Process

Abstract

Disclosed herein is a method of extracting metal from a metal sulfide containing material comprising the steps of: a) providing an aqueous acidic oxidant mixture comprising water, an acid, an oxidising means, and a halide ion source, wherein the aqueous acidic oxidant mixture has a pH of less than 7; wherein 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; b) 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; wherein the metal comprises copper, nickel, lead, zinc, or combinations thereof.

Description

practical Full description Field of invention The present invention deals with methods of extracting a metal from a material containing a metal sulfide, where the metal includes copper, nickel, lead, and zinc. background invention Copper, nickel, lead, and zinc have a wide variety of uses and applications. In recent years, the demand for these metals and their salts has increased significantly, leading to a desire to extract them efficiently from associated mineral deposits. Other methods for extracting metals are well-known in the field. For example, methods for extracting precious metals (such as gold or silver) are known. Generally, these methods involve extracting the precious metal from the metal-bearing material (a process commonly referred to as "leaching") and then collecting the leached precious metal from the solution. For example, some methods use highly toxic inorganic cyanides to extract the precious metal from the metal-bearing material. These processes raise significant environmental concerns (as accidental leaks can lead to environmental pollution), as well as significant health and safety concerns (as unintentional cyanide exposure can cause serious health problems). Other methods for extracting precious metals were disclosed in international patent application WO 2017 / 158561. However, these methods have only been used to extract what are generally referred to as precious metals (such as gold and / or silver, as well as other metals such as platinum and palladium).The aforementioned field also includes international patent publication WO2023 / 057754, which deals with methods for extracting lithium, and international patent publication WO2023 / 026041, which primarily evaluates the extraction of gold and / or silver. These methods often involve the flotation of the various minerals followed by processing in a smelter. Meanwhile, copper, nickel, lead, and zinc are metals of different natures, as evidenced by their varying positions in the periodic table. Furthermore, copper, nickel, lead, and zinc are often found in materials containing their associated metals as sulfide salts. Historically, this has presented challenges in efficient extraction due to the tendency of sulfides to interfere with the leaching process, for example, because of the metal's poor selectivity and its reaction with sulfur before extraction. Passivation is also believed to pose a further challenge, as it prevents leaching mixtures from reaching the desired metals. Consequently, extracting copper, nickel, lead, and / or zinc, particularly from materials containing these metals as one or more sulfide salts, presents significant challenges. Current extraction methods from sulfide-containing materials often lack suitable kinetics or have poor environmental characteristics. Accordingly, new methods are still needed for extracting copper, nickel, lead and / or zinc, especially from materials that contain these metals in one or more sulfide salt forms. General description of the invention This document reveals a method for extracting a metal from a material containing metal sulfide, which includes the following steps: a) Provide an aqueous acid oxidizing mixture that includes water, acid, an oxidizing agent, and a source of halide ions, where the aqueous acid oxidizing mixture has a pH of less than 7; The oxidation medium includes hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromous acid, hypoiodous acid, hypochlorite salt, hypobromite salt, hypoiodate salt, percarbonate salt, persulfate salt, permanganate salt, an anode connected to a power source, or combinations thereof; b) Contact of the aqueous acidic oxidizing mixture with the metal sulfide-containing material to extract the metal from the metal sulfide-containing material and form a metal halide solution; The metal contains copper, nickel, lead, zinc, or combinations thereof. Surprisingly, an aqueous acid-oxidizing mixture was found to achieve highly successful extraction of copper, nickel, lead, and / or zinc from materials containing one or more copper, nickel, lead, and / or zinc sulfide salts. The combination of water, acid, oxidizing agent, and a halide ion source is believed to overcome the challenges associated with extraction in the presence of sulfide salts, address the potential for passivation, and improve mineral kinetics. Furthermore, it was found, surprisingly, that enhanced extraction can be achieved using more environmentally friendly components, rather than less environmentally friendly ones such as cyanide, pyrotechnic techniques, or ferrous oxidizers. Moreover, extracting copper, nickel, lead, and / or zinc in halide form offers significant advantages due to the increased solubility of the halide salt in water, allowing for the use of less water and thus further reducing the environmental impact and carbon footprint. Detailed description of the invention The phrase "reaches up to," wherever it is used, means "reaches up to and including". The phrase "within a range," wherever it is used, is understood to include both ends of that range. The present disclosure relates to a method for extracting a metal from a metal sulfide-containing material, where the metal includes copper, nickel, lead, zinc, or combinations thereof. It is understood that the method described here is for extracting copper, nickel, lead, zinc, or combinations thereof, and that the metal sulfide-containing material contains one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. In some cases, the metal includes copper, nickel, and / or zinc, and the metal sulfide-containing material is a material containing copper sulfide, nickel sulfide, and / or zinc sulfide (i.e., a material containing one or more sulfide salts of copper, nickel, and / or zinc). Ideally, the metal should include copper and / or zinc, and the metal sulfide-containing material should be a material containing copper sulfide and / or zinc sulfide (i.e., a material containing one or more sulfide salts of copper and / or zinc).Better still, the metal should contain copper, and the material containing the metal sulfide should be a material containing copper sulfide (i.e., a material containing one or more copper sulfide salts). The method described here relates to extraction from a metal sulfide material, that is, a material containing one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. It is important to note that a variety of sulfide salts may be present in a metal sulfide material, even for a single metal. Furthermore, other components may be present in a metal sulfide salt; a metal sulfide salt is not necessarily composed exclusively of sulfides in addition to copper, nickel, lead, and / or zinc. For example, a metal sulfide material may contain sulfide salts such as CuFeS₂, Cu₂S, Cu₅FeS₄, (FeNi)₁₀S₈, PbS, (Zn,Fe)S, or combinations thereof. Ideally, the metal sulfide material should contain CuFeS₂, Cu₂S, Cu₅FeS₄, (Zn,Fe)S, or combinations thereof. Even better, the material containing the metal sulfide should include CuFeS2, Cu2S, Cu5FeS4, or combinations thereof. This document presents various examples of metal sulfide-containing material. In some cases, metal sulfide-containing material may fall under a general category of materials—in which case, it is worth noting that the metals mentioned (such as copper, nickel, lead, zinc, or combinations thereof) may not be present in all materials within the general category. For example, metal sulfide-containing material may be an ore (a naturally occurring rock or deposit)—but not all ores contain one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. A skilled person will recognize and be able to determine whether a given material constitutes a metal sulfide-containing material, that is, a material containing one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. Metal sulfide-containing material can take various forms, as a knowledgeable person will recognize. It is worth noting that metal sulfide-containing material may also contain other mineral salts besides sulfides. For example, metal sulfide-containing material can be sourced from an ore (a naturally occurring rock or deposit), including the concentrate of that ore, seawater, underground brines, waste, an alloy, a component of the human body, a medical device, or a consumer product. Examples of ores include mineral deposits (such as veins) and the like, obtained from waterways, dams, mines, and other known earth-related sources. Preferred ore examples include chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), pentlandite (FeNi)9S8, galena (PbS), sphalerite (Zn,Fe)S, or a combination thereof. Examples of components of the human body include teeth, bones, heart, muscles, joints, legs, arms, hands, fingers, knees, feet, and others.Examples of medical devices include life support systems and equipment, such as diagnostic devices, dialysis machines, medical implants (e.g., pacemakers), dental fillings, dental enamel, dental fillings, dentures, artificial joints, prostheses, or other prosthetics, or materials removed after diagnostic, radiological, or therapeutic administration, including, for example, metal nanoparticles. Examples of consumer products include jewelry, electronic devices, and other metal products such as ingots, bars, and coins. Examples of jewelry include rings, bracelets, necklaces, and so on. Examples of electronic devices include computers, monitors, power supplies, amplifiers, preamplifiers, digital-to-analog converters, analog-to-digital converters, batteries (e.g., lead-acid batteries), telephones, and so on. Examples of waste include former mining tailings, organic waste, and waste from wastewater treatment plants. A skilled person will recognize that a metal sulfide material may contain varying levels of copper, nickel, lead, and / or zinc, depending on the type of metal sulfide. The methods described here are effective at different levels. For example, a metal sulfide material may contain copper, nickel, lead, and / or zinc in concentrations ranging from 0.001% to 15% by weight. A metal sulfide material may contain copper, nickel, lead, and / or zinc at levels as low as 0.001% by weight, as low as 0.01% by weight, or as low as 0.05% by weight. A metal sulfide material may contain copper, nickel, lead, and / or zinc at levels as high as 15% by weight, as high as 12% by weight, or as high as 10% by weight. A metal sulfide material may contain copper at levels ranging from 0.05% to 7% by weight. The material containing the metal sulfide may contain nickel at levels in the range of 3-5% by weight. The sulfide-containing material should ideally be an ore (i.e., an ore containing one or more sulfide salts of copper, nickel, lead, and / or zinc), a groundwater brine, a battery, or a combination thereof. Even better, the sulfide-containing material should be an ore of chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), pentlandite (FeNi)9S8, galena (PbS), sphalerite (Zn,Fe)S, a groundwater brine, a battery, or a combination thereof. Ideally, the sulfide-containing material should be an ore of chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), or a combination thereof. Ideally, the material containing the metal sulfide should be a battery, particularly a used or partially used one. In these cases, the method described here provides an efficient means of recycling used or partially used batteries. As such, the method described here offers a novel and surprising way to recycle batteries. By applying the method described here to a battery, especially a used or partially used one, the metal halide can be extracted and used for a variety of different industrial purposes. It is important to note that the term "used or partially used" refers to batteries that have been used wholly or partially for a particular purpose. The sulfide-containing material should ideally be an ore (i.e., an ore containing one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof). Ideally, the sulfide-containing material should be an ore containing copper, nickel, lead, and / or zinc at a level of 0.001 to 15% by weight, preferably 0.05 to 10% by weight. As will be appreciated by a skilled professional, the ore can undergo preliminary steps such as particle size reduction and / or particle agglomeration to obtain controlled-size agglomerates. The ore can be reduced to a manageable slurry, which is then applied to the oxidizing mixture in tanks. Crushing the ore to a size of 1–1000 microns is preferred, ideally 5–200 microns. The ore may also undergo pretreatment in a pressure oxidizing system, which may involve heating to temperatures between 200°C and 2000°C, but more commonly to 600°C and 1300°C. The ore can also be concentrated, separately or in combination with the above, by gravity concentration or flotation. Here, the step of providing an aqueous acid-oxidizing mixture containing water, an acid, an oxidizing agent, and a halide ion source (also referred to as the "halide ion source") is revealed. The aqueous acid-oxidizing mixture has a pH less than 7. This step is referred to here as Step A. In Step A, without adhering to any specific theory, it is assumed that the oxidizing agent reacts with the halide ion to form halide species such as [Hal]OH (where [Hal] is a halide), but it is also assumed that other similar species, such as Hal2 and Hal3, may form. - . The term "aqueous acid-oxidizing mixture," as used here, refers to a mixture formed by combining water, an acid, an oxidizing agent, and a source of halide ions. The water used may be tap water, well water, distilled water, recycled water, or seawater. The oxidizing agent described here includes hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromous acid, hypoiodous acid, hypochlorite salt, hypobromite salt, hypoiodate salt, percarbonate salt, persulfate salt, permanganate salt, an anode connected to a power source, or combinations thereof. It is understood that the term "oxidizing agent" takes its usual definition in the field, referring to a component capable of acting as an oxidant. This could be, for example, a chemical reagent (often referred to as an oxidizing agent) or a component of a system suitable for achieving oxidation by electrolysis, such as an anode connected to a power source. The oxidation agent should ideally include hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromous acid, hypoiodous acid, hypochlorite salt, hypobromite salt, hypoiodate salt, percarbonate salt, persulfate salt, permanganate salt, or a combination thereof. Ideally, the oxidation agent should include hydrogen peroxide, ozone, chlorine, bromine, iodine, hypochlorous acid, hypobromous acid, hypoiodous acid, hypochlorite salt, hypobromite salt, hypoiodate salt, percarbonate salt, persulfate salt, permanganate salt, or a combination thereof. Hydrogen peroxide is the most preferable oxidation agent. When the oxidizing agent is a chemical reagent (such as hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromoic acid, hypoiodous acid, hypochlorite salt, hypobromite salt, hypoiodate salt, percarbonate salt, persulfate salt, permanganate salt, or combinations thereof), the chemical reagent can be used in varying quantities to form an aqueous acidic oxidizing mixture. When the oxidizing agent is a chemical reagent (such as hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromoic acid, hypoiodous acid, hypochlorite salt, hypobromite salt, hypoiodate salt, percarbonate salt, persulfate salt, permanganate salt, or combinations thereof), the amount of oxidizing agent added to form the aqueous acid oxidizing mixture relative to the amount of halide ion source added to form the aqueous acid oxidizing mixture should be in the range of 0.1:1 to 10:1 by weight, and preferably in the range of 1:1 to 10:1 by weight. A skilled person will realize that an oxidation medium can be generated on-site when necessary. A knowledgeable person will recognize that "ozone" refers to O3. Ozone can be introduced as a gas by pumping it as bubbles through the remaining components to form an aqueous acidic oxidizing mixture. Ozone can be generated on-site in several ways, as a knowledgeable person will also understand. A knowledgeable person will understand that "chlorine" refers to Cl2. Chlorine can be introduced as a gas by pumping it as bubbles through the remaining components to form an aqueous acidic oxidizing mixture. Chlorine can be generated on-site in several ways, as a knowledgeable person will also know. On-site generation is preferred due to its lower toxicity. A skilled person will understand that "oxygen" refers to O2. Oxygen can be introduced as a gas by pumping it as bubbles through the remaining components to form an aqueous acidic oxidizing mixture, including dissolved oxygen. Oxygen can be generated on-site in several ways, as a skilled person will also understand. A skilled person will recognize that "bromine" refers to Br₂. Bromine can be introduced in liquid or gaseous form. For example, bromide can be supplied for use in the method as part of an aqueous solution of which concentrations can vary; possible concentrations are 5–100% wt, 5–70% wt, 20–70% wt, 30–70% wt, or 30–60% wt. Bromide can be introduced in gaseous form by pumping it as bubbles through the remaining components to form an aqueous acid-oxidizing mixture, and / or bromide can be generated on-site in several ways, as a skilled person will know. A skilled person will recognize that "iodine" refers to I2. Iodine can be added directly as a solid to form the aqueous acid-oxidizing mixture, or it can be supplied for use in the method as part of an aqueous solution of which concentrations can vary; possible concentrations are 5-100% by weight, 5-70% by weight, 20-70% by weight, 30-70% by weight, or 30-60% by weight. A skilled person will recognize that "hypochlorous acid" refers to HOCl. It can be supplied for use in the method as part of an aqueous solution of which concentrations can vary; possible concentrations are 5-100% by weight, 5-70% by weight, 20-70% by weight, 30-70% by weight, and 30-60% by weight. A skilled person will recognize that "hypobromous acid" refers to HOBr. It can be supplied for use in the method as part of an aqueous solution of which concentrations can vary; possible concentrations are 5-100% wt, 5-70% wt, 20-70% wt, 30-70% wt, or 30-60% wt. A skilled person will recognize that "hypoiodic acid" refers to HIO. It can be supplied for use in the method as part of an aqueous solution of which concentrations can vary; possible concentrations are 5-100% wt, 5-70% wt, 20-70% wt, 30-70% wt, or 30-60% wt. A knowledgeable person will understand that "hypochlorite salt" refers to any salt capable of generating the hypochlorite anion (ClO₂). − In solution. The hypochlorite salt should preferably be an alkali metal hypochlorite salt, for example, lithium hypochlorite, potassium hypochlorite, calcium hypochlorite, and / or sodium hypochlorite. Sodium hypochlorite is the preferred hypochlorite salt. A knowledgeable person will recognize that "hypobromite salt" refers to any salt capable of generating the hypobromite anion (BrO₂). − In solution. The hypobromite salt should preferably be an alkali metal hypobromite salt, for example, lithium hypobromite, potassium hypobromite, and / or sodium hypobromite. Sodium hypobromite is the preferred hypobromite salt. A skilled person will recognize that hypodate salt refers to any salt capable of generating the hypodate anion (IO₃). − In solution. The hypoiodate salt should preferably be an alkali metal hypoiodate salt, for example, lithium hypoiodate, potassium hypoiodate, and / or sodium hypoiodate. Sodium hypoiodate is preferred. A knowledgeable person will recognize that a percarbonate salt refers to any salt with the formula X₂H₃CO₆, where X is a cation such as lithium, potassium, or sodium. Ideally, the percarbonate salt should be an alkali metal percarbonate, for example, lithium percarbonate, potassium percarbonate, and / or sodium percarbonate. Sodium percarbonate is the preferred choice. A knowledgeable person will recognize that persulfate salt refers to any salt capable of generating persulfate anions (SO5). 2− and / or S2O8 2− In solution, this includes caroacid. The persulfate salt should preferably be lithium persulfate, potassium persulfate, calcium persulfate, and / or sodium persulfate. Sodium persulfate is preferred as the persulfate salt. A knowledgeable person will recognize that "permanganate salt" refers to any salt capable of generating the permanganate anion (MnO4). − In solution. The permanganate salt should preferably be an alkali metal permanganate salt, for example, lithium permanganate, potassium permanganate, and / or sodium permanganate. Potassium permanganate is the preferred permanganate salt. A knowledgeable person will understand that an anode is an electrode where oxidation occurs. Generally, the anode is at least partially (or completely) immersed in an aqueous acidic oxidizing mixture. The anode is connected to a power source capable of applying an electric current so that electrons flow away from the anode, allowing oxidation (i.e., loss of electrons) to occur at the anode. This is commonly referred to as oxidation by electrolysis, and therefore a knowledgeable person will understand that the power source is usually connected to a cathode. A knowledgeable person will recognize that "hydrogen peroxide" refers to H₂O₂. Using hydrogen peroxide offers economic, commercial, and environmental advantages compared to other oxidizers. Hydrogen peroxide is particularly favored. More specifically, it is widely available commercially, and its decomposition products are water and oxygen, giving it environmentally friendly properties. Different amounts of hydrogen peroxide can be used to form an aqueous acid oxidizing mixture. Ideally, the ratio of hydrogen peroxide added to the halide ion source added to form the mixture should be between 0.1:1 and 10:1 by weight, with 1:1 to 10:1 by weight being preferable. Hydrogen peroxide can be supplied for use in the method as part of an aqueous solution of which concentrations can vary; possible concentrations are 5-100% by weight, 5-70% by weight, 20-70% by weight, 30-70% by weight, or 30-60% by weight. Hydrogen peroxide is commercially available from numerous companies and can be widely supplied by road or rail. These companies include, but are not limited to, Evonik, Solvay GmbH, Kemira, and Arkema. Some companies offer on-site generation, which may be compatible with the method described here. The inventors of the current application found that the halide ion source can take many different forms and still lead to the successful extraction of copper, nickel, lead, and / or zinc. The halide ion source can be supplied as a liquid (e.g., an aqueous solution or suspension), a solid, or a gas. For example, the halide ion source can be generated from a halide gas (e.g., when generating a chloride ion source), a halide gas / liquid (e.g., when generating a bromide ion source), or a halide solid / liquid (e.g., when generating an iodide ion source). The inventors of the current application found that the halide ion source can include a variety of different halides and still yield successful extraction of copper, nickel, lead, and / or zinc. However, it is preferable for the halide ion source to include a bromide ion source, a chloride ion source, an iodide ion source, or combinations thereof. Even better is for the halide ion source to include a bromide ion source, a chloride ion source, or combinations thereof, as these scenarios lead to particularly good extraction. In some cases, the halide ion source may include at least one bromide ion source. The source of halide ions can be a halide salt. Ideally, the source of the halide ions should be at least one metal halide. When the source of the halide ions is at least one metal halide, the metal can be lithium, potassium, sodium, calcium, magnesium, or a combination thereof. Ideally, the halide ion source should be at least one alkali metal halide. When the halide ion source is at least one alkali metal halide, this alkali metal can be lithium, potassium, sodium, or a combination thereof. In the preferred scenario, the halide ion source should be sodium halide and / or potassium halide, especially when the halide is a chloride. Different amounts of halide ion source can be used to form an aqueous acid oxidizer mixture. The amount of halide ion source added to form the aqueous acid oxidizer mixture can range, for example, from 1 to 20% by weight, depending on the total weight of the aqueous acid oxidizer mixture. The amount of halide ion source added to form the aqueous acid oxidizer mixture can be at least 1%, preferably at least 5%, depending on the total weight of the aqueous acid oxidizer mixture. The amount of halide ion source added to form the aqueous acid oxidizer mixture can range up to 20% by weight, preferably up to 15% by weight, depending on the total weight of the aqueous acid oxidizer mixture. The aqueous acid-oxidizing mixture described here contains an acid. Various acids are suitable for the current description. However, the acid should ideally be formic acid, acetic acid, citric acid, carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, or a combination thereof. Ideally, the acid should contain sulfuric acid, hydrochloric acid, nitric acid, or a combination thereof, as good results have been achieved using these acids, as demonstrated by the examples. Ideally, the acid should contain sulfuric acid, hydrochloric acid, or a combination thereof. Ideally, the acid should contain sulfuric acid, as this provides particularly good results, as demonstrated by the examples. The acid can be added as a concentrated acid or as a dilute solution. A skilled person will also know that carbonic acid, for example, can be added directly to an aqueous acid-oxidizing mixture, or it can be formed in situ by adding carbon dioxide. The preferred order of addition for forming an aqueous acid-oxidizing mixture is to add the acid after the remaining ingredients. In other words, the preferred order of addition is to first combine water, the oxidizing agent, and the halide ion source to form an aqueous oxidizing and halide mixture, and then add the acid to this aqueous oxidizing and halide mixture to form an aqueous acid-oxidizing mixture. The term "aqueous oxidizing and halide mixture" refers to the mixture formed by combining water, the oxidizing agent, and the halide ion source. It is also preferable to stir the reaction until it becomes homogeneous, monitoring the increase in oxidation-reduction potential and the formation of the filtrate before adding any metal source. The leaching process can be restarted after the initial extraction by adding the required chemicals. What has been revealed here is that the aqueous acid oxidizer mixture has a pH < 7. It is understood that a pH < 7 indicates an acidic pH. It has been shown that the aqueous acid oxidizer mixture can take on a variety of different acidic pH values ​​and still provide successful extraction. For example, the aqueous acid oxidizer mixture can have a pH greater than or equal to 0.1, greater than or equal to 0.4, or greater than or equal to 0.8. The acid-hydroxy mixture can have a pH 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 pH of the acid-hydroxy mixture should be less than or equal to 3, and ideally less than or equal to 2. As can be seen from the examples, when the pH of the acid-hydroxy mixture is in the range of 0.1-1.5, particularly good extraction is achieved. A skilled person will know how to modify an acid-oxidizing-hydroxy mixture to achieve a specific pH. The pH is measured using standard methods known in the field, for example, with a standard electronic pH meter or a color-coded test strip, across temperatures ranging from 5°C to 75°C. A skilled person will understand that the oxidizing agent and the halide ion source are not necessarily mutually exclusive terms; they may be of the same type or different types. For example, the oxidizing agent and the halide ion source could both be hypobromous acid (thus providing a direct source of BrOH for the aqueous acid-oxidizing mixture) and / or dissolved bromine. However, it is preferable for the oxidizing agent and the halide ion source to be of different types. A knowledgeable person will understand that an acid and a halide ion source are not necessarily mutually exclusive terms; they may be of the same type or different types. For example, the halide ion source and the acid could both be hypobromous acid or hypochlorous acid. However, it is preferable for the halide ion source and the acid to be of different types. A skilled person will understand that an acid and an oxidizing agent are not necessarily mutually exclusive terms; they may be of the same type or different types. For example, both the acid and the oxidizing agent could be hypobromous acid or hypochlorous acid. However, it is preferable for the acid and the oxidizing agent to be of different types. It is preferable that all three oxidizing agents, the source of the halide ions, and the acid, be of different types. The amount of metal sulfide material that comes into contact with the aqueous acid-oxidizing mixture can be adjusted depending, for example, on the type of metal sulfide material. It can be added in amounts ranging from 1 g to 1000 g, preferably from 10 g to 800 g, and even better from 30 g to 600 g. The weight ratio of the metal sulfide material to the aqueous acid-oxidizing mixture can also be adjusted depending, for example, on the type of metal sulfide material and the scope of the procedure. It can range, for example, from 1:0.2 to 1:10000. The weight ratio of the metal sulfide material to the aqueous acid-oxidizing mixture can be at least 1:0.2, preferably at least 1:1, and ideally at least 1:2. The ratio, by weight, of materials containing metal sulfide: The aqueous acid oxidation mixture can reach 1:10000, up to 1:1000, up to 1:10, preferably up to 1:8, and preferably even higher up to 1:7. It is preferable that the aqueous acid oxidizer mixture be stirred for at least 5 minutes before the aqueous acid oxidizer mixture comes into contact with the material containing metal sulfide. In some applications, steps (a) and (b) are performed sequentially. That is, the aqueous acid oxidizing mixture is supplied and then it comes into contact with the material containing the metal sulfide. In other manifestations, steps (a) and (b) occur simultaneously. For example, the metal sulfide-containing material may come into contact with an intermediate mixture containing one or more (but not all) of the components of the aqueous acid oxidizer mixture, and the remaining components of the aqueous acid oxidizer mixture are added later. It is understood that in this scenario, the aqueous acid oxidizer mixture is in direct contact with the metal sulfide-containing material during its formation. Thus, the provision of the aqueous acid oxidizer mixture in step (a) and the contact of this mixture with the metal sulfide-containing material in step (b) occur simultaneously. The step of contacting the aqueous acid oxidizer mixture with the metal sulfide-containing material to extract the metal and form a metal halide solution has been demonstrated here. The same metal sulfide-containing material can then be optionally separated from the metal halide solution and washed, preferably with a fresh aqueous acid oxidizer mixture as described here. Washing the metal sulfide-containing material with a fresh aqueous acid oxidizer mixture will form an additional metal halide solution. What has been revealed here is that the method mentioned here could be a method for extracting nickel from a material containing nickel sulfide, to extract nickel from the material containing nickel sulfide and form a nickel halide solution. It has been revealed here that the method mentioned here could be a method for extracting lead from lead sulfide-containing material, for extracting lead from lead sulfide-containing material and forming a lead halide solution. It has been revealed here that the method mentioned here could be a method for extracting zinc from zinc sulfide-containing material, for extracting zinc from zinc sulfide-containing material and forming a zinc halide solution. The method described here is particularly applicable to the extraction of copper, nickel, and / or zinc. Therefore, it is best understood as a method for extracting copper, nickel, and / or zinc from material containing copper sulfide, nickel sulfide, and / or zinc sulfide, and forming a solution of copper halide, nickel halide, and / or zinc halide. The method described here is particularly applicable to the extraction of copper and / or zinc. Therefore, it is best understood as a method for extracting copper and / or zinc from copper sulfide and / or zinc sulfide-containing material, and for forming a copper and / or zinc halide solution. As the examples demonstrate, particularly good results have been obtained in copper extraction. Therefore, the method described here is best understood as a method for extracting copper from copper sulfide-containing material, or for extracting copper from copper sulfide-containing material and forming a copper halide solution. What is revealed here is the contact step between the aqueous acid-oxidizing mixture and the metal sulfide-containing material to extract the metal from the sulfide-containing material and form a metal halide solution. As used here, 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 "leaching" 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 the metal halide, which can then be isolated or converted into other forms of the metal. For example, the metal halide can be converted into another metal salt (such as the metal carbonate and / or the metal hydroxide), and / or the metal itself. 0 It is understood that the metal 0 It refers to the metal in question in a zero oxidation state, for example, copper. 0 Nickel 0 lead 0 Zinc 0 This contrasts with referring to the metal in question as a cation or salt. Accordingly, the method may also include a step to convert the metal halide (extracted from the sulfide-containing material) into another metal salt and / or the metal itself. 0 This refers to the step of converting the metal halide into another metal salt and / or the metal itself. 0 (In step C). A skilled person will realize that there are different ways to convert a metal halide into another metal salt and / or metal. 0 He will be familiar with the appropriate reagents and conditions. A skilled person will realize that there are different ways to convert a metal halide into metal. 0 The metal carbonate and / or metal hydroxide will be used, and the appropriate reagents and conditions will be known. However, it is preferable that step c) includes contacting the metal halide solution with carbon dioxide, carbon monoxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid, a reducing agent, sodium hydroxide, potassium hydroxide, oxygen, ozone, or combinations thereof. Another benefit is realized when the method includes a step to convert the metal halide (extracted from the metal sulfide-containing material) into another metal salt (such as the metal carbonate, and / or metal hydroxide), and / or the metal itself. 0 This allows for efficient halide recycling, providing an effective method, at least in terms of reactant usage. It is clear, therefore, that the method described here encompasses scenarios where recycled leaching is present. When step C) involves the contact of the metal halide solution with carbon dioxide, carbon monoxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid, or a combination thereof, the metal halide is converted to the metal carbonate. When step c) includes the step of contacting the metal halide solution with a reducing agent, the metal halide is converted into metal. 0 . It is preferable that step C) be carried out by electrolysis, thereby converting the metal halide into metal. 0 The term electroplating takes its usual definition in the field, referring to the passing of an electric current through a metal halide solution so that the metal is deposited onto a cathode via an electroplating process. Electroplating is preferred due to the low formation of byproducts. When step C) involves 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 the metal hydroxide. A skilled person will understand that a reducing agent is a component capable of acting as a reducing agent. This could be, for example, a chemical reagent (often referred to as a reducing agent) or a component in a system suitable for carrying out electrolytic reduction, such as a cathode connected to a power source. Ideally, the reducing agent should be a chemical reagent. The preferred reducing medium is zinc, sodium metabisulfite, hydrogen gas, and / or a cathode connected to a power source. A person familiar with the process will understand that a cathode is an electrode where reduction occurs. Generally, the cathode is at least partially (or fully) immersed in a metal halide solution. The cathode is connected to a power source capable of applying an electric current so that electrons flow towards the cathode, allowing reduction (i.e., electron gain) to occur at the cathode. This is commonly referred to as electrolytic reduction, and a person familiar with the process will understand that the power source is usually connected to an anode. More preferably, the reducing agent is zinc, sodium metabisulfite, and / or hydrogen gas. It is preferable to convert the metal halide to the metal carbonate, as the overall reactions in this scenario lead to the consumption of carbon dioxide, thus achieving further improvement in environmental aspects. What has been revealed here is a method that could be used to extract nickel from a material containing nickel sulfide, to extract nickel from the nickel sulfide-containing material and form a nickel halide solution, optionally including the step of converting the nickel halide to nickel. 0 Nickel carbonate, and / or nickel hydroxide. What has been revealed here is a method that could be used to extract lead from a material containing lead sulfide, to extract lead from the lead sulfide-containing material and form a lead halide solution, optionally including the step of converting the lead halide back into lead. 0 Lead carbonate, and / or lead hydroxide. What has been revealed here is a method that could be used to extract zinc from a zinc sulfide-containing material, to extract zinc from the zinc sulfide-containing material and form a zinc halide solution, optionally including the step of converting the zinc halide to zinc. 0 Zinc carbonate, and / or zinc hydroxide. The method described here is particularly applicable to the extraction of copper and / or zinc. Therefore, it is preferable that the method described here be for extracting copper and / or zinc from a material containing copper sulfide and / or zinc sulfide, for extracting copper and / or zinc from a material containing copper sulfide and / or zinc sulfide and forming a copper and / or zinc halide solution, optionally including the step of converting the copper 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. As can be seen from the examples, particularly good results have been obtained for copper extraction. Therefore, the method described here is a method for 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 including the step of converting the copper halide to copper, copper carbonate, and / or copper hydroxide. What has been revealed here is that the metal is extracted from the metal sulfide-containing material to form a metal halide, which can then be recovered and thus isolated from the remaining reactants, and / or converted into other forms of the metal, which can in turn be recovered and thus isolated from the remaining reactants. Accordingly, the methods announced here may also include the step of recovering the metal halide, and / or may also include the step of recovering the other form(s) of the metal into which the metal halide has been converted. The term "recovery" is understood to mean the collection, removal, or isolation of the metal species in question (i.e., the metal halide, and / or the other form(s) of the metal into which the metal halide has been converted) from the reactant mixture. This can be achieved by using appropriate solid-liquid separation techniques (e.g., sieving) when the metal species in question is a solid (e.g., a metal carbonate), by solvent extraction, which may or may not include various chelating agents, by reverse osmosis, by using activated carbon, by electrowinning, or by using one or more ion-exchange resins.It is understood that the phrase "other form(s) of the metal to which the metal halide has been transformed" refers to forms that have been detected in other locations of the current discovery and thus could include another metal salt (e.g., metal carbonate, and / or metal hydroxide), metal. 0 Or a combination thereof, and are subject to the same degrees of preference revealed here. The use of ion-exchange resins is a preferred method for recovering the metal species, i.e., the metal halide, and / or other forms of the metal to which the metal halide has been converted. As detailed elsewhere in this disclosure, these other forms of the metal may include a salt of another metal (such as a metal carbonate and / or metal hydroxide). 0 or a combination thereof. Accordingly, steps b) and c) (where applicable) may involve the use of resins. Ion exchange resins capture the metal species, thus isolating the metal species from the solution and allowing for good recovery of the metal species from the reactant mixture. Ion exchange resins can be used in the method described here with metal sulfide materials containing varying concentrations of the metal, but they are effective even when the metal level in the metal sulfide material is low. When used in the method described here, it is preferable that the ion-exchange resins have an organic polymer structure to which a series of functional groups are attached. These functional groups must contain at least one heteroatomic atom. In this preferred scenario, the resins provide improved metal capture compared to capture using activated carbon. Without adhering to any specific theory, it is believed that the improved metal capture is due to the presence of at least one heteroatomic atom within the functional group series. This at least one heteroatomic atom is thought to coordinate with the metal species in question, facilitating the formation of a complex between the metal and the resin. Therefore, these resins may be referred to as chelating resins. Step b) may also involve contacting the aqueous acid-oxidizing mixture with a resin, preferably an ion-exchange resin consisting of an organic polymer structure to which a series of functional groups are attached. These functional groups must contain at least one heteroatomic atom. The use of a resin in step b) is believed to allow the formation of a metal halide resin complex. The term "metal halide resin complex" refers to the type formed by the reaction between a metal halide (i.e., the metal extracted from the sulfide-containing material) and the resin. Therefore, a metal halide resin complex refers to a resin on which or within which a metal halide forms a complex. In step B, the resin and the metal sulfide-containing material can be added simultaneously or sequentially. "Sequentially" means adding them one after the other. For example, when adding the resin and the metal sulfide-containing material to the aqueous acid oxidizing mixture sequentially, the resin can be added before (i.e., prior to), or after the metal sulfide-containing material. Accordingly, the resin can be added simultaneously with, before, or after the metal sulfide-containing material. The timing of these steps can be tailored to the processing facilities. It should be noted that when adding the resin and the metal sulfide-containing material either simultaneously or in direct succession, a metal halide may form and then react directly to form a metal halide resin complex. This scenario is referred to as the "resin-in-leaching" process. Therefore, in step B, the resin and the metal sulfide-containing material can be added simultaneously to the aqueous acid oxidizing mixture. Alternatively, in step B, the resin can be added to the aqueous acid oxidizing mixture before the metal sulfide-containing material is added. Or, in step B, the resin can be added to the aqueous acid oxidizing mixture after the metal sulfide-containing material is added. The amount of resin used in step B can vary depending on the application, but it may range, for example, from 0.1 to 100 g per 100 mL of the aqueous acid-oxidizing mixture. The amount of resin used in step B can be as low as 0.1 g, as low as 1 g, as low as 2 g, or preferably as low as 5 g per 100 mL of the aqueous acid-oxidizing mixture. Alternatively, the amount of resin used in step B can be as high as 100 g, as low as 80 g, as low as 50 g, or preferably as low as 20 g per 100 mL of the aqueous acid-oxidizing mixture. Step C may also involve contacting the metal halide solution with a resin, preferably an ion-exchange resin consisting of an organic polymer structure to which a series of functional groups are attached. These functional groups contain at least one heteroatomoid. The use of a resin in Step C is thought to allow the formation of a complex between the resin and the metal form(s) into which the metal halide has been converted. As detailed elsewhere in this report, this other metal form(s) could include a salt of another metal (e.g., a metal carbonate and / or metal hydroxide). 0 Or a combination thereof. For example, when a metal halide is converted into a metal 0 The metal carbonate and / or metal hydroxide are believed to be used in step C, allowing for the formation of a metal-resin complex. 0 Metal carbonate resin complex, and / or metal hydroxide resin complex. The terms "metal resin complex" are understood to mean... 0 The terms "metal carbonate resin complex" and "metal hydroxide resin complex" each refer to the type of resin formed by the reaction between the metal and the resin. It is understood, therefore, that the terms "metal resin complex" 0 “Metal carbonate resin complex” and “metal hydroxide resin complex” refer to a resin on which or within which the metal species in question is a complex. In step c), the resin may be added before, simultaneously with, or after the conversion of the metal halide to another form(s) of the metal. As detailed elsewhere in this disclosure, this other form(s) of the metal may include a salt of another metal (such as a metal carbonate and / or metal hydroxide). 0 Or a combination thereof. The timing of these steps can be tailored to suit the processing facilities. It will be noted that when resin is added and the metal halide is converted to another form(s) of metal either simultaneously or in direct succession, the other form(s) of metal may then react directly to form a complex between the resin and the metal species in question (e.g., a metal-resin complex). 0 (metal carbonate resin complex, and / or metal hydroxide resin complex). In step (c), it is preferable to add the resin concurrently with, or after, the conversion of the metal halide to another form(s) of the metal. As detailed elsewhere in this disclosure, this other form(s) of the metal may include a salt of another metal (such as a metal carbonate and / or metal hydroxide). 0 Or a combination thereof. More preferably, the resin is added after the metal halide has been converted to another form(s) of the metal, in which case step c) may also involve contacting the mixture of the other form(s) of the metal with a resin, preferably an ion-exchange resin consisting of an organic polymer structure to which a series of functional groups are attached. The functional groups said contain at least one heteroatomoid, in order to form a complex between the resin and the metal species in question. The amount of resin used in step (c) can vary depending on the application, but may range, for example, from 0.1 to 100 g per 100 mL of metal halide solution, or of a mixture of other forms of the metal to which the metal halide has been converted. As detailed elsewhere in this disclosure, such other forms of the metal may include a salt of another metal (e.g., metal carbonate, and / or metal hydroxide), or a metal 0 The amount of resin used in step C can be at least 0.1 g, 1 g, 2 g, or preferably at least 5 g per 100 mL of the metal halide solution, or of the mixture of other metal forms into which the metal halide has been converted. Alternatively, the amount of resin used in step C can be up to 100 g, 80 g, 50 g, or preferably up to 20 g per 100 mL of the metal halide solution, or of the mixture of other metal forms into which the metal halide has been converted. The term "ion exchange resin" takes its usual definition in the field, referring to a substance that acts as an ion exchange medium and is generally insoluble in aqueous media. This implies that the ion exchange resin is substantially insoluble in the aqueous solutions and mixtures listed here, such as an aqueous acid-oxidizing mixture, a metal halide solution, or the other mixture of the metal form(s) into which the metal halide has been converted. "Substantially insoluble" means that less than 0.1 mg / mL of the resin dissolves in the aqueous solutions and mixtures listed here (such as an aqueous acid-oxidizing mixture, a metal halide solution, or the other mixture of the metal form(s) into which the metal halide has been converted) at 25 °C. As used here, the definitions relating to ion exchange resins generally refer to the properties of the ion exchange resin itself, i.e., before its addition to the aqueous solutions and mixtures described here. After its addition, it will be understood that, depending on the pH of the medium, proteation or deproteation of some ion exchange resin groups may occur. Ion exchange resins should ideally be porous. The porosity of the ion exchange resin increases the surface area available for ion exchange. In keeping with what will be understood from the term "ion exchange resin," an ion exchange resin, when used in the method announced here, consists of a polymer structure (sometimes referred to as a polymer matrix) to which a series of functional groups are attached. Specifically, an ion-exchange resin, when used, consists of an organic polymer structure to which a series of functional groups are attached. An ion-exchange resin may primarily consist of an organic polymer structure to which a series of functional groups are attached. When used in the method described here, ion exchange resins are commercially available from multiple sources; commercially available resins include, but are not limited to, the following types, all of which are ion exchange resins with functionally modified polystyrene structures in the following groups: SEPLITE® LSC660: Functionally modified with guanidine groups SEPLITE® LSC740: Functionally modified with thiol groups SEPLITE® LSC710: Functionally modified with iminodiacetic acid groups - AMBERSEP® 21K XLT Mesh Anion Exchange Resin (Cl-): Functionally modified with quaternary ammonium groups - Purogold™ MTA5015SO4: Functionally modified with quaternary ammonium groups - LEWATIT® MonoPlus TP 214: Functionally modified with thiourea groups - PurometTM MTS9140: Functionally modified with thiourea groups - LEWATIT MP 62 WS: Functionally modified with tertiary amine groups - LEWATIT TP 106: Functionally modified with quaternary ammonium groups As used here, the term "polymer" in this context refers to its established meaning within the field, denoting a homopolymer or copolymer formed by the polymerization of one or more monomers. Accordingly, this term includes, for example, linear polymers, branched polymers, and cyclic polymers. As used here, the term "homogeneous polymer," according to its usual definition in the field, refers to a polymer whose polymer chains consist of only one type of monomer. Similarly, the term "copolymer," according to its usual definition in the field, refers to a polymer whose polymer chains consist of two or more different types of monomers. Therefore, a specialist in the field will understand that the term "copolymer" encompasses polymers that include three different types of monomers (which are sometimes specifically referred to in the field as "terpolymers"). The term "block copolymer," according to its usual definition in the field, refers to a copolymer whose polymer chains consist of two or more blocks of monomers, each block being composed of a specific type of monomer, with at least two of these blocks containing a different type of monomer. The terms "biblock copolymer," "triblock copolymer," and "tetrablock copolymer" refer to copolymers composed of two, three, and four monomer blocks, respectively. As used here, the term "monomer," according to its usual definition in the field, refers to a molecular compound that can chemically bond to another monomer to form a polymer. Unless otherwise expressly stated, it should be understood that any monomer referred to here includes all mirror-image isomers, non-mirror-image isomers, racemic mixtures, and mixtures of the monomers concerned. It is understood that the term "polymer structure" refers to a series of covalently linked atoms that form a continuous molecular chain which acts as a support to which functional groups are attached. In line with the prevailing definition in the field, the polymer structure is generally the longest continuous molecular chain, of which other chains and functional groups can be considered as branched parts. It is understood that the term "organic polymer structure" refers to a polymer structure that includes carbon-carbon covalent bonds. The structure of an organic polymer can be cross-linked or non-cross-linked. Ideally, the organic polymer structure is cross-linked using a cross-linking agent such as diphenylbenzene, hexamethylenetetraamine, functionally modified silane, isocyanate, peroxide, or combinations thereof. Diphenylbenzene is particularly preferred for cross-linking. The amount of cross-linking agent can vary, but it may be, for example, 1% to 50% by weight, depending on the total weight of the polymer structure and the cross-linking agent. The structure of an organic polymer can be, for example, polystyrene, polyvinyltoluene, poly(vinylbenzyl chloride), polyvinyl acetate, polyvinyl butyral, polyvinyl ether, polyethylene, polyurethane, or acrylonitrile butadiene styrene. Ideally, the organic polymer structure is a vinyl polymer structure, understood to refer to a polymer structure formed from vinyl monomers (i.e., those monomers whose structure includes the formula −CH=CH2). For example, the organic polymer structure could be polystyrene, polyvinyltoluene, poly(vinylbenzyl chloride), polyvinyl acetate, polyvinyl butyral, or polyvinyl ether. Even more ideally, the organic polymer structure is polystyrene. In a particularly preferred embodiment, the organic polymer structure is polystyrene cross-linked with divinylbenzene. What is revealed here is a series of functional groups attached to the organic polymer structure. This attachment is generally achieved through covalent bonding with the organic polymer structure. This bonding can be accomplished using standard procedures well-established in the field. The term "chain" refers to the presence of multiple functional groups attached to the polymer structure. For a given ion-exchange resin, these functional groups may be similar or different. Functional groups contain at least one heteroatomic atom. The term "heteroatomic atom" has its usual definition in the field, referring to an atom that is neither carbon nor hydrogen. Ideally, a heteroatomic atom is one or more of N (nitrogen), S (sulfur), O (oxygen), or P (phosphorus). More preferably, a heteroatomic atom is one or more of N, S, and O; even more preferably, one or more of N and S. It will be assumed that when a heteroatomic atom is one or more of the listed options, additional heteroatoms—besides those listed here—may also be present within the functional groups. Unless otherwise expressly stated, the types of atoms identified for a heteroatomic atom will be understood to include that type regardless of whether it is in a neutral state. Specifically, when a series of functional groups contains N, this includes cases where N is positively charged, for example, as part of a quaternary ammonium group. Ideally, the functional chain should include one or more of the following: an iminodiacetic acid group, a thiourea group, a quaternary ammonium group, a guanidine group, an amine group, and a thiol group. The specialist will be familiar with the molecular structure to which these groups refer. In this context, the functional groups in the chain could be iminodiacetic acid groups, thiourea groups, quaternary ammonium groups, guanidine groups, amine groups, or thiol groups. More specifically, the functional chain includes one or more thiourea groups, quaternary ammonium groups, and guanidine groups. In this sense, the functional groups in the chain can be thiourea groups, quaternary ammonium groups, or guanidine groups. The functional groups revealed here can be linked to the polymer structure using standard reaction procedures known in the field, so that the functional group and the structure are positioned at a convenient point in the molecular structure of the functional group, as appreciated by the expert in the field. The term "iminodiacetic acid" refers to the formula HN(CH2CO2H)2. When the functional group sequence includes an iminodiacetic acid group, the functional groups include one or more of the following: The term "thiourea" refers to the formula where the groups can be R 1 R 2 R 3 and R 4 Similar or different, each chosen independently from the H or alkyl group. Preferably, the R groups. 1 R 2 R 3 and R 4 Similar or different, each chosen independently from the H or C1-C6 alkyl group. Within this embodiment, the groups are R 1 R 2 R 3 and R 4 Similar or different, each can be chosen independently from the H or C1-C3 alkyl group. Preferably, both R 3 and R 4 It is H. When the functional group sequence includes a thiourea group, the functional groups include one or more of the following subunits, with R retained. 1 R 2 R 3 and R 4 With the same meanings and preferences mentioned above: The term "quaternary ammonium" refers to the formula [NR 5 R 6 R 7 R 8 ] + Where R can be 5 R 6 R 7 and R 8 Similar or different, each chosen independently from the H or alkyl group. Preferably, R 5 R 6 R 7 and R 8 Similar or different, each is chosen independently from the H or C1-C6 alkyl group. Preferably, both R 5 R 6 R 7 and R 8 It is an alkyl group, preferably a C1-C6 alkyl group, and can be similar or different. Preferably, R 5 R 6 R 7 and R 8 It is an alkyl group C1-C3, and they can be the same or different. When the functional group sequence includes a quaternary ammonium group, the functional groups include one or more of the following subunits, with R retained. 5 R 6 R7 has the same meanings and preferences mentioned above: The term "guanidine" refers to the formula (R 9 R 10 N)(R 11 R 12 N)C=NR 13 Where R can be 9 R 10 R 11 R 12 and R 13 Similar or different, each chosen independently from the H or alkyl group. Preferably, the alkyl group is C1-C6, more preferably C1-C3. More preferably, the term "guanidine" refers to the formula HN=C(NH2)2, a formula that a knowledgeable person in the field will recognize as representing underived guanidine—where R 9 R 10 R 11 R 12 and R 13 It is H. When the functional group sequence includes a guanidine group, the functional groups include one or more of the following subunits, with R retained. 9 R 10 R 11 R 12 and R 13 With the same meanings and preferences mentioned above: The term "thiol" refers to the formula R 14 -SH, where R 14 It is an alkyl group, preferably the C1-C6 group, and even more preferably, the C1-C3 alkyl group. When a functional group series includes a thiol group, the functional groups include one or more of the following subunits: The term "amine" refers to the NR formula. 15 R 16 R 17 Where the groups can be R 15 R 16 and R 17 Similar or different, each chosen independently from the H or alkyl group. Preferably, R 15 R 16 and R 17 Similar or different, each chosen independently from the H or C1-C6 alkyl group. R is preferred. 15 R 16 and R 17 Similar or different, each consisting of an alkyl group, preferably the C1-C6 alkyl group. Ideally, both R 15 R 16 and R 17 It is an alkyl group C1-C3, and can be similar or different. When a functional group sequence includes an amine group, the functional groups include one or more of the following subunits, with R retained. 15 and R 16 With the same meanings and preferences mentioned above: It is understood from the usage here that the symbol " This indicates the end of the molecular fragment and thus the point at which the molecular fragments are attached to the polymer structure. The fragments can be attached directly to the polymer structure, for example, via a direct bond, or they can be attached via an alkyl group, such as the C1-C alkyl group. 10 Preferably the C1-C6 alkyl group, and even more preferably the C1-C3 alkyl group. The term "alkyl," as used here, refers to a straight or branched alkyl group that is either saturated or unsaturated. Ideally, the alkyl group should be a saturated alkyl group; even more preferably, the alkyl group should be a straight alkyl group. As used here, the term "alkyl (C a -C b )" - where a and b are integers, refers to an alkyl with a straight or branched chain containing carbon atoms from a to b. Thus, for example, the alkyl group C1-C 10 The C1-C6 group refers to a group containing 1 to 10 carbon atoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, and decyl. The C1-C6 group, on the other hand, refers to a group containing 1 to 6 carbon atoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and n-hexyl. Resins may be available in a variety of granules with a particle size distribution such that over 95% of the particles have diameters between 0.1 and 10 mm, 0.2 and 5 mm, 0.1 and 2.5 mm, or 0.2 and 1.5 mm. Apparent densities may vary, for example, from 100 g / L to 2000 g / L, preferably from 200 and 900 g / L, preferably greater than 500 g / L to 900 g / L, or from 600 g / L to 850 g / L. Absolute densities may also vary, for example, from 100 to 2000 g / L, preferably from 200 to 1500 g / L, preferably greater than 500 to 1200 g / L. When using resins in the method described here, the process may also include the extraction of metal species (i.e., metal halide and / or other forms of metal to which a metal halide has been transformed) from the metal-species resin complex. An expert in the field will appreciate the feasibility of achieving this through a variety of possible means. For example, the resin, including the metal species complex (metal-species resin complex), may be removed from the residual components according to the method described here using appropriate liquid-solid separation techniques (e.g., sieving) before the resin is subjected to a suitable method for separating the metal species from the resin. For example, metal species may be extracted from the metal-species resin complex by stripping, flaking, incineration, or burning the resin. The method described here may include an additional step of decontaminating the extracted material. This decontamination process involves contacting the material with one or more of the ion-exchange resins with the preferred properties and characteristics described here. Certain functional groups, such as thiol groups, have been shown to be selective for impurities like arsenic and mercury. Therefore, some of the resins described here are not only useful for selectively extracting the metal and preferentially removing impurities, but they can also be used to remove contaminants from the residual material (sometimes referred to as "tailings"), thus providing a "purification" process for these tailings. The method described here can be performed at a variety of temperatures, for example, from 5 to 100 degrees Celsius. It can also be performed within a range of different pressures; for example, under high pressures within a sealed system, although it is typically performed at atmospheric pressure. The following unlimited examples illustrate invention. Examples 1-8 Examples 1-8 show the results of extracting copper from an ore containing copper sulfide. The results are shown in Table 1 below, where Example 1 corresponds to "Test 1", Example 2 corresponds to "Test 2", and so on. Copper recovery was evaluated using fire titration and induction-coupled plasma (ICP) methods as follows. The amount of copper in the raw ore (i.e., the ore before extraction) was measured using the industry-standard fire titration method, as was the amount of copper in the flotation tailings (i.e., the depleted ore material remaining after extraction). The copper level in the raw ore was compared to the copper level remaining in the flotation tailings; the greater the difference between the copper level in the raw ore and the copper level remaining in the flotation tailings, the higher the copper recovery efficiency. Table 1 shows the difference between the copper level in the primary ore and the residual copper level in the flotation tailings as % of the copper level in the primary ore (i.e., primary – tailings / primary*100). Table 1 The following is the complete methodology for examples 1-8. Example 1 Water (156) was placed in a cylindrical container, and sodium bromide solution (46%, 20.6 mL), hydrogen peroxide (34%, 24.4 mL), and sufficient sulfuric acid were added to lower the pH to 0.5. The mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (50 g) was added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 1". Example 2 Water (176 mL) was placed in a cylindrical container, and sodium bromide solution (46%, 0.4 mL) and hydrogen peroxide (34%, 24.4 mL) were stirred into the water. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (50 g) was then added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 2". Example 3 Water (164 mL) was placed in a cylindrical container, and hydrobromic acid (48%, 13.8 mL) and hydrogen peroxide (34%, 24.4 mL) were stirred into the water. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (50 g) was then added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract solution, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 3". Example 4 Water (177 mL) was placed in a cylindrical container, and sodium chloride (7.4 g), hydrogen peroxide (34%, 24.4 mL), and sufficient hydrochloric acid were added to lower the pH to 0.5. The mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (50 g) was added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 4". Example 5 Water (156 mL) was placed in a cylindrical container, and sodium bromide solution (46%, 20.6 mL) and hydrogen peroxide (34%, 24.4 mL) were stirred into the water. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Then, copper sulfide-containing ore (25 g), previously crushed to 50 µm, was added. The reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 5". Example 6 Water (176 mL) was placed in a cylindrical container, and sodium bromide solution (46%, 0.4 mL) and hydrogen peroxide (34%, 24.4 mL) were stirred into the water. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (25 g) was then added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 6". Example 7 Water (164 mL) was placed in a cylindrical container, and hydrobromic acid (48%, 13.8 mL) and hydrogen peroxide (34%, 24.4 mL) were stirred into the water. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (25 g) was added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract solution, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was then analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 7". Example 8 Water (177 mL) was placed in a cylindrical container, and sodium chloride (7.4 g) and hydrogen peroxide (34%, 24.4 mL) were stirred in. Sufficient hydrochloric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (redox potential) exceeded 650. Pre-crushed copper sulfide ore (25 g) was added, and the reaction was stirred using a bottle roller for 60 minutes, with samples taken at 15, 30, and 60 minutes. The solution was filtered, and the flotation tailings were washed with 20 mL of the fresh extract, after the initial solution was set aside for analysis. The flotation tailings were then washed with water, dried, and sent for fire titration. The solution was analyzed for copper using a titrated ICP. The results are shown in Table 1 under "Test 8". Example 9 An aqueous acid oxidizing mixture was provided and brought into contact with four different samples of the ore. The samples were thoroughly dried until they were dry (friable) and crushed to -150 mesh (105 microns). The samples were analyzed in triplicate using thermal mining and acid digestion methods to determine the amount of metals in each sample. The amount of gold was determined using fire titration with final analysis using an inductively coupled spectrophotometer (ICP-OES). The amounts of other metals and the sulfur content were analyzed using acid digestion methods and ICP-OES analysis. All samples were analyzed prior to testing to establish reference readings for the various elements, as described above. Subsequently, portions of each sample were treated under varying conditions using an aqueous acid oxidizing mixture to determine the extraction efficiency of the elements present in the samples. The samples were filtered at 23°C (room temperature) for up to 60 minutes, with sampling occurring at 20-minute intervals. Stirring during the filtering cycle was performed using horizontal rotating containers equipped with internal baffles. Multiple variations of the aqueous acid oxidizing mixture were used to refine the results for the different samples. Subsamples of the aqueous acid oxidizing mixture were also tested at each interval to assess the economic viability and filtration conditions, including pH, ORP, and temperature. The aqueous samples were then analyzed using an inductively coupled spectrophotometer (ICP), and the results are reported below. Finally, the flotation residues resulting from the process described here were recalibrated to determine their residual values.Quality control metrics were monitored and the minimum process guidelines disclosed herein were met. The results are shown in Tables 2 and 3 below: Table 2 Table 3 As shown in Tables 2 and 3, the results are positive with respect to both the time taken and the quantity of elements extracted from the four tested ore samples. Accordingly, Tables 2 and 3 illustrate the promising results obtained by the method described here for extracting lead and zinc. Example 10 A series of aqueous acid oxidizing mixtures were applied to copper ore. The results are shown in Figure 1. As observed, all mixtures achieved high yields and yields beneficial to Cu, with the best extraction achieved using sulfuric acid, low pH, and higher halide concentrations. Example 11 A series of acidic aqueous oxidizing mixtures with a pH of 0.5 were formulated and applied to copper ore. NaCl concentrations were varied from 2 to 6.5 wt%, the mixture temperature from 30 to 80 °C, and the contact time from 15 to 45 minutes. Copper extraction was determined using ICP analysis of the solutions, and the results are shown in Table 4 below. Extraction levels exceeding 70% were observed in all tested mixtures. Test concentration NaCl (by weight) ٪ ) temperature (degrees Celsius) Time (minutes) Extraction ( ٪) 1 6,5 30 15 92,7 2 2 80 15 81,3 3 6,5 80 15 82,8 4 6,5 30 45 91,6 5 2 80 45 84,3 6 6,5 80 45 85 7 4,25 55 30 98,9 8 4,25 55 30 92,3 9 2 55 30 87,2 10 4,25 30 30 74,6 11 4,25 80 30 98 12 4,25 55 15 99,2 13 4,25 55 45 97,8 14 4,25 55 30 98,1 15 4,25 55 30 91 Table 4 Example 12 A series of aqueous acid oxidizing mixtures were formulated with variations in acid type, temperature, halide mixture, and pH, and subjected to contact with copper ore for varying operating periods. The halide concentration was kept constant. Copper extraction was determined using ICP analysis of the solutions, and the results are shown in Table 5 below. Extraction levels exceeded 70% for all tested mixtures. Test pH Temperature (degrees Celsius) Cl Frac 1 acid 2 Time (minutes) Extraction 3 ، ( ٪ ) 1 0,5 40 0,5 H 60 89,1 2 0,5 40 1,0 H 30 86,9 3 1,0 40 0,5 S 60 88,8 4 1,0 40 1,0 S 30 94,8 5 0,5 80 1,0 S 60 100,7 6 0,5 80 0,5 S 30 100,6 Table 5 1 Cl Frac = Part of the total halide in the formation of Cl (1.0 = 100% Cl, 0.5 = 50% Cl + 50% Br) 2 Acid: H = HCl, S = H2SO4 3 The extraction was calculated based on the average of the initial calibration.

Claims

1. A method of extracting metal from a metal sulfide containing material comprising the steps of:a) providing an aqueous acidic oxidant mixture comprising water, an acid, an oxidising means, and a halide ion source, wherein the aqueous acidic oxidant mixture has a pH of less than 7;wherein 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;b) 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;wherein the metal comprises copper, nickel, lead, zinc, or combinations thereof.

2. The method of claim 1, wherein the acid comprises, acetic acid, citric acid, carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, or combinations thereof.

3. The method of claim 1, wherein the acid comprises sulfuric acid, hydrochloric acid, nitric acid or combinations thereof.

4. The method of claim 1, wherein the acid comprises sulfuric acid.

5. The method of any preceding claim, wherein the aqueous acidic oxidant mixture has a pH in the range of 0.1-6.9.

6. The method of any preceding claim, wherein the aqueous acidic oxidant mixture has a pH in the range of 0.8-6.9.

7. The method of any preceding claim, wherein the aqueous acidic oxidant mixture has a pH less than or equal to 6, preferably less than or equal to 5, more preferably less than or equal to 4.

8. The method of any preceding claim, wherein the oxidising means comprises hydrogen peroxide, ozone, a percarbonate salt, a persulfate salt, a permanganate salt, or combinations thereof.

9. The method of any preceding claim, wherein the oxidising means comprises hydrogen peroxide.

10. The method of any preceding claim, wherein the halide ion source comprises a bromide ion source, a chloride ion source, an iodide ion source, or combinations thereof.

11. The method of any preceding claim, wherein the halide ion source comprises a bromide ion source, a chloride ion source, or combinations thereof.

12. The method of any preceding claim, wherein the halide ion source comprises a bromide ion source.

13. The method of any preceding claim, wherein the halide ion source is at least one metal halide, said metal being lithium, potassium, sodium, calcium, or combinations thereof.

14. The method of any preceding claim, wherein the halide ion source is at least one alkali metal halide, said alkali metal being lithium, potassium, sodium, or combinations thereof.

15. The method of any preceding claim, further comprising the step of: c) converting the metal halide to metal0, metal carbonate, and / or metal hydroxide.

16. The method of claim 15, wherein the halide is subsequently recycled for further use.

17. The method of any one of claims 15-16, wherein 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 (such as zinc, sodium metabisulfite, hydrogen gas, and / or a cathode connected to a power source), sodium hydroxide, potassium hydroxide, oxygen, ozone, or combinations thereof.

18. The method of any one of claims 15-17, wherein 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, or combinations thereof, thereby converting the metal halide to metal carbonate.

19. The method of any one of claims 15-18, wherein step c) comprises the step of contacting the metal halide solution with a reducing means (such as zinc, sodium metabisulfite, hydrogen gas, and / or a cathode connected to a power source), thereby converting the metal halide to metal0.

20. The method of any one of claims 15-19, wherein step c) is carried out by electrowinning, thereby converting the metal halide to metal0.

21. The method of any one of claims 15-20, wherein step c) comprises the step of contacting the metal halide solution with sodium hydroxide, potassium hydroxide, oxygen, ozone, or combinations thereof, thereby converting the metal halide to metal hydroxide.

22. The method of any one of claims 1-14, further comprising the step of recovering the metal halide.

23. The method of any one of claims 15-21, further comprising the step of recovering the metal0, metal carbonate, and / or metal hydroxide.

24. The method of any preceding claim, wherein step b further comprises contacting the aqueous acidic oxidant mixture with a resin, said resin 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.

25. The method of any one of claims 15-21, wherein step c further comprises contacting the metal halide solution with a resin, said resin 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.

26. The method of any one of claims 15-21, wherein step c further comprises contacting the metal0, metal carbonate, and / or metal hydroxide with a resin, said resin 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.

27. The method of any preceding claim, wherein the metal sulfide containing material comprises an ore, a subsurface brine, a battery, or combinations thereof.

28. The method of any preceding claim, wherein the metal sulfide containing material comprises an ore.

29. The method of any preceding claim, wherein the metal comprises copper, such that said method 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.

30. The method of any preceding claim, wherein steps a) and b) occur sequentially or simultaneously. 

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