process

Abstract

This article discloses a method for extracting metals from metal sulfide-containing materials, the method comprising the following steps: a) providing an aqueous acidic oxidant mixture comprising water, acid, an oxidizing agent, and a halide ion source, wherein the pH of the aqueous acidic oxidant mixture is less than 7; wherein the oxidizing agent includes hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, an anode connected to a power source, or a combination 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 forming a metal halide solution; wherein the metal includes copper, nickel, lead, zinc, or a combination thereof.

Description

Technical Field

[0001] This disclosure relates to a method for extracting metals from materials containing metal sulfides, wherein the metals include copper, nickel, lead, and zinc. Background Technology

[0002] 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, creating a need for the efficient extraction of these metals from related metal-containing materials.

[0003] Extraction processes for other metals are known in the art. For example, methods for extracting precious metals (e.g., gold or silver) are known. Generally, such methods involve extracting the precious metal from a precious metal-containing material (often referred to as “leaching” the precious metal from the precious metal-containing material) and then capturing the leached precious metal from a solution. For example, some methods use highly toxic inorganic cyanide to extract precious metals from precious metal-containing materials. Such processes are associated with considerable environmental problems (where accidental spills can cause environmental pollution) and considerable health and safety problems (where unintentional exposure to cyanide can cause significant human health problems). Other methods for extracting precious metals are disclosed in WO 2017 / 158561. However, these methods are only used for extracting substances generally referred to as precious metals (e.g., gold and / or silver, and others such as platinum and palladium). Also in the prior art are WO2023 / 057754, which relates to a method for extracting lithium, and WO2023 / 026041, which primarily evaluates the extraction of gold and / or silver. Methods typically involve the flotation of different metals followed by processing in a smelter.

[0004] Meanwhile, copper, nickel, lead, and zinc are metals with distinct properties, as evidenced by their different positions in the periodic table. Furthermore, copper, nickel, lead, and zinc typically exist as sulfide salts in the relevant metal-containing materials, which has historically posed a challenge to achieving efficient extraction. This is because sulfides tend to interfere with the leaching process, for example, due to poor selectivity for the metal and reactions with sulfur prior to metal extraction. Another challenge is believed to be the formation of a passivation layer, which prevents the leaching mixture from reaching the metal to be extracted. As a result, the extraction of copper, nickel, lead, and / or zinc presents challenges, particularly from materials containing these metals as one or more sulfide salts. Existing methods for extraction from sulfide-containing materials lack favorable kinetics or exhibit poor environmental performance.

[0005] Therefore, new methods for extracting copper, nickel, lead, and / or zinc are still needed, particularly from materials containing these metals as one or more sulfide salts. Summary of the Invention

[0006] This article discloses a method for extracting metals from materials containing metal sulfides, the method comprising the following steps:

[0007] a) Provide an aqueous acidic oxidant mixture comprising water, acid, oxidizing agent and halide ion source, wherein the pH of the aqueous acidic oxidant mixture is less than 7;

[0008] The oxidation methods include hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodite, percarbonate, persulfate, permanganate, an anode connected to a power source, or a combination thereof.

[0009] b) Contacting an aqueous acidic oxidant mixture with a metal sulfide-containing material to extract the metal from the metal sulfide-containing material and form a metal halide solution;

[0010] The metals include copper, nickel, lead, zinc, or combinations thereof.

[0011] Surprisingly, aqueous acidic oxidant mixtures have been found to achieve particularly 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 agents, and halide ion sources is believed to overcome the challenges associated with extraction in the presence of sulfide salts, resolve challenges related to the formation of any potential passivation layers, and provide improved kinetics for metal extraction. Furthermore, it has been surprisingly found that improved extraction can be achieved using more environmentally friendly components, rather than relying on less environmentally friendly components such as cyanides, high-temperature techniques, or ferric oxidants, for example. Moreover, the extraction of copper, nickel, lead, and / or zinc in halide form offers significant advantages because halide salts have higher solubility in water, allowing for the use of less water and thus further reducing environmental impact and carbon footprint. Detailed Implementation

[0012] The word "at most" used throughout the text means "at most including".

[0013] It should be understood that the phrase “within the scope of” used throughout the text includes the endpoints of that scope.

[0014] This disclosure relates to a method for extracting metals from a metal sulfide material, wherein the metal includes copper, nickel, lead, zinc, or combinations thereof. It should be understood that the method disclosed herein is a method for extracting copper, nickel, lead, zinc, or combinations thereof, and the metal sulfide material comprises one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. In some embodiments, the metal includes copper, nickel, and / or zinc, and the metal sulfide material is a material containing copper sulfides, nickel sulfides, and / or zinc sulfides (i.e., a material containing one or more sulfide salts of copper, nickel, and / or zinc). Preferably, the metal includes copper and / or zinc, and the metal sulfide material is a material containing copper sulfides and / or zinc sulfides (i.e., a material containing one or more sulfide salts of copper and / or zinc). More preferably, the metal includes copper, and the metal sulfide material is a copper sulfide material (i.e., a material containing one or more sulfide salts of copper).

[0015] The methods disclosed herein relate to extraction from metal sulfide-containing materials, specifically extraction from materials containing one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. It should be understood that, even for a given metal, a variety of possible sulfide salts may be present in the metal sulfide-containing material. It should also be understood that other components may be present in a given metal sulfide salt, wherein the metal sulfide salt need not consist entirely of sulfides and copper, nickel, lead, and / or zinc. For example, the metal sulfide-containing material may include sulfide salts such as CuFeS2, Cu2S, Cu5FeS4, (FeNi)9S8, PbS, (Zn,Fe)S, or combinations thereof. Preferably, the metal sulfide-containing material includes CuFeS2, Cu2S, Cu5FeS4, (Zn,Fe)S, or combinations thereof. More preferably, the metal sulfide-containing material includes CuFeS2, Cu2S, Cu5FeS4, or combinations thereof.

[0016] This document discloses various examples of metal sulfide-containing materials. In some instances, metal sulfide-containing materials may belong to a broad class of materials—in such instances, it should be understood that the stated metal (i.e., copper, nickel, lead, zinc, or combinations thereof) may not be included in all materials of that broad class. For example, metal sulfide-containing materials may be, for instance, ores (naturally occurring rocks or sediments)—however, not all ores contain one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof. Those skilled in the art will understand and be able to determine whether and when a particular material constitutes a metal sulfide-containing material, i.e., a material containing one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof.

[0017] As those skilled in the art will understand, metal sulfide-containing materials can take various forms. It should be understood that metal sulfide-containing materials may contain additional non-sulfide metal salts. Metal sulfide-containing materials can be, for example, selected from ores (naturally occurring rocks or sediments), including concentrates of such ores, seawater, underground brine, waste, metal mixtures, human components, medical devices, or consumer products. Examples of ores include deposits (e.g., veins) obtained from waterways, causeways, mines, and other soil sources known in the art. Preferred examples of ores include chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), nickel pyrite ((FeNi)9S8), galena (PbS), sphalerite ((Zn,Fe)S), or combinations thereof. Examples of human components include teeth, bones, heart, muscles, joints, legs, arms, hands, fingers, knees, feet, etc. Examples of medical devices include life support systems and equipment such as diagnostic machines, dialysis machines, medical implants (e.g., pacemakers), dental fillings, enamel, dental inlays, dentures, artificial joints, artificial limbs, or other artificial attachments, or materials removed after diagnostic, radiological, or therapeutic administration that contain, for example, metal-containing nanoparticles. Examples of consumer products include jewelry, electronic items, and other metal products such as ingots, bars, or circulating coins. Examples of jewelry include rings, bracelets, and necklaces. Examples of electronic items include computers, monitors, power supplies, amplifiers, preamplifiers, digital-to-analog converters, analog-to-digital converters, batteries (e.g., lead-acid batteries), and telephones. Examples of waste include tailings from previous mining operations, biological waste, and waste originating from wastewater treatment plants.

[0018] Those skilled in the art will understand that metal sulfide materials can contain varying amounts of copper, nickel, lead, and / or zinc, depending on the type of metal sulfide material. The methods disclosed herein are effective at a variety of contents. For example, metal sulfide materials can contain 0.001% to 15% by weight of copper, nickel, lead, and / or zinc. Metal sulfide materials can contain at least 0.001%, at least 0.01%, or at least 0.05% by weight of copper, nickel, lead, and / or zinc. Metal sulfide materials can contain up to 15%, up to 12%, or up to 10% by weight of copper, nickel, lead, and / or zinc. Metal sulfide materials can contain copper in the range of 0.05% to 7% by weight. Metal sulfide materials can contain nickel in the range of 3% to 5% by weight.

[0019] Preferably, the metal sulfide-containing material is an ore (i.e., an ore containing one or more sulfide salts of copper, nickel, lead, and / or zinc), underground brine, a battery, or a combination thereof. More preferably, the metal sulfide-containing material is an ore of chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), nickel pyrite ((FeNi)9S8), galena (PbS), sphalerite ((Zn,Fe)S), underground brine, a battery, or a combination thereof. Most preferably, the metal sulfide-containing material is an ore of chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4), or a combination thereof.

[0020] Preferably, the metal sulfide-containing material is a battery, particularly a spent or partially spent battery. In such cases, the method disclosed herein provides an effective means of recycling spent or partially spent batteries. Therefore, the method disclosed herein offers a surprisingly new means of recycling batteries. By applying the method disclosed herein to batteries, particularly spent or partially spent batteries, metal halides can be extracted and used for a variety of different industrial purposes. It should be understood that "spoiled or partially spent" refers to batteries that have been wholly or partially used for a specific purpose.

[0021] Preferably, the metal sulfide-containing material is an ore (i.e., an ore containing one or more sulfide salts of copper, nickel, lead, zinc, or combinations thereof). More preferably, the metal sulfide-containing material is an ore containing 0.001% to 15% by weight, preferably 0.05% to 10% by weight, of copper, nickel, lead, and / or zinc.

[0022] As those skilled in the art will understand, the ore can undergo pretreatment steps, such as reducing its particle size and / or agglomerating the particles to provide aggregates of controlled sizes. The ore size can be reduced for processing as a fluid slurry and contact with an oxidant mixture in a large vat. Preferably, the ore is pulverized, wherein the pulverized size is in the range of 1 micrometer to 1000 micrometers, more preferably in the range of 5 micrometers to 200 micrometers. The ore can also be pretreated in a pressure oxidation system, which may include heating to temperatures of 200°C to 2000°C, but more typically to temperatures of 600°C to 1300°C. The ore can also be enriched by gravity separation or flotation, alone or in combination with the above.

[0023] This document discloses steps for providing an aqueous acidic oxidant mixture comprising water, an acid, an oxidizing agent, and a halide ion source (also referred to as a "source of halide ions"), wherein the pH of the aqueous acidic oxidant mixture is less than 7. This is referred to herein as step a). In step a), it is not intended to be theoretically constrained to assume that the oxidizing agent interacts with halide ions to form halide species, such as [Hal]OH (where [Hal] is a halide), but theoretically other such species can also be formed, such as Hal2, Hal3. - .

[0024] The "aqueous acidic oxidant mixture" disclosed in this article refers to a mixture formed when water, acid, an oxidizing agent, and a halide ion source are mixed. The water present can be tap water, well water, distilled water, recycled water, or seawater.

[0025] The oxidation methods disclosed herein include hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, an anode connected to a power source, or combinations thereof. It should be understood that the term "oxidation method" is used with its usual definition in the art and therefore refers to a component capable of acting as an oxidant, and may be, for example, a chemical reagent (commonly referred to as an oxidant), or a component of a system suitable for achieving oxidation by electrolysis, such as an anode connected to a power source.

[0026] Preferably, the oxidation method includes hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, or a combination thereof. More preferably, the oxidation method includes hydrogen peroxide, ozone, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, or a combination thereof. Even more preferably, the oxidation method includes hydrogen peroxide, ozone, percarbonate, persulfate, permanganate, or a combination thereof. Most preferably, the oxidation method includes hydrogen peroxide.

[0027] When the oxidizing agent is a chemical reagent (e.g., hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, or a combination thereof), the chemical reagent can be used in various amounts to form an aqueous acidic oxidizing agent mixture. Preferably, when the oxidizing agent is a chemical reagent (e.g., hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, or a combination thereof), the amount of the oxidizing agent added to form the aqueous acidic oxidizing agent mixture relative to the amount of the halide ion source added to form the aqueous acidic oxidizing agent mixture is in the range of 0.1:1 to 10:1 by weight, more preferably in the range of 1:1 to 10:1 by weight.

[0028] Those skilled in the art will understand that, where appropriate, oxidation can be performed in situ.

[0029] Those skilled in the art will understand that "ozone" refers to O3. Ozone can be introduced as a gas through bubbling of the remaining components to form an aqueous acidic oxidant mixture. As those skilled in the art will understand, ozone can be generated in situ by a variety of possible methods.

[0030] Those skilled in the art will understand that "chlorine" refers to Cl2. Chlorine can be introduced as a gas through bubbling to form an aqueous acidic oxidant mixture. As those skilled in the art will understand, chlorine can be generated in situ by a variety of possible methods. In-situ generation is preferred due to reduced toxicity.

[0031] Those skilled in the art will understand that "oxygen" refers to O2. Oxygen can be introduced as a gas through bubbling to form an aqueous acidic oxidant mixture, including dissolved oxygen. As those skilled in the art will understand, oxygen can be generated in situ by a variety of possible methods.

[0032] Those skilled in the art will understand that "bromine" refers to Br2. Bromine can be introduced as a liquid or a gas. For example, bromide can be provided as part of an aqueous solution for use in the method, the concentration of which can vary, possibly from 5% to 100% by weight, 5% to 70% by weight, 20% to 70% by weight, 30% to 70% by weight, or 30% to 60% by weight. As those skilled in the art will understand, bromide can be introduced as a gas through bubbling of the remaining components to form an aqueous acidic oxidant mixture, and / or bromide can be generated in situ by a variety of possible methods.

[0033] Those skilled in the art will understand that “iodine” refers to I2. Iodine can be added directly as a solid to form an aqueous acidic oxidant mixture, or it can be provided as part of an aqueous solution for use in the method, the concentration of which can vary, possibly from 5% to 100% by weight, 5% to 70% by weight, 20% to 70% by weight, 30% to 70% by weight, or 30% to 60% by weight.

[0034] Those skilled in the art will understand that "hypochlorous acid" refers to HOCl. It can be provided as part of an aqueous solution for use in the method, the concentration of which can vary, possibly from 5% to 100% by weight, 5% to 70% by weight, 20% to 70% by weight, 30% to 70% by weight, or 30% to 60% by weight.

[0035] Those skilled in the art will understand that "hypobromous acid" refers to HOBr. It can be provided as part of an aqueous solution for use in the method, the concentration of which can vary, possibly from 5 wt% to 100 wt%, 5 wt% to 70 wt%, 20 wt% to 70 wt%, 30 wt% to 70 wt%, or 30 wt% to 60 wt%.

[0036] Those skilled in the art will understand that "hypoiodic acid" refers to HIO. It can be provided as part of an aqueous solution for use in the method, the concentration of which can vary, possibly from 5 wt% to 100 wt%, 5 wt% to 70 wt%, 20 wt% to 70 wt%, 30 wt% to 70 wt%, or 30 wt% to 60 wt%.

[0037] Those skilled in the art will understand that "hypochlorite" refers to salts that can generate hypochlorite anions (ClO) in solution. − Any salt of ), preferably, is an alkali metal hypochlorite, such as lithium hypochlorite, potassium hypochlorite, calcium hypochlorite, and / or sodium hypochlorite. Preferably, the hypochlorite is sodium hypochlorite.

[0038] Those skilled in the art will understand that "hypobromate" refers to salts capable of generating hypobromate anions (BrO) in solution. − Any salt of ), preferably, is an alkali metal hypobromite, such as lithium hypobromite, potassium hypobromite, and / or sodium hypobromite. Preferably, the hypobromite is sodium hypobromite.

[0039] Those skilled in the art will understand that hypoiodates refer to salts capable of generating hypoiodate anions (IO3-) in solution. −Any salt of ), preferably, is an alkali metal hypoiodate, such as lithium hypoiodate, potassium hypoiodate, and / or sodium hypoiodate. Preferably, the hypoiodate is sodium hypoiodate.

[0040] Those skilled in the art will understand that percarbonate refers to any salt with the chemical formula X₂H₃CO₆, where X is a cation, such as lithium, potassium, or sodium. Preferably, the percarbonate is an alkali metal percarbonate, such as lithium percarbonate, potassium percarbonate, and / or sodium percarbonate. Preferably, the percarbonate is sodium percarbonate.

[0041] Those skilled in the art will understand that persulfate refers to salts capable of generating persulfate anions (SO5) in solution. 2− and / or S2O8 2− Any salt thereof, including peroxymonosulfate (Caro's acid). Preferably, the persulfate is lithium persulfate, potassium persulfate, calcium persulfate, and / or sodium persulfate. Preferably, the persulfate is sodium persulfate.

[0042] Those skilled in the art will understand that "permanganate" refers to a substance capable of generating permanganate anions (MnO4) in solution. − Any salt of lithium permanganate. Preferably, the permanganate is an alkali metal permanganate, such as lithium permanganate, potassium permanganate, and / or sodium permanganate. Preferably, the permanganate is potassium permanganate.

[0043] Those skilled in the art will understand that the anode is the electrode where oxidation occurs. Generally, the anode is at least partially (or completely) immersed in an aqueous acidic oxidizing agent mixture. The anode is connected to a power source capable of applying current, causing electrons to flow away from the anode, thereby allowing oxidation (i.e., the loss of electrons) to occur at the anode. This is generally referred to as oxidation by electrolysis, and thus those skilled in the art will understand that the power source is typically connected to the cathode.

[0044] Those skilled in the art will understand that "hydrogen peroxide" refers to H2O2. The use of hydrogen peroxide offers economic, commercial, and environmental advantages over other oxidants. Hydrogen peroxide is particularly preferred. More specifically, hydrogen peroxide is commercially available on a very large scale, and its decomposition products are water and oxygen, making it environmentally friendly.

[0045] Various amounts of hydrogen peroxide can be used to form an aqueous acidic oxidant mixture. Preferably, the weight ratio of the amount of hydrogen peroxide added to form the aqueous acidic oxidant mixture to the amount of halide ion source added to form the aqueous acidic oxidant mixture is in the range of 0.1:1 to 10:1, more preferably in the range of 1:1 to 10:1.

[0046] Hydrogen peroxide can be provided as part of an aqueous solution for use in the method, the concentration of which can vary, possibly from 5 wt% to 100 wt%, 5 wt% to 70 wt%, 20 wt% to 70 wt%, 30 wt% to 70 wt%, or 30 wt% to 60 wt%.

[0047] Hydrogen peroxide is commercially available from many companies and can be supplied on a large scale by road or rail. These companies include, but are not limited to, Evonik, Solvay GmbH, Kemira, and Arkema. Some companies offer on-site generation concepts that are compatible with the methods disclosed herein.

[0048] The inventors of this application have discovered that halide ion sources can take various possible forms and still successfully extract copper, nickel, lead, and / or zinc. Halide ion sources can be provided as liquids (e.g., containing aqueous solutions or dispersions), solids, or gases. Halide ion sources can be generated, for example, from halide gases (e.g., when generating chloride ion sources), halide gas / liquid (e.g., when generating bromide ion sources), or halide solid / liquid (e.g., when generating iodide ion sources).

[0049] The inventors of this application have discovered that halide ion sources can include a variety of different possible halides and can still successfully extract copper, nickel, lead, and / or zinc. However, preferably, the halide ion source includes a bromide ion source, a chloride ion source, an iodide ion source, or a combination thereof. More preferably, the halide ion source includes a bromide ion source, a chloride ion source, or a combination thereof, because such approaches achieve particularly good extraction. In some embodiments, the halide ion source can be at least one bromide ion source.

[0050] The halide ion source can be a halide salt. Preferably, the halide ion source is at least one metal halide. When the halide ion source is at least one metal halide, the metal can be lithium, potassium, sodium, calcium, magnesium, or a combination thereof.

[0051] More preferably, the halide ion source is at least one alkali metal halide. When the halide ion source is at least one alkali metal halide, the alkali metal may be lithium, potassium, sodium, or a combination thereof. In a preferred embodiment, the halide ion source is sodium halide and / or potassium halide, particularly when the halide is a chloride.

[0052] Various amounts of halide ion sources can be used to form an aqueous acidic oxidant mixture. The amount of halide ion source added to form the aqueous acidic oxidant mixture can, for example, range from 1% to 20% by weight based on the total weight of the aqueous acidic oxidant mixture. The amount of halide ion source added to form the aqueous acidic oxidant mixture can be at least 1% by weight, preferably at least 5% by weight, based on the total weight of the aqueous acidic oxidant mixture. The amount of halide ion source added to form the aqueous acidic oxidant mixture can be at most 20% by weight, preferably at most 15% by weight, based on the total weight of the aqueous acidic oxidant mixture.

[0053] The aqueous acidic oxidant mixtures disclosed herein contain acids. Various acids are compatible with this disclosure. However, preferably, the acids include formic acid, acetic acid, citric acid, carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, or combinations thereof. More preferably, the acids include sulfuric acid, hydrochloric acid, nitric acid, or combinations thereof, with which good results have been obtained, as can be seen from the examples. Preferably, the acids include sulfuric acid, hydrochloric acid, or combinations thereof. Most preferably, the acids include sulfuric acid, as this provides particularly good results, as can be seen from the examples.

[0054] The acid can be added as a concentrated acid or as a diluent solution. Those skilled in the art will also understand that, for example, carbonic acid can be added directly to the aqueous acidic oxidant mixture, or it can be formed in situ by adding carbon dioxide. The preferred order of addition for forming the aqueous acidic oxidant mixture is to add the acid after the remaining components. In other words, the preferred order of addition is to first mix water, the oxidizing agent, and the halide ion source to form an aqueous oxidant-halide mixture, and then add the acid to the aqueous oxidant-halide mixture to form the aqueous acidic oxidant mixture. The term "aqueous oxidant-halide mixture" refers to a mixture formed by mixing water, an oxidant, and a halide ion source.

[0055] It is also preferable to stir the reaction until homogeneous, monitor the increase in redox potential, and form the leaching agent before adding any metal source. After the first extraction, the leaching agent can be regenerated by adding the desired chemicals.

[0056] The aqueous acidic oxidant mixtures disclosed herein have a pH value less than 7. It should be understood that a pH value less than 7 means pH < 7, i.e., an acidic pH. It has been found that aqueous acidic oxidant mixtures can be used at a variety of different acidic pH values ​​and still provide successful extraction. For example, the pH value of the aqueous acidic oxidant mixture can be greater than or equal to 0.1, greater than or equal to 0.4, or greater than or equal to 0.8. The pH value of the aqueous acidic oxidant mixture can be 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. Preferably, the pH value of the aqueous acidic oxidant mixture is less than or equal to 3, more preferably less than or equal to 2. As can be seen from the examples, particularly good extraction is achieved when the pH value of the aqueous acidic oxidant mixture is in the range of 0.1 to 1.5.

[0057] Those skilled in the art will understand how to adjust aqueous acidic oxidant mixtures to achieve a specific pH value. The pH value is measured using standard methods known in the art, such as using a standard electronic pH meter or color-coded test strips, within a temperature range of 5°C to 75°C.

[0058] Those skilled in the art will understand that the oxidizing agent and the halide source are not necessarily mutually exclusive terms and can therefore be the same or different species. For example, the oxidizing agent and the halide source can both be hypobromic acid (thus providing a direct source of BrOH to the aqueous acidic oxidant mixture) and / or dissolved bromine. However, preferably, the oxidizing agent and the halide source are different species.

[0059] Those skilled in the art will understand that acid and halide source are not necessarily mutually exclusive terms, and therefore can be the same or different species. For example, the halide source and acid can both be hypobromous acid or hypochlorous acid. However, preferably, the halide source and acid are different species.

[0060] Those skilled in the art will understand that acid and oxidizing agent are not necessarily mutually exclusive terms, and therefore can be the same or different species. For example, the acid and oxidizing agent can both be hypobromous acid or hypochlorous acid. However, preferably, the acid and oxidizing agent are different species.

[0061] More preferably, the oxidation method, the halide ion source, and the acid are all different species.

[0062] The amount of metal sulfide material in contact with the aqueous acidic oxidant mixture can be adjusted depending on, for example, the type of metal sulfide material, but can be added, for example, in amounts from 1 g to 1000 g, preferably from 10 g to 800 g, more preferably from 30 g to 600 g. The weight ratio of the metal sulfide material to the aqueous acidic oxidant mixture can be adjusted depending on, for example, the type of metal sulfide material and the scale of the method, and can be, for example, in the range of 1:0.2 to 1:10000. The weight ratio of the metal sulfide material to the aqueous acidic oxidant mixture can be at least 1:0.2, preferably at least 1:1, more preferably at least 1:2. The weight ratio of the metal sulfide material to the aqueous acidic oxidant mixture can be at most 1:10000, at most 1:1000, at most 1:10, preferably at most 1:8, more preferably at most 1:7.

[0063] Preferably, the aqueous acidic oxidant mixture is stirred for at least 5 minutes before contacting the material containing metal sulfides.

[0064] In some implementations, steps a) and b) occur sequentially. That is, an aqueous acidic oxidant mixture is provided and then contacted with a metal sulfide-containing material.

[0065] In other embodiments, steps a) and b) occur simultaneously. For example, the metal sulfide-containing material can be contacted with an intermediate mixture having one or more (but not all) components of an aqueous acidic oxidant mixture, followed by the addition of the remaining components of the aqueous acidic oxidant mixture. It should be understood that in this embodiment, the aqueous acidic oxidant mixture is contacted with the metal sulfide-containing material immediately upon formation. Therefore, the provision of the acidic aqueous oxidant mixture in step a) and the contact of this mixture with the metal sulfide-containing material in step b) occur simultaneously.

[0066] This document discloses a procedure for contacting a mixture of aqueous acidic oxidants with a metal sulfide-containing material to extract metal from the metal sulfide-containing material and form a metal halide solution. Optionally, the same metal sulfide-containing material can then be separated from the metal halide solution and washed, preferably with a fresh mixture of the aqueous acidic oxidant mixture disclosed herein. In the example where the metal sulfide-containing material is washed with a fresh mixture of the aqueous acidic oxidant mixture disclosed herein, this will form an additional metal halide solution.

[0067] The method disclosed herein can be a method for extracting nickel from nickel-containing sulfide materials, to extract nickel from nickel-containing sulfide materials and form a nickel halide solution.

[0068] The method disclosed herein can be a method for extracting lead from lead-containing sulfide materials, to extract lead from lead-containing sulfide materials and form a lead halide solution.

[0069] The method disclosed herein can be a method for extracting zinc from zinc-containing sulfide materials, to extract zinc from zinc-containing sulfide materials and form zinc halide solutions.

[0070] The methods disclosed herein are particularly applicable to the extraction of copper, nickel, and / or zinc. Therefore, preferably, the method herein is a method for extracting copper, nickel, and / or zinc from materials containing copper sulfides, nickel sulfides, and / or zinc sulfides, to extract copper, nickel, and / or zinc from the materials containing copper sulfides, nickel sulfides, and / or zinc sulfides and to form copper halide solutions, nickel halide solutions, and / or zinc halide solutions.

[0071] The methods disclosed herein are particularly applicable to the extraction of copper and / or zinc. Therefore, preferably, the method herein is a method for extracting copper and / or zinc from materials containing copper sulfides and / or zinc sulfides, to extract copper and / or zinc from the materials containing copper sulfides and / or zinc sulfides and to form copper halide solutions and / or zinc halide solutions.

[0072] As can be seen from the examples, particularly good results have been obtained for copper extraction. Therefore, more preferably, the method described herein is a method for extracting copper from copper-containing sulfide materials to extract copper from copper-containing sulfide materials and form a copper halide solution.

[0073] This document discloses a procedure for contacting a mixture of aqueous acidic oxidizing agents with a metal sulfide-containing material to extract a metal from the metal sulfide-containing material and form a metal halide solution. As used herein, the extraction of a metal from a metal sulfide-containing material may be referred to as leaching a metal from a metal sulfide-containing material, and the term "leaching agent" may be used to refer to the mixture / solution used for metal extraction. The extraction of a metal from a metal sulfide-containing material to form a metal halide can then be separated or converted to other forms of the metal discussed. For example, the metal halide can be converted to another metal salt (e.g., a metal carbonate and / or a metal hydroxide) and / or a metal... 0 It should be understood that metals 0 This refers to the metal being discussed being in a zero oxidation state, such as copper. 0 ,nickel 0 ,lead 0 and / or zinc 0 This refers not to the cation or salt form of the metal in question. Therefore, the method may also include converting a metal halide (extracted from a metal sulfide-containing material) into another metal salt and / or metal... 0 The steps involve converting a metal halide into another metal salt and / or metal.0 The step described herein is referred to as step c). Those skilled in the art will understand that there are various ways to convert a metal halide into another metal salt and / or metal. 0 They will also become familiar with suitable reagents and conditions.

[0074] Those skilled in the art will understand that there are multiple ways to convert metal halides into metals. 0 Metal carbonates and / or metal hydroxides, and suitable reagents and conditions will be familiar to the user. However, preferably, step c) includes contacting the metal halide solution with carbon dioxide, carbon monoxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid, reducing agents, sodium hydroxide, potassium hydroxide, oxygen, ozone, or a combination thereof.

[0075] When the method involves converting a metal halide (extracted from a metal sulfide-containing material) into another metal salt (e.g., a metal carbonate and / or a metal hydroxide) and / or a metal... 0 This step offers additional benefits. It allows for the efficient recovery of halides. Therefore, it provides an efficient method, at least in terms of the use of reactants. It should thus be understood that the methods disclosed herein cover schemes involving recycled leaching agents.

[0076] When step c) includes contacting 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 thereby converted into a metal carbonate.

[0077] When step c) includes contacting the metal halide solution with a reducing agent, the metal halide is thereby converted into a metal. 0 .

[0078] Preferably, step c) is performed by electrolytic deposition, thereby converting the metal halide into a metal. 0 Electrolytic deposition, as it is commonly defined in the art, refers to the process of passing an electric current through a metal halide solution, causing the metal to be deposited onto the cathode via an electroplating process. Electrolytic deposition is preferred due to the reduction in the formation of byproducts.

[0079] When step c) includes contacting the metal halide solution with sodium hydroxide, potassium hydroxide, oxygen, ozone, or a combination thereof, the metal halide is converted into a metal hydroxide.

[0080] Those skilled in the art will understand that a reducing means is a component capable of acting as a reducing agent, and can be, for example, a chemical reagent (commonly referred to as a reducing agent), or a component of a system suitable for achieving reduction by electrolysis, such as a cathode connected to a power source. Preferably, the reducing means is a chemical reagent.

[0081] Preferably, the reduction method is zinc, sodium metabisulfite, hydrogen gas, and / or a cathode connected to a power source. Those skilled in the art will understand that the cathode is the electrode where reduction occurs. Generally, the cathode is at least partially (or completely) immersed in a metal halide solution. The cathode is connected to a power source capable of applying current, causing electrons to flow towards the cathode, thereby allowing reduction (i.e., gaining electrons) to occur at the cathode. This is generally referred to as reduction by electrolysis, and thus those skilled in the art will understand that the power source will then typically be connected to the anode.

[0082] More preferably, the reducing means are zinc, sodium metabisulfite and / or hydrogen.

[0083] Preferably, the metal halide is converted into a metal carbonate because in this approach, the overall reaction results in the consumption of carbon dioxide, thereby further improving environmental performance.

[0084] The method disclosed herein can be a method for extracting nickel from nickel-containing sulfide materials, to extract nickel from nickel-containing sulfide materials and form a nickel halide solution, optionally also including converting the nickel halide into nickel. 0 The steps of nickel carbonate and / or nickel hydroxide.

[0085] The method disclosed herein can be a method for extracting lead from lead-containing sulfide materials, to extract lead from lead-containing sulfide materials and form a lead halide solution, optionally also including converting lead halide into lead. 0 The steps involve lead carbonate and / or lead hydroxide.

[0086] The method disclosed herein can be a method for extracting zinc from zinc-containing sulfide materials, to extract zinc from zinc-containing sulfide materials and form a zinc halide solution, optionally also including converting the zinc halide into zinc. 0 The steps of zinc carbonate and / or zinc hydroxide.

[0087] The methods disclosed herein are particularly suitable for the extraction of copper and / or zinc. Therefore, preferably, the method herein is a method for extracting copper and / or zinc from materials containing copper sulfides and / or zinc sulfides, to extract copper and / or zinc from the materials containing copper sulfides and / or zinc sulfides and to form copper halide solutions and / or zinc halide solutions, optionally further comprising converting the copper halides and / or zinc halides into copper. 0 and / or zinc 0 The steps include copper carbonate and / or zinc carbonate, copper hydroxide and / or zinc hydroxide, or combinations thereof.

[0088] As can be seen from the examples, particularly good results have been obtained for copper extraction. Therefore, more preferably, the method described herein is a method for extracting copper from copper-containing sulfide materials to extract copper from the copper-containing sulfide materials and form a copper halide solution, optionally further including the step of converting the copper halide into copper, copper carbonate, and / or copper hydroxide.

[0089] This document discloses the extraction of metals from metal sulfide-containing materials to form metal halides, which can be recovered and separated from the remaining reactants, and / or can be converted into other forms of metal, which can then be recovered and separated from the remaining reactants. Therefore, the methods disclosed herein may also include a step of recovering the metal halide and / or a step of recovering one or more other forms of the metal that the metal halide has been converted into. It should be understood that by “recovery,” it means that the metal species in question (i.e., the metal halide, and / or one or more other forms of the metal that the metal halide has been converted into) is collected, removed, or separated from the reaction mixture. This can be achieved by appropriate solid-liquid separation techniques (e.g., sieving), and when the metal species in question is a solid (e.g., a metal carbonate), by solvent extraction processes (which may or may not contain various chelates), by reverse osmosis, by using activated carbon, by electrolytic deposition, or by using one or more ion exchange resins. It should be understood that "one or more other forms of the metal into which the metal halide has been converted" refers to those forms detailed elsewhere in this disclosure, and therefore may include another metal salt (e.g., metal carbonates and / or metal hydroxides), metal... 0 Or a combination thereof, and having the same degree of preference as those detailed herein.

[0090] The use of ion exchange resins is a preferred method for recovering metal species (i.e., metal halides and / or other forms of metals to which metal halides have been converted). As detailed elsewhere in this disclosure, these other forms of metals may include another metal salt (e.g., metal carbonates and / or metal hydroxides), metal... 0 Or a combination thereof. Therefore, steps b) and (if present) c) may involve the use of a resin. Ion exchange resins capture metal species to separate them from the solution, thereby allowing for good recovery of the metal species from the reactant mixture. Ion exchange resins can be used in the methods disclosed herein with metal-containing sulfide materials containing varying amounts of metal, but are effective even when the metal content in the metal-containing sulfide material is low.

[0091] When used in the methods disclosed herein, the ion exchange resin preferably consists of an organic polymer backbone to which a series of functional groups are attached, said functional groups containing at least one heteroatom. In this preferred embodiment, the resin provides improved metal species capture compared to the use of activated carbon. Without being bound by theory, it is believed that the improved metal species capture effect is due to at least one heteroatom in the series of functional groups. It is believed that the coordination of at least one heteroatom with the discussed metal species promotes the formation of a complex between the metal species and the resin. Therefore, such resins can be referred to as chelating resins.

[0092] Step b) may further include contacting an aqueous acidic oxidant mixture with a resin, preferably an ion-exchange resin composed of an organic polymer backbone to which a series of functional groups, each containing at least one heteroatom, are attached. It is believed that the use of a resin in step b) allows for the formation of metal halide resin complexes. It should be understood that the term "metal halide resin complex" refers to a species formed by the interaction between a metal halide (i.e., a metal already extracted from a metal sulfide-containing material) and a resin. Therefore, it should be understood that a metal halide resin complex refers to a resin to which or in which a metal halide is complexed.

[0093] In step b, the resin and the metal sulfide-containing material can be added simultaneously or sequentially. "Sequentially" means one after the other. For example, when the resin and the metal sulfide-containing material are added sequentially to an aqueous acidic oxidant mixture, the resin can be added before (i.e., prior to) or after the addition of the metal sulfide-containing material. Therefore, the resin can be added simultaneously with, before, or after the addition of the metal sulfide-containing material. The timing of these steps can be adjusted according to the convenience of the processing facility. It should be understood that when the resin and the metal sulfide-containing material are added simultaneously or immediately afterward, metal halides can form and then react immediately, resulting in the formation of a metal halide resin complex. This approach is referred to as a "resin leaching" process.

[0094] Therefore, in step b, the resin and the metal sulfide-containing material can be added to the aqueous acidic oxidant mixture simultaneously. Alternatively, in step b, the resin can be added to the aqueous acidic oxidant mixture before the metal sulfide-containing material is added. Alternatively, in step b, the resin can be added to the aqueous acidic oxidant mixture after the metal sulfide-containing material is added.

[0095] The amount of resin used in step b) may vary depending on the application discussed, but may, for example, range from 0.1 g to 100 g per 100 ml of the aqueous acidic oxidizing agent mixture. The amount of resin used in step b) may be at least 0.1 g, at least 1 g, at least 2 g, preferably at least 5 g per 100 ml of the aqueous acidic oxidizing agent mixture. The amount of resin used in step b) may be at most 100 g, at most 80 g, at most 50 g, preferably at most 20 g per 100 ml of the aqueous acidic oxidizing agent mixture.

[0096] Step c may further include contacting the metal halide solution with a resin, preferably an ion exchange resin composed of an organic polymer backbone to which a series of functional groups are attached, each functional group containing at least one heteroatom. It is believed that the use of a resin in step c) allows for the formation of a complex between the resin and one or more forms of the metal to which the metal halide has been converted. Other forms of such metals, as detailed elsewhere in this disclosure, may include another metal salt (e.g., metal carbonates and / or metal hydroxides), metal... 0 Or a combination thereof. For example, when a metal halide has been converted into a metal. 0 When metal carbonates and / or metal hydroxides are used, it is believed that the use of resin in step c) allows for the formation of metals. 0 Resin complexes, metal carbonate resin complexes, and / or metal hydroxide resin complexes. It should be understood that the term "metal" refers to... 0 "Resin complex", "metal carbonate resin complex", and "metal hydroxide resin complex" each refer to a species formed by the interaction between the corresponding metal species discussed and the resin. Therefore, it should be understood that "metal..." 0 "Resin complex", "metal carbonate resin complex" and "metal hydroxide resin complex" refer to resins in which the corresponding metal species are compounded.

[0097] In step c), the resin may be added before, simultaneously with, or after the metal halide is converted into one or more other forms of the metal. As detailed elsewhere in this disclosure, these other forms of the metal may include another metal salt (e.g., a metal carbonate and / or a metal hydroxide), a metal... 0 Or a combination thereof. The timing of these steps can be adjusted according to the convenience of the processing facility. It should be understood that when the addition of the resin and the conversion of the metal halide into one or more other forms of the metal occur simultaneously or immediately thereafter, one or more other forms of the metal can be formed and then react immediately, thereby reacting the resin with the metal species discussed (e.g., metal). 0 Complexes are formed between resin complexes, metal carbonate resin complexes and / or metal hydroxide resin complexes.

[0098] In step c), the resin is preferably added simultaneously with or after the metal halide is converted into one or more other forms of the metal. As detailed elsewhere in this disclosure, these other forms of the metal may include another metal salt (e.g., metal carbonates and / or metal hydroxides), metal... 0 Or a combination thereof. More preferably, the resin is added after the metal halide has been converted into one or more other forms of the metal—in which case step c may further include contacting the resin with a mixture of one or more other metal forms of the metal, the resin preferably being an ion-exchange resin consisting of an organic polymer backbone to which a series of functional groups containing at least one heteroatom are attached, thereby forming a complex between the resin and the metal species in question.

[0099] The amount of resin used in step c) may vary depending on the application discussed, but may, for example, range from 0.1 g to 100 g per 100 ml of metal halide solution or a mixture of one or more other forms of metal to which the metal halide has been converted. As detailed elsewhere in this disclosure, other forms of such metals may include another metal salt (e.g., metal carbonates and / or metal hydroxides), metal... 0 Or a combination thereof. The amount of resin used in step c) may be at least 0.1 g, at least 1 g, at least 2 g, preferably at least 5 g per 100 ml of metal halide solution or a mixture of one or more other forms of metal to which the metal halide has been converted. The amount of resin used in step c) may be at most 100 g, at most 80 g, at most 50 g, preferably at most 20 g per 100 ml of metal halide solution or a mixture of one or more other forms of metal to which the metal halide has been converted.

[0100] The term "ion exchange resin" is used by its usual definition in the art and therefore refers to a material that serves as an ion exchange medium and is generally insoluble in aqueous media. Thus, it should be understood that ion exchange resins are substantially insoluble in the aqueous solutions and mixtures disclosed herein (e.g., aqueous acidic oxidant mixtures, metal halide solutions, or other mixtures of metals in which metal halides have been converted). By "substantially insoluble," it means that at 25°C, less than 0.1 mg / ml of the resin dissolves in the aqueous solutions and mixtures disclosed herein (e.g., aqueous acidic oxidant mixtures, metal halide solutions, or other mixtures of metals in which metal halides have been converted).

[0101] As used herein, the definition of ion exchange resin generally refers to the characteristics of the ion exchange resin itself (i.e., before it is added to the aqueous solutions and mixtures disclosed herein). After its addition, it should be understood that, depending on the pH of the medium discussed, certain groups of the ion exchange resin may undergo protonation or deprotonation.

[0102] Ion exchange resins are preferably porous materials. The porosity of ion exchange resins increases the surface area available for ion exchange.

[0103] Consistent with the understanding from the term "ion exchange resin", when used in the methods disclosed herein, an ion exchange resin consists of a polymer backbone (sometimes referred to as a polymer matrix) to which a series of functional groups are attached.

[0104] Specifically, when using ion exchange resins, the resin consists of an organic polymer backbone with a series of functional groups attached to it. Ion exchange resins can essentially consist of an organic polymer backbone with a series of functional groups attached to it.

[0105] When used in the methods disclosed herein, ion exchange resins are commercially available from a variety of sources, including but not limited to the following, all of which are ion exchange resins having a polystyrene backbone functionalized with the following groups:

[0106] - SEPLITE® LSC660: Guanidinium functionalization

[0107] - SEPLITE® LSC740: Thiol-functionalized

[0108] - SEPLITE® LSC710: Functionalized with iminodiacetic acid groups

[0109] - AMBERSEP® 21K XLT Mesh anion exchange resin (Cl-): functionalized with quaternary ammonium groups

[0110] - Purogold TM MTA5015SO4: Functionalized with quaternary ammonium groups

[0111] - LEWATIT® MonoPlus TP 214: Functionalized with thiourea groups

[0112] - Puromet TM MTS9140: Functionalized with thiourea groups

[0113] - LEWATIT MP 62 WS: Functionalized with tertiary amine groups

[0114] - LEWATIT TP 106: Functionalized with quaternary ammonium groups

[0115] As used herein, the term "polymer" is used with its usual definition in the art and therefore refers to a homopolymer or copolymer formed by the polymerization of one or more monomers. Thus, the term encompasses, for example, linear polymers, branched polymers, and cyclic polymers.

[0116] As used herein, the term "homogeneous polymer" is used with its usual definition in the art and therefore refers to a polymer whose polymer chain comprises one type of monomer. As used herein, the term "copolymer" is used with its usual definition in the art and therefore refers to a polymer whose polymer chain comprises two or more different types of monomers. Therefore, those skilled in the art will understand that the term "copolymer" encompasses polymers comprising three different types of monomers (sometimes specifically referred to in the art as "terpolymer"). The term "block copolymer" is used with its usual definition in the art and therefore refers to a copolymer whose polymer chain comprises two or more monomer blocks. Each block consists of a specific monomer type, wherein at least two blocks contain different monomer types from each other. Diblock copolymers, triblock copolymers, and tetrablock copolymers each refer to copolymers having two, three, and four monomer blocks, respectively.

[0117] As used herein, the term "monomer" is used with its usual definition in the art and therefore refers to a molecular compound that can be chemically bonded to another monomer to form a polymer. Unless explicitly stated to the contrary, any monomer referred to herein should be understood to include all enantiomers, diastereomers, racemates, and mixtures thereof of the monomers discussed.

[0118] It should be understood that the term "polymer backbone" refers to a series of covalently bonded atoms that create a continuous molecular chain, to which functional groups are attached. Consistent with the usual definition in the art, the polymer backbone is generally the longest continuous molecular chain, to which other chains and functional groups can be considered as overhangs.

[0119] It should be understood that the term "organic polymer backbone" refers to a polymer backbone that includes carbon-carbon covalent bonds.

[0120] The organic polymer backbone may be cross-linked or uncross-linked. Preferably, the organic polymer backbone is cross-linked with a cross-linking agent such as divinylbenzene, hexamethylenetetramine, functionalized silane, isocyanate, peroxide, or a combination thereof. More preferably, the organic polymer backbone is cross-linked with divinylbenzene. The amount of cross-linking agent may vary, but may be, for example, from 1% to 50% by weight, based on the total weight of the polymer backbone and the cross-linking agent.

[0121] The organic polymer backbone can be, for example, polystyrene, polyethylene toluene, poly(vinyl benzyl chloride), polyvinyl acetate, polyvinyl butyral, polyvinyl ether, polyethylene, polyurethane, or acrylonitrile-butadiene-styrene.

[0122] Preferably, the organic polymer backbone is a vinyl polymer backbone, which will be understood as a polymer backbone formed from vinyl monomers (i.e., monomers whose structure contains the formula −CH=CH2). For example, the organic polymer backbone can be polystyrene, polyethylenetoluene, 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.

[0123] This document discloses a series of functional groups attached to an organic polymer backbone. It should be understood that this attachment is generally achieved through covalent bonding to the organic polymer backbone. This attachment can be accomplished using standard procedures known in the art. The term "series" indicates the presence of multiple functional groups attached to the polymer backbone. For a given ion exchange resin, the functional groups may be the same or different.

[0124] The functional group contains at least one heteroatom. The term "heteroatom" is used with its usual definition in the art and therefore refers to an atom that is not carbon or hydrogen. Preferably, the heteroatom is one or more of N (nitrogen), S (sulfur), O (oxygen), and P (phosphorus). More preferably, the heteroatom is one or more of N, S, and O, and even more preferably one or more of N and S. It should be understood that when the heteroatom is one or more of the listed options, additional heteroatoms may also be present in the functional group besides those listed. Unless explicitly stated otherwise, the given atomic species of heteroatoms should be understood to encompass that species regardless of whether it is in a neutral state. In particular, when a series of functional groups contains N, this covers schemes where N is positively charged, for example, as part of a quaternary ammonium group.

[0125] Particularly preferred is when the series of functional groups includes one or more of iminodiacetic acid groups, thiourea groups, quaternary ammonium groups, guanidine groups, amine groups, and thiol groups. Those skilled in the art will be familiar with the molecular structures implied by these groups. In this embodiment, the series of functional groups may be iminodiacetic acid groups, thiourea groups, quaternary ammonium groups, guanidine groups, amine groups, or thiol groups.

[0126] Even more preferably, the series of functional groups includes one or more of thiourea groups, quaternary ammonium groups, and guanidine groups. In this embodiment, the series of functional groups can be thiourea groups, quaternary ammonium groups, or guanidine groups.

[0127] The functional groups disclosed herein can be attached to the polymer backbone via standard reaction procedures known in the art, wherein the attachment between the functional group and the backbone is located at an appropriate position within the functional group's molecular framework, as will be understood by those skilled in the art.

[0128] The term "iminodiacetic acid" refers to the molecular formula HN(CH2CO2H)2. When a series of functional groups includes an iminodiacetic acid group, the functional group contains one or more of the following parts:

[0129]

[0130]

[0131] The term "thiourea" refers to the formula S=C(NR) 1 R 2 (NR) 3 R 4 ), where R 1 R 2 R 3 and R 4 They can be the same or different, and each is independently selected from H or alkyl groups. Preferably, R 1 R 2 R 3 and R 4 They may be the same or different, and each is independently selected from H or C. 1- C6 alkyl. In this embodiment, R 1 R 2 R 3 and R 4 They may be the same or different, and each can be independently selected from H or C. 1- C3 alkyl. More preferably, R 3 and R 4 Both are H.

[0132] When the series of functional groups includes a thiourea group, the functional group comprises one or more of the following portions, wherein R 1 R 2 R 3 and R 4 It has the same meaning and preference as above:

[0133]

[0134]

[0135] The term "quaternary ammonium" refers to the formula [NR] 5 R 6 R 7 R 8 ] + , where R5 R 6 R 7 and R 8 They can be the same or different, and each is independently selected from H or alkyl groups. Preferably, R 5 R 6 R 7 and R 8 They may be the same or different, and each is independently selected from H or C1-C6 alkyl groups. More preferably, R 5 R 6 R 7 and R 8 Each is an alkyl group, preferably C1-C6 alkyl, and may be the same or different. Preferably, R 5 R 6 R 7 and R 8 Each is a C1-C3 alkyl group and may be the same or different.

[0136] When a series of functional groups includes quaternary ammonium groups, the functional groups contain one or more of the following moieties, wherein R 5 R 6 and R 7 It has the same meaning and preference as above:

[0137]

[0138] The term "guanidine" refers to formula (R 9 R 10 N)(R 11 R 12 N)C=NR 13 , where R 9 R 10 R 11 R 12 and R 13 They may be the same or different, and each is independently selected from H or alkyl. Preferably, the alkyl group is C1-C6 alkyl, more preferably C1-C3 alkyl. More preferably, the term "guanidine" refers to the formula HN=C(NH2)2, which, as those skilled in the art will understand, is a non-derivative guanidine, where R 9 R 10 R 11 R 12 and R 13 Each one is H.

[0139] When a series of functional groups includes a guanidinyl group, the functional group comprises one or more of the following portions, wherein R 9 R 10 R 11 R 12 and R 13It has the same meaning and preference as above:

[0140]

[0141]

[0142]

[0143] The term "thiol" refers to formula R 14 -SH, where R 14 It is an alkyl group, preferably a C1-C6 alkyl group, and more preferably a C1-C3 alkyl group.

[0144] When a series of functional groups includes thiol groups, the functional groups contain one or more of the following:

[0145]

[0146] The term "amine" refers to the NR formula. 15 R 16 R 17 , where R 15 R 16 and R 17 They can be the same or different, and each is independently selected from H or alkyl groups. Preferably, R 15 R 16 and R 17 They may be the same or different, and each is independently selected from H or C1-C6 alkyl groups. More preferably, R 15 R 16 and R 17 They may be the same or different, and each is an alkyl group, preferably C1-C6 alkyl. Preferably, R 15 R 16 and R 17 Each is a C1-C3 alkyl group and may be the same or different.

[0147] When a series of functional groups includes an amino group, the functional group comprises one or more of the following moieties, wherein R 15 and R 16 It has the same meaning and preference as above:

[0148]

[0149] As used throughout the text, it should be understood that the symbol " "" indicates the end of a molecular segment, and therefore refers to the point where that segment is attached to the polymer backbone. These segments can be directly attached to the polymer backbone, for example, by direct bonding, or they can be attached via alkyl groups, such as C1-C. 10 Alkyl groups, preferably C1-C6 alkyl groups, and more preferably C1-C3 alkyl groups.

[0150] As used herein, the term "alkyl" refers to a straight-chain or branched saturated or unsaturated alkyl group. Preferably, the alkyl group is a saturated alkyl group. More preferably, the alkyl group is a straight-chain alkyl group. As used herein, the term "(C a -C b "alkyl" where a and b are integers refers to a straight-chain or branched alkyl group having a to b carbon atoms. Therefore, by way of example, C1-C 10 Alkyl groups are those having 1 to 10 carbon atoms, and therefore include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, heptyl, octyl, nonyl, and decyl. Meanwhile, C1-C6 alkyl groups are those having 1 to 6 carbon atoms, and therefore include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0151] The resin can be supplied as multiple beads with a particle size distribution such that more than 95% of the particles have a diameter of 0.1 mm to 10 mm, 0.2 mm to 5 mm, 0.1 mm to 2.5 mm, or 0.2 mm to 1.5 mm. The bulk density can vary, for example from 100 g / L to 2000 g / L, preferably from 200 g / L 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 g / L to 2000 g / L, preferably from 200 g / L to 1500 g / L, more preferably from 500 g / L to 1200 g / L.

[0152] When resin is present in the methods disclosed herein, the method may further include a step of recovering the metal species (i.e., metal halides, and / or other forms of metals to which the metal halides have been converted) from the metal species resin complex. Those skilled in the art will understand that this can be done by a variety of possible means. For example, the resin (metal species resin complex) containing the metal species can be removed from the remaining components of the methods disclosed herein by suitable solid-liquid separation techniques (e.g., sieving) before the resin is subjected to suitable methods to separate the metal species from the resin. For example, the metal species can be recovered from the metal species resin complex by stripping, incineration, ashing, or combustion of the resin.

[0153] The methods disclosed herein may include an additional step of decontaminating the material from which metals have been extracted, the decontamination step comprising contacting the material with one or more ion exchange resins having the specific and preferred characteristics disclosed herein. It has been found that certain functional groups, such as thiol groups, are selective for impurities such as arsenic and mercury. Therefore, not only can certain resins disclosed herein be used to selectively extract metals preferentially over impurities, but some of the resins disclosed herein can then be used to decontaminate the material left by the method (sometimes referred to as “tailings”), providing a “cleanup” operation for the tailings left by the method.

[0154] The methods disclosed herein can be performed at a variety of different temperatures, for example, from 5 degrees Celsius to 100 degrees Celsius. The methods disclosed herein can be performed within different pressure ranges, and can be performed, for example, at elevated pressures in sealed systems, but more typically at atmospheric pressure.

[0155] The following non-limiting embodiments illustrate the present invention.

[0156] Examples 1 to 8

[0157] Examples 1 to 8 report the results of copper extraction from copper-containing sulfide ores.

[0158] The results are shown in Table 1 below. Example 1 corresponds to "Experiment 1", Example 2 corresponds to "Experiment 2", and so on.

[0159] The percentage of copper extracted was evaluated using fire assay and ICP (inductively coupled plasma) as follows. The copper content in the headstock (ore before extraction) was measured using industry-standard fire assay, and the copper content in the tailings (waste ore material remaining after extraction) was measured using the same method. The copper content in the headstock was compared with the remaining copper content in the tailings. The greater the difference between the copper content in the headstock and the remaining copper content in the tailings, the better the copper extraction effect.

[0160] Table 1 reports the difference between the copper content in the headstock and the remaining copper content in the tailings, expressed as a percentage of the copper content in the headstock (i.e., headstock - tailings / headstock × 100).

[0161]

[0162] Table 1

[0163] The complete methods of Examples 1 to 8 are as follows.

[0164] Example 1

[0165] Water (156 ml) was placed in a round flask, and sodium bromide aqueous solution (46%, 20.6 ml), hydrogen peroxide (34%, 24.4 ml) were stirred. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (50 g), previously crushed to 50 microns, was added, and the reaction was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 1".

[0166] Example 2

[0167] Water (176 ml) was placed in a round flask, and sodium bromide aqueous solution (46%, 0.4 ml), hydrogen peroxide (34%, 24.4 ml) were stirred. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (50 g), previously crushed to 50 microns, was added, and the reaction was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 2".

[0168] Example 3

[0169] Water (164 ml) was placed in a round flask, and hydrobromic acid aqueous solution (48%, 13.8 ml), hydrogen peroxide (34%, 24.4 ml) were stirred. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (50 g), previously crushed to 50 microns, was added, and the reaction was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 3".

[0170] Example 4

[0171] Water (177 ml) was placed in a round flask, and sodium chloride (7.4 g) and hydrogen peroxide (34%, 24.4 ml) were added. Sufficient hydrochloric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (50 g), previously crushed to 50 microns, was added, and the mixture was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 4".

[0172] Example 5

[0173] Water (156 ml) was placed in a round flask, and sodium bromide aqueous solution (46%, 20.6 ml), hydrogen peroxide (34%, 24.4 ml) were stirred. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (25 g), previously crushed to 50 microns, was added, and the mixture was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 5".

[0174] Example 6

[0175] Water (176 ml) was placed in a round flask, and sodium bromide aqueous solution (46%, 0.4 ml), hydrogen peroxide (34%, 24.4 ml) were stirred. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (25 g), previously crushed to 50 microns, was added, and the reaction was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 6".

[0176] Example 7

[0177] Water (164 ml) was placed in a round flask, and hydrobromic acid aqueous solution (48%, 13.8 ml), hydrogen peroxide (34%, 24.4 ml) were stirred. Sufficient sulfuric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (25 g), previously crushed to 50 microns, was added, and the reaction was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 7".

[0178] Example 8

[0179] Water (177 ml) was placed in a round flask, and sodium chloride (7.4 g) and hydrogen peroxide (34%, 24.4 ml) were added. Sufficient hydrochloric acid was added to lower the pH to 0.5, and the mixture was stirred for 30 minutes until the ORP (oxidation-reduction potential) reached above 650. Copper sulfide ore (25 g), previously crushed to 50 microns, was added, and the mixture was stirred with a roller for 60 minutes, taking samples at 15, 30, and 60 minutes. The solution was filtered, and after setting the initial solution aside for analysis, the tailings were washed with 20 ml of fresh leaching agent. The tailings were then washed with water, dried, and submitted for fire assay analysis. Copper in the solution was analyzed using calibrated ICP. The results are shown in Table 1 as "Experiment 8".

[0180] Example 9

[0181] A mixture of aqueous acidic oxidizing agents was provided and contacted with four different ore samples. The samples were dried to constant weight (brittle) and pulverized to -150 mesh (105 microns).

[0182] Triple samples were analyzed using pyrometallurgical methods and acid digestion to determine the metal content in each sample. The gold content was analyzed using pyrometallurgical assay combined with intracytoplasmic reticulum spectroscopy (ICP-OES). The amounts of other metals and sulfur content were analyzed using acid digestion combined with ICP-OES.

[0183] All samples were analyzed prior to testing to establish baseline readings for each element as described above. A portion of each sample was then subjected to various conditions using an aqueous acidic oxidant mixture to determine the extraction quality of the leaching agent for the elements in the sample. Samples were leached at 23°C (room temperature) for up to 60 minutes, with sampling every 20 minutes. Stirring was performed using a horizontally rolling vessel with baffles during the leaching cycle. Several variations of the aqueous acidic oxidant mixture were used to optimize the results obtained for various samples. At each interval, equal portions of the aqueous acidic oxidant mixture were taken to test the economic value of the sample and the leaching conditions (pH, ORP, and temperature). The aqueous samples were then analyzed by spectrophotometry (ICP), and the results are reported below. Tailings from the methods disclosed herein were then reanalyzed to determine residual value. Quality control measures were monitored and met the minimum guidance requirements of the process disclosed herein.

[0184] The results are shown in Tables 2 and 3 below:

[0185]

[0186] Table 2

[0187]

[0188] Table 3

[0189] As shown in Tables 2 and 3, favorable results were obtained in terms of both time spent and the amount of elements extracted for the four types of ore samples tested. Therefore, Tables 2 and 3 demonstrate that the method disclosed herein provides beneficial results for lead and zinc.

[0190] Example 10

[0191] A series of aqueous acidic oxidizing agent mixtures were provided and contacted with copper ore. The results are shown in... Figure 1 The results show that all mixtures advantageously yielded high Cu% extraction rates, with the best extraction results achieved using sulfuric acid, lower pH, and higher halide concentrations.

[0192] Example 11

[0193] A series of aqueous acidic oxidant mixtures with a pH of 0.5 were prepared and contacted with copper ore. NaCl concentrations ranged from 2 wt% to 6.5 wt%, mixture temperatures varied from 30°C to 80°C, and contact times ranged from 15 min to 45 min. Copper extraction rates were determined using ICP analysis of the solutions, and the results are shown in Table 4 below. Extraction rates were observed to be higher than 70% for all test mixtures.

[0194]

[0195] Table 4

[0196] Example 12

[0197] A series of aqueous acidic oxidant mixtures with varying acid types, temperatures, halide mixtures, and pH values ​​were prepared and contacted with copper ore for varying run times. The halide concentration was kept constant. Copper extraction rates were determined using ICP analysis of the solutions, and the results are shown in Table 5 below. Extraction rates higher than 70% were observed for all test mixtures.

[0198]

[0199] Table 5

[0200] 1 Cl fraction = the proportion of total halides present in the form of Cl (1.0 = 100% Cl, 0.5 = 50% Cl + 50% Br)

[0201] 2 Acids: H = HCl, S = H₂SO₄

[0202] 3 The extraction rate is calculated based on the average measured value of the raw ore.

Claims

1. A method for extracting metals from a metal sulfide-containing material, comprising the following steps: a) Provide an aqueous acidic oxidant mixture comprising water, acid, oxidizing agent and halide ion source, wherein the pH of the aqueous acidic oxidant mixture is less than 7; The oxidation means mentioned therein includes hydrogen peroxide, ozone, oxygen, chlorine, bromine, iodine, hypochlorous acid, hypobromic acid, hypoiodic acid, hypochlorite, hypobromite, hypoiodide, percarbonate, persulfate, permanganate, an anode connected to a power source, or a combination thereof; b) Contact the aqueous acidic oxidant mixture with the metal sulfide material to extract the metal from the metal sulfide material and form a metal halide solution; The metals mentioned include copper, nickel, lead, zinc, or combinations thereof.

2. The method according to claim 1, wherein the acid comprises acetic acid, citric acid, carbonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, or a combination thereof.

3. The method according to claim 1, wherein the acid comprises sulfuric acid, hydrochloric acid, nitric acid, or a combination thereof.

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

5. The method according to any one of the preceding claims, wherein the pH value of the aqueous acidic oxidant mixture is in the range of 0.1 to 6.

9.

6. The method according to any one of the preceding claims, wherein the pH value of the aqueous acidic oxidant mixture is in the range of 0.8 to 6.

9.

7. The method according to any one of the preceding claims, wherein the pH value of the aqueous acidic oxidant mixture is less than or equal to 6, preferably less than or equal to 5, and more preferably less than or equal to 4.

8. The method according to any one of the preceding claims, wherein the oxidation means comprises hydrogen peroxide, ozone, percarbonate, persulfate, permanganate, or a combination thereof.

9. The method according to any one of the preceding claims, wherein the oxidation means comprises hydrogen peroxide.

10. The method according to any one of the preceding claims, wherein the halide ion source comprises a bromide ion source, a chloride ion source, an iodide ion source, or a combination thereof.

11. The method according to any one of the preceding claims, wherein the halide ion source comprises a bromide ion source, a chloride ion source, or a combination thereof.

12. The method according to any one of the preceding claims, wherein the halide ion source comprises a bromide ion source.

13. The method according to any one of the preceding claims, wherein the halide ion source is at least one metal halide, and the metal is lithium, potassium, sodium, calcium, or a combination thereof.

14. The method according to any one of the preceding claims, wherein the halide ion source is at least one alkali metal halide, and the alkali metal is lithium, potassium, sodium, or a combination thereof.

15. The method according to any one of the preceding claims, further comprising the step of: c) Convert the metal halide into a metal 0 Metal carbonates and / or metal hydroxides.

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

17. The method according to any one of claims 15 to 16, wherein step c) comprises contacting the metal halide solution with carbon dioxide, carbon monoxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid, reducing agents such as zinc, sodium metabisulfite, hydrogen, and / or a cathode connected to a power source, sodium hydroxide, potassium hydroxide, oxygen, ozone, or combinations thereof.

18. The method according to any one of claims 15 to 17, wherein step c) comprises contacting the metal halide solution with carbon dioxide, carbon monoxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid, or a combination thereof, thereby converting the metal halide into a metal carbonate.

19. The method according to any one of claims 15 to 18, wherein step c) comprises contacting the metal halide solution with a reducing agent such as zinc, sodium metabisulfite, hydrogen, and / or a cathode connected to a power source, thereby converting the metal halide into a metal. 0 .

20. The method according to any one of claims 15 to 19, wherein step c) is performed by electrolytic deposition, thereby converting the metal halide into a metal. 0 .

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

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

23. The method according to any one of claims 15 to 21, the method further comprising recovering metals. 0 The steps of metal carbonates and / or metal hydroxides.

24. The method according to any one of the preceding claims, wherein step b further comprises contacting the aqueous acidic oxidant mixture with a resin, the resin being an ion exchange resin composed of an organic polymer backbone, a series of functional groups attached to the organic polymer backbone, the functional groups containing at least one heteroatom.

25. The method according to any one of claims 15 to 21, wherein step c further comprises contacting the metal halide solution with a resin, the resin being an ion exchange resin composed of an organic polymer backbone, a series of functional groups attached to the organic polymer backbone, the functional groups containing at least one heteroatom.

26. The method according to any one of claims 15 to 21, wherein step c further comprises placing the metal 0 Metal carbonates and / or metal hydroxides are in contact with a resin, which is an ion exchange resin composed of an organic polymer backbone, with a series of functional groups attached to the organic polymer backbone, each functional group containing at least one heteroatom.

27. The method according to any one of the preceding claims, wherein the metal sulfide-containing material comprises ore, underground brine, battery, or a combination thereof.

28. The method according to any one of the preceding claims, wherein the metal sulfide-containing material comprises ore.

29. The method according to any one of the preceding claims, wherein the metal comprises copper, such that the method is a method for extracting copper from a copper-containing sulfide material to extract the copper from the copper-containing sulfide material and form a copper halide solution.

30. The method according to any one of the preceding claims, wherein steps a) and b) occur sequentially or simultaneously.

Images