. More preferably, the organic polymer backbone is polystyrene. In a particularly preferred embodiment, the organic polymer backbone is polystyrene crosslinked with divinylbenzene.
  • the functional groups contain at least one heteroatom.
  • heteroatom takes its usual definition in the art, and so refers to an atom that is not carbon or hydrogen.
  • the heteroatom is one or more of N (nitrogen), S (sulphur), O (oxygen), and P (phosphorus). More preferably, the heteroatom is one or more of N, S, and O, more preferably one or more of N and S.
  • additional heteroatoms other than those recited in this list may also be present in the functional groups.
  • the atomic species given for the heteroatom are to be understood as encompassing that species irrespective of whether or not it is in a neutral state. In particular, when the series of functional groups contain N, this encompasses scenarios where the N is positively charged, for example as part of a quaternary ammonium group.
  • the series of functional groups includes one or more of an iminodiacetic acid group, a thiourea group, a quaternary ammonium group, a guanidine group, an amine group, and a thiol group.
  • the functional groups of the series can be iminodiacetic acid groups, thiourea groups, quaternary ammonium groups, guanidine groups, amine groups, or thiol groups.
  • the series of functional groups includes one or more of a thiourea group, a quaternary ammonium group, and a guanidine group.
  • the functional groups of the series can be thiourea groups, quaternary ammonium groups or guanidine groups.
  • the functional groups disclosed herein can be attached to the polymer backbone by standard reaction procedures known in the art, with the attachment between the functional group and the backbone being located at an appropriate point of the molecular framework of the functional group, as will be appreciated by the skilled person.
  • iminodiacetic acid refers to the formula HN(CH 2 CO2H) 2 .
  • the functional groups comprise one or more of the following moieties:
  • R 1 , R 2 , R 3 and R 4 are the same or different and are each independently selected from H or a Ci-Ce alkyl group.
  • R 1 , R 2 , R 3 and R 4 are the same or different and can each be independently selected from H or a C1-C3 alkyl group. More preferably, R 3 and R 4 are both H.
  • the series of functional groups includes a thiourea group
  • the functional groups comprise one or more of the following moieties, with R 1 , R 2 , R 3 and R 4 taking the same meaning and preferences as those stated above:
  • the functional groups comprise one or more of the following moieties, with R 5 , R 6 and R 7 taking the same meaning and preferences as those stated above:
  • the alkyl group is a Ci-Ce alkyl group, more preferably a C1-C3 alkyl group.
  • the series of functional groups includes a guanidine group
  • the functional groups comprise one or more of the following moieties, with R 9 , R 10 , R 11 , R 12 and R 13 taking the same meaning and preferences as those stated above:
  • amine refers to the formula NR 15 R 16 R 17 , where R 15 , R 16 and R 17 may be the same or different and are each independently selected from H or an alkyl group.
  • R 15 , R 16 and R 17 are the same or different and are each independently selected from H or a Ci-Ce alkyl group. More preferably, R 15 , R 16 and R 17 are the same or different and are each an alkyl group, preferably a Ci-Ce alkyl group.
  • R 15 , R 16 and R 17 are each a C1-C3 alkyl group, and may be the same or different.
  • the moieties may be attached directly to the polymer backbone e.g. by way of a direct bond, or, they may be attached via an alkyl group, such as a C1-C10 alkyl group, preferably a Ci-Ce alkyl group, more preferably a C1-C3 alkyl group.
  • alkyl refers to a straight or branched saturated or unsaturated alkyl group.
  • the alkyl group is a saturated alkyl group. More preferably, the alkyl group is a straight alkyl group.
  • (Ca-Cb)alkyl wherein a and b are integers refers to a straight or branched chain alkyl having from a to b carbon atoms.
  • a C1-C10 alkyl group refers to a group having from 1 to 10 carbon atoms, and so includes methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl and decyl.
  • Ci-Ce alkyl group refers to a group having from 1 to 6 carbon atoms, and so includes methyl, ethyl, n-propyl, isopropyl, n- butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl.
  • the resin may be provided as a plurality of beads with a particle size distribution such that more than 95% of the particles have a diameter of 0.1 to 10mm, 0.2 to 5mm, 0.1 to 2.5mm or 0.2 to 1.5mm.
  • the bulk density can vary, for example from 100 g/l to 2000 g/l, preferably from 200 to 900 g/l, more preferably from 500 g/l to 900 g/l, or from 600 g/l to 850 g/l.
  • the absolute density can vary, for example from 100 to 2000 g/l, preferably from 200 to 1500, more preferably from 500 to 1200 g/l.
  • the method may further comprise the step of recovering the metal species (i.e. the metal halide, and/or the other form(s) of metal to which the metal halide has been converted) from the metal species resin complex.
  • the metal species i.e. the metal halide, and/or the other form(s) of metal to which the metal halide has been converted
  • the resin, complete with the complexed metal species can be removed from the remaining components of the method disclosed herein by appropriate solid-liquid separation techniques (such as sieving, for example), before subjecting the resin to a suitable method to separate the metal species from the resin.
  • the metal species can be recovered from the metal species resin complex by stripping, incineration, ashing or burning of the resin.
  • the method disclosed herein may comprise the additional step of subjecting the material from which the metal has been extracted to a decontamination step, said decontamination step comprising the step of contacting the material with one or more ion exchange resins with specifics and preferred features disclosed herein.
  • a decontamination step comprising the step of contacting the material with one or more ion exchange resins with specifics and preferred features disclosed herein.
  • certain functional groups such as thiol groups, have selectivity for impurities such as arsenic, and mercury. Therefore, not only can certain resins disclosed herein be used to selectively extract metal in preference to impurities, but certain resins disclosed herein can then be used to decontaminate the material leftover from the method (sometimes referred to as “tailings”), providing a “clean up” operation for the tailings leftover from the method.
  • the method disclosed herein may be carried out at a variety of different temperatures, for example from 5-100 degrees C.
  • the method disclosed herein may be carried out at a range if different pressures, and can for example be carried out at elevated pressures in a sealed system, but more typically is carried out at atmospheric pressure.
  • Example 1 corresponding to “Text 1”
  • Example 2 corresponding to “Test 2”, and so on.
  • the % copper extraction was assessed using fire assay and ICP (inductively coupled plasma) as follows.
  • the amount of copper in the head ore i.e. the ore prior to the extraction process
  • the amount of copper in the tails i.e. spent ore material left over after the extraction process.
  • the level of copper in the head ore was compared to the level of copper remaining in the tails. The bigger the difference between the level of copper in the head ore and the level of copper remaining in the tails, the better the copper extraction.
  • Table 1 reports the difference between the level of copper in the head ore and the level of copper remaining in the tails as a % of the level of copper in the head ore (i.e. heads-tails/heads*100).
  • a series of aqueous acidic oxidant mixtures with a pH of 0.5 were formulated and contacted with a copper ore.
  • the NaCI concentrations were varied from 2-6.5 wt.%, the temperature of the mixture was varied from 30-80°C, and the contact time was varied from 15-45 minutes.
  • the copper extraction was determined using

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Abstract

La divulgation concerne un procédé d'extraction de métal à partir d'un matériau contenant du sulfure métallique comprenant les étapes consistant à : a) fournir un mélange oxydant acide aqueux comprenant de l'eau, un acide, un agent oxydant et une source d'ions halogénure, le mélange oxydant acide aqueux ayant un pH inférieur à 7 ; l'agent oxydant comprenant du peroxyde d'hydrogène, de l'ozone, de l'oxygène, du chlore, du brome, de l'iode, de l'acide hypochloreux, de l'acide hypobromeux, de l'acide hypoïde, un sel d'hypochlorite, un sel d'hypobromite, un sel d'hypoiodite, un sel de percarbonate, un sel de persulfate, un sel de permanganate, une anode connectée à une source d'alimentation, ou des combinaisons de ces éléments ; b) mettre en contact le mélange oxydant acide aqueux avec le matériau contenant du sulfure métallique pour extraire le métal du matériau contenant du sulfure métallique et former une solution d'halogénure métallique ; le métal comprenant du cuivre, du nickel, du plomb, du zinc ou des combinaisons de ces éléments.
PCT/GB2025/050085 2024-01-18 2025-01-17 Processus Pending WO2025153829A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2128597A (en) * 1982-10-22 1984-05-02 Davy Mckee Recovery of metal values from sulphide concentrates
WO2007071021A1 (fr) * 2005-12-23 2007-06-28 Harris G Bryn Procédé d'extraction d'un métal de base d'un minerai sulfuré
US20090013829A1 (en) * 2003-09-30 2009-01-15 Harris G Bryn Process for the recovery of value metals from base metal sulfide ores
US20120103138A1 (en) * 2009-05-26 2012-05-03 Metaleach Limited Method of oxidative leaching of sulfide ores and/or concentrates
WO2017158561A1 (fr) 2016-03-17 2017-09-21 Cycladex Inc. Récupération de métaux précieux et de terres rares à l'aide de cyclodextrine
WO2023026041A1 (fr) 2021-08-27 2023-03-02 Cycladex Ltd Procédé
WO2023049967A1 (fr) * 2021-09-30 2023-04-06 Commonwealth Scientific And Industrial Research Organisation Procédé et appareil de lixiviation de métaux
WO2023057754A1 (fr) 2021-10-06 2023-04-13 Cycladex Ltd Procédé

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2128597A (en) * 1982-10-22 1984-05-02 Davy Mckee Recovery of metal values from sulphide concentrates
US20090013829A1 (en) * 2003-09-30 2009-01-15 Harris G Bryn Process for the recovery of value metals from base metal sulfide ores
WO2007071021A1 (fr) * 2005-12-23 2007-06-28 Harris G Bryn Procédé d'extraction d'un métal de base d'un minerai sulfuré
US20120103138A1 (en) * 2009-05-26 2012-05-03 Metaleach Limited Method of oxidative leaching of sulfide ores and/or concentrates
WO2017158561A1 (fr) 2016-03-17 2017-09-21 Cycladex Inc. Récupération de métaux précieux et de terres rares à l'aide de cyclodextrine
WO2023026041A1 (fr) 2021-08-27 2023-03-02 Cycladex Ltd Procédé
WO2023049967A1 (fr) * 2021-09-30 2023-04-06 Commonwealth Scientific And Industrial Research Organisation Procédé et appareil de lixiviation de métaux
WO2023057754A1 (fr) 2021-10-06 2023-04-13 Cycladex Ltd Procédé

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