Dry metallurgical recycling of used batteries

Abstract

According to the present invention, a method for extracting one or more valuable base metals from used battery waste comprises the steps of: obtaining used battery waste having a certain amount of one or more valuable metals; and providing black mass to a dry metallurgical furnace defined by a turbulent bath containing one or more sulfidants, one or more fluxes, and one or more fuels, thereby extracting about 10 -13 ~about 10 -4 A method is provided which includes the steps of: providing an oxygen partial pressure of atm; forming a base metal mat and a slag, wherein the slag contains less than approximately 5% by weight of base metal; separating the mat and the slag; and obtaining one or more valuable base metals by further refining the base metal mat.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority to Australian Provisional Patent Application No. 2023902216, filed on July 11, 2023, and No. 2023903803, filed on November 27, 2023. The contents of AU’216 and AU’803 are hereby incorporated by reference in their entirety.

[0002] The present invention relates to a method for treating used batteries to recover one or more valuable base metals (such as Ni, Co, Cu, Zn, Pb, Mn, etc.) and related base metals (such as Au, Ag, Pt, etc.) in a molten matte phase with a high recovery rate. The matte phase can then be processed at a base metal refinery. The residual slag can be sold or disposed of safely.

[0003] More particularly, the present invention relates to a method for extracting valuable battery materials and / or valuable metals such as cobalt, copper, nickel, lithium, etc. from used batteries, preferably lithium - ion batteries.

[0004] Even more particularly, the present invention is a method for smelting used lithium - ion batteries, comprising feeding a mixture of these materials with a sulfiding agent, a flux, and a fuel into a furnace, and injecting air and / or oxygen into the molten charge to achieve an oxygen partial pressure of 10 -6 atm to -11 10 atm, thereby forming a base metal matte into which most of the valuable metals migrate. A slag containing less than 5 wt% of base metals is also formed. The molten slag is then either sold (as an aggregate), processed to recover non - base metals (such as lithium), or discarded. The molten base metal matte may be further processed at a base metal refinery or smelted by known techniques.

[0005] The present invention is described below with reference to its preferred embodiments, but those skilled in the art will understand that the spirit and scope of the invention can be embodied in many other forms. [Background technology]

[0006] Throughout this specification, no consideration of prior art should ever be considered to be of widespread knowledge or to form part of the common general knowledge in the art.

[0007] The rate at which valuable metals are extracted from their constituent ores is increasing exponentially. Because the overall supply is strictly finite, some metals are already under pressure to meet both supply and sustainability challenges. Without widespread recycling practices, the global supply of certain metals will inevitably be depleted long before consumer demand declines. Examples of such metals include nickel, copper, manganese, cobalt, and lithium.

[0008] The value of cobalt lies primarily in its usefulness in industries such as alloys, batteries, catalysts, pigments, radioisotopes, electroplating, and porcelain enamel.

[0009] Nickel is used in many industrial and consumer products, including stainless steel, Alnico magnets, coins, rechargeable batteries (such as nickel-iron), electric guitar strings, microphone capsules, plating for plumbing fixtures, and specialty alloys such as permalloy, elimvar, and invar. It is also widely used in many other alloys, such as nickel brass and bronze, and alloys with copper, chromium, aluminum, lead, cobalt, silver, and gold.

[0010] Manganese has industrial uses in steelmaking, alloying, batteries, resistors, coinage, and ceramic coloring.

[0011] At the industrial level, lithium is becoming increasingly popular due to its diverse applications in ceramics, glass, batteries, electronics, lubricants, metallurgy, pyrotechnics, air purification, optics, polymer chemistry, military applications, and medical applications. One of lithium's primary applications is batteries, and demand for it is expected to continue to increase in the coming years as electric vehicles (among other emerging technologies) become more widespread. Lithium is extremely well-suited for battery use due to its high electrode potential (the highest of all metals) and low atomic mass, which result in high charge-to-weight ratios and power-to-weight ratios. Lithium batteries are preferred over other batteries due to their relatively high charge density (long lifespan), but currently have the problem of relatively high cost per unit. Depending on the design and the compound used, lithium batteries can generate voltages ranging from 1.5V (equivalent to zinc-carbon or alkaline batteries) to approximately 3.7V.

[0012] As environmental awareness in society increases and the demand for battery power as an alternative to fossil fuels rises, a new stream of waste from discarded batteries is inevitable. However, this awareness and the resulting waste stream work together to inevitably lead to a rapid increase in recycling technologies. For example, at least some of the valuable metals contained in discarded batteries are now recovered and recycled for future use.

[0013] By 2030, it is estimated that approximately 1.2 million tons of lithium-ion batteries will reach the end-of-life stage. This includes an estimated 125,000 tons of lithium, 35,000 tons of cobalt, and 86,000 tons of nickel that could potentially be recovered for use in the manufacture of new batteries. These figures must be considered in light of the fact that the global supply of these elements is strictly finite, and without effective recycling practices, technological advancements in lithium-ion batteries may be limited by supply rather than by the emergence of new and better battery technologies.

[0014] "End-of-life battery waste" is an industry term referring to a type of electronic waste (e-waste) that includes crushed and shredded used battery cells. It contains a mixture of valuable metals such as lithium, manganese, cobalt, and nickel, along with graphite and other casing or electrode materials. First, waste batteries are collected, sorted, discharged, and disassembled. This is followed by mechanical crushing, drying, sorting, sieving, and thermal decomposition at 700°C to remove any residual electrolytes and potentially fluorine-containing components that could be harmful to health. The resulting material is referred to as "treated end-of-life battery waste" in the battery recycling industry.

[0015] In conventional battery recycling, metals are typically extracted after the final or most significant processing stage. Examples include wet and dry metallurgy. Wet metallurgy (see, e.g., Wang, H., Friedrich, B. Development of a Highly Efficient Hydrometallurgical Recycling Process for Automotive Li-Ion Batteries. J. Sustain. Metal. 1, 168-178, 2015) refers to the extraction of metals by preparing an aqueous solution of a metal salt and recovering the metal from the solution. Typical operations include leaching or dissolving the metal or metal compound in water (usually with additives), separating waste and purifying the leachate, and precipitation of the metal or one of its pure compounds from the leachate by chemical or electrolytic means. Common leaching agents include sulfuric acid, hydrochloric acid, and hydrogen peroxide. Multiple steps are required, and large amounts of wastewater are generated.

[0016] Dry metallurgy (see, for example, Assefi, et al., Pyrometallurgical recycling of Li-ion, Ni-Cd and Ni-MH batteries: A minireview, Current Opinion in Green and Sustainable Chemistry, 24, 26-31, 2020) refers to the extraction and purification of metals through processes involving heat. The most important operations are roasting, smelting, and refining. Such processes are extremely energy-intensive, consume many environmentally harmful chemicals, and generate harmful gases.

[0017] The recovery of valuable metals from used battery waste using conventional wet or dry metallurgy methods incurs significant environmental and, consequently, monetary costs. Naturally, several alternative technologies have emerged in recent years.

[0018] U.S. Patent No. 11,661,638 (Umicore) describes a process and slag suitable for recovering Ni and Co from lithium-ion batteries or their waste. The slag composition is specified as follows: 10% <MnO<40%;(CaO+1.5 * Li2O) / Al2O3 > 0.3; CaO + 0.8 * MnO+0.8 * Li2O<60%; (CaO+2 * Li2O+0.4 * The composition is MnO / SiO2 ≥ 2.0; Li2 ≥ 1%; and Al2O3 + SiO2 + CaO + Li2O + MnO + FeO + MgO > 85%. This composition is particularly suitable for limiting or avoiding corrosion in furnaces lined with magnesia-containing refractory bricks.

[0019] U.S. Patent Application Publication No. 2020 / 0263276 (Sumitomo Metal Mining Co., Ltd.) describes a method for processing lithium-ion battery waste using a converter in a copper smelting process, wherein, before the process of feeding copper matte produced in a self-smelting furnace into a converter and blowing oxygen into the converter to produce crude copper, lithium-ion battery waste is introduced into the converter or into a ladle used when feeding the copper matte into the converter, and then the lithium-ion battery waste is burned using the residual heat in the converter or ladle.

[0020] International Publication No. 2022 / 045973 (Green Li-Ion Pte. Ltd.) describes a method for treating leachate obtained from black mass of spent lithium-ion batteries (essentially synonymous with spent battery waste), comprising setting the pH of the leachate to approximately pH 1.2 to 2.5, adding iron powder to induce copper cementation, adding lime after copper cementation, and, after adding lime, shifting the pH of the leachate to approximately pH 6 to extract calcium fluoride, titanium hydroxide, aluminum hydroxide, iron hydroxide, and iron phosphate. A black mass recycling system is also disclosed, comprising an impurity removal reactor configured to receive sodium hydroxide feed, iron powder feed, and lime feed.

[0021] U.S. Patent No. 9,484,606 (Hulico LLC) describes a method for recycling and regenerating battery electrode materials. For example, one disclosed embodiment provides a method comprising: obtaining a certain amount of waste electrode material; reacting the waste electrode material with the lithium aqueous solution in an autoclave while heating the waste electrode material and the lithium aqueous solution to form hydrothermally reacted waste electrode material; removing the hydrothermally reacted waste electrode material from the lithium aqueous solution; and sintering the hydrothermally reacted waste material to form recycled electrode material.

[0022] U.S. Patent No. 9,312,581 (Commissariat a L'energie Atomique Et Aux Energies Alternatives) relates to lithium batteries, more specifically to lithium-ion batteries, and to methods for recycling the electrodes of such batteries. This method includes a) a step of pulverizing the electrode and / or the battery; b) a step of dissolving the organic components and / or polymer components of the electrode and / or the battery in an organic solvent; c) a step of separating undissolved metals present in the suspension obtained in step b); d) a step of filtering the suspension obtained in step c) through a filter press; e) a step of recovering the solids held on the filter press in step d) and suspending these solids in water; f) a step of recovering the material that has settled or aggregated in step e), resuspending the settled material in water, and adjusting the pH of the resulting suspension to less than 5, preferably less than 4; g) a step of filtering the suspension obtained in step f) on a filter press; and h) a step of separating iron by precipitation of iron phosphate on one side and separating lithium by precipitation of lithium salt on the other side.

[0023] Conventional recycling plants often focus on specific metals such as cobalt, neglecting other valuable metals like manganese and nickel. Generally, these plants lack the equipment to handle different types of lithium-ion batteries and the impurities they introduce.

[0024] Existing dry metallurgical methods for processing lithium-ion batteries each face challenges related to manipulating the molten metal bath in the furnace. Because the molten metal has a high liquidus temperature, high operating temperatures are required. These high operating temperatures generate highly corrosive and erosive slag, shortening furnace life and making it difficult to monitor furnace operation. Furthermore, because the molten metal solidifies easily (i.e., has high thermal conductivity), maintaining the furnace bath in a molten state, managing deposits in the tap troughs during tapping, and reducing the number of downstream processing options present challenges. Additionally, base metal alloys cannot be processed in existing base metal refineries due to a lack of sulfur in the alloy phase.

[0025] The object of the present invention is to overcome or improve upon at least one of the drawbacks of the prior art, or to provide a useful alternative.

[0026] An object of a particularly preferred embodiment of the present invention is to provide an extraction process that can recycle valuable metals and / or materials from used battery waste. Most preferably, the valuable metal is selected from the group consisting of cobalt, nickel, manganese, and lithium.

[0027] An object of a particular preferred embodiment of the present invention is to provide a smelting process that can simultaneously achieve one or more of the following results: namely, producing a base metal-rich material having a melting point below about 1350°C; producing a glassy slag material containing Si, Al, Mn and other oxides and having a low concentration of base metal; producing purified exhaust gas; lowering the operating temperature of the furnace; reducing the corrosiveness of the furnace slag; lowering the liquidus temperature (freezing point) of the base metal alloy; and enabling the base metal product to be processed in a base metal smelter.

[0028] Although the present invention is described with reference to specific embodiments, those skilled in the art will understand that the present invention can be embodied in many other forms.

[0029] definition In the description and claims of this invention, the following terms are used according to the definitions set forth below. It should also be understood that the terms used herein are intended solely to describe and not to limit specific embodiments of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this invention pertains.

[0030] "End-of-life battery material" essentially refers to whole or crushed end-of-life battery waste. To avoid ambiguity, the end-of-life battery waste covered by this invention is "raw" end-of-life battery waste. It has not undergone any pretreatment (e.g., pyrolysis to remove battery electrolytes, or sodium hydroxide leaching and ultrasonic treatment to remove aluminum). The economic potential of an effective recycling method that avoids expensive pretreatment processes is clear.

[0031] "Valuable base metal" refers to all metals that may be present in used battery waste, including, but not limited to, one or more of the following: Li, Au, Ag, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V. "Valuable base metal" may also include oxides of such metals, such as SiO2, CaO, Al2O3, Li2O, MnO, and MgO.

[0032] Unless otherwise explicitly required by the context, throughout this description and the claims, terms such as “comprise,” “comprising,” and so on should be interpreted in a comprehensive sense, that is, “including, but not limited to,” and not in an exclusive or exhaustive sense.

[0033] When used herein, the phrase "consisting of" excludes any element, process, or component not explicitly stated in the claims. If the phrase "consists of" (or a variation thereof) appears in a section of the claim rather than immediately following the preamble, the phrase limits only the elements described in that section, and other elements are not excluded from the claim as a whole. When used herein, the phrase "consisting essentially of" limits the claims to any element or process that does not substantially affect the basis and novel features of the claimed subject matter.

[0034] With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” when any of these three terms is used herein, the present disclosure and the claimed subject matter may include the use of any of the other two terms. Accordingly, in some embodiments not expressly described elsewhere, any example of “comprising” may be replaced by “consisting of” or “consisting essentially of.”

[0035] Except in the operating examples or unless otherwise indicated, all numerical values ​​representing the amounts of components or reaction conditions used herein should be understood to be modified in all cases by the term “approximately,” taking into account the usual tolerances in the art. The examples are not intended to limit the scope of the invention. In the following, or unless otherwise indicated, “%” means “weight percent,” “ratio” means “weight ratio,” and “parts” means “parts by weight.”

[0036] Units and measurements are provided based on the metric system, with the exception of pressure, which is expressed in atmospheric pressure (atm).

[0037] As used herein, the term “substantially” means, unless otherwise indicated, more than 50% by weight where applicable.

[0038] The term "approximately" should be interpreted by those skilled in the art, taking into account the usual tolerances in the relevant art.

[0039] When specifying a numerical range using endpoints, it includes all numbers contained within that range (for example, 1-5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0040] The terms “preferred” and “preferred” refer to embodiments of the invention that can provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the enumeration of one or more preferred embodiments does not imply that other embodiments are unhelpful, nor is it intended to exclude other embodiments from the scope of the invention.

[0041] When used herein and in the appended claims, it should also be noted that the singular forms “a,” “an,” and “the” refer to multiple objects unless the context clearly indicates otherwise.

[0042] Prior art referenced herein is incorporated entirely by reference unless otherwise specifically disclaimed.

[0043] While exemplary embodiments of the disclosed technology are described in detail herein, it should be understood that other embodiments are contemplated. Therefore, the disclosed technology is not intended to be limited to the structural and arrangement details of the components described or shown in the drawings. Other embodiments of the disclosed technology are possible and can be implemented or performed in a variety of ways.

[0044] This specification is constructed with consideration to the principles of general application. Therefore, where this specification discloses principles of general application, the claims may be drafted in corresponding general terms (Biogen v Medeva

[1997] RPC 1 at 48). “Principles of general application” means general principles that can be applied in practice when manufacturing a group of products or carrying out a process, including cases where the claims define the product or process in terms of the results to be achieved.

[0045] Features in claims described in general terms represent a principle of general applicability if it is reasonably expected (reasonably predicted) that the claimed invention will function with respect to all things to which those general terms apply. Such features described in general terms may be the main part of the claim or simple descriptive words. In either case, features expressed in general terms are sufficiently possible if the disclosure enables at least one form or one application of the general principle relating to that feature, and if a person skilled in the art can reasonably expect that the invention will function with respect to all things to which those general terms apply. (Kirin-Amgen Inc. v Hoechst Marion Roussel Ltd

[2005] RPC 9 at

[0112] ).

[0046] Where the claims are drafted more broadly, they are deemed implementable if superficially they satisfy the following conditions: a) the disclosure teaches a principle that a person skilled in the art must follow in order to achieve all embodiments included in the claims, and b) the specification discloses at least one example of the application of that principle and provides sufficient information to enable a person skilled in the art to perform alternative applications of the principle in a manner obvious to a person skilled in the art, even if not explicitly disclosed (T484 / 92).

[0047] Finally, unless otherwise specified, the term "purity" refers to a molar basis. [Brief explanation of the drawing]

[0048] Preferred embodiments of the present invention will be described with reference to the accompanying drawings. [Figure 1] This flowchart illustrates a preferred embodiment of the present invention and defines a method for extracting one or more valuable base metals from spent battery material. The method includes the steps of: obtaining a mass of spent battery material having a certain amount of one or more valuable base metals ("raw material preparation"); providing black mass to a dry metallurgical furnace (e.g., an ISASMELT® furnace) defined by a molten turbulence bath containing one or more sulfidants, one or more fluxes, and one or more fuels, thereby providing an oxygen partial pressure of about 10⁻¹³ to about 10⁻⁴ atm; providing exhaust gas to a gas scrubber to provide purified exhaust gas and emissions; forming a base metal mat (i.e., a molten metal sulfide phase) and a slag (i.e., a molten metal oxide phase), wherein the slag contains less than about 5% by weight of base metal, with the remainder migrating to the mat; and separating the mat from the slag in a settling furnace. [Overview of the project]

[0049] The present invention relates in general to a method for dry metallurgical treatment of used battery materials, preferably lithium-ion batteries, mixed with a low-temperature (below 900°C) sulfidating agent, which can overcome at least some of the known drawbacks of conventional high-temperature waste battery treatment methods. Such a treatment method is shown in Figure 1.

[0050] This invention utilizes a "sulfur-deficient mat." The advantage of a sulfur-deficient mat is that the operator can adjust the liquidus temperature of the mat phase according to the amount of sulfur in the molten material. This means that if the liquidus temperature of the slag is high, the operator can use a sulfur-deficient mat to prevent the formation of an overheated mat. While a normal mat is a molten sulfide (such as NiS-Cu2S-CoS-FeS), a sulfur-deficient mat is in an intermediate state between metal and a normal mat (such as Ni-NiS-Cu-Cu2S-Fe-FeS-Co-CoS).

[0051] According to a first aspect of the present invention, a method for extracting one or more valuable base metals from spent battery materials, comprising: a) obtaining a spent battery material having a certain amount of one or more valuable base metals; b) subjecting the spent battery material to a dry metallurgical furnace defined by a molten turbulent bath containing one or more low-temperature (less than 950 °C) sulfiding agents, one or more fluxes, and one or more fuels and / or coolants, thereby providing an oxygen partial pressure of about 10 ~ about 10 -13 ~ about 10 -4 atm; c) forming a base metal matte and slag, wherein the slag contains less than about 5 wt% of the base metal and the remainder migrates to the matte; d) separating the matte from the slag.

[0052] In one embodiment, the extraction method of the present invention is completed in less than about 1 minute. At these high temperatures, the reaction rate is very fast. One skilled in the art will understand that the size of the furnace is usually based on the handling constraints of the raw materials and products rather than the residence time in the vessel.

[0053] In one embodiment, the method further comprises: e) separating and purifying one or more valuable base metals by further refining the base metal matte.

[0054] In one embodiment, the slag contains more than 0.1 wt% sulfur. In contrast, the slag formed by the method of US Patent No. 11,661,638 (supra) does not contain sulfur.

[0055] In one embodiment, the one or more low-temperature sulfiding agents include sulfur, gypsum, metal sulfides and / or metal sulfates, such as sodium, calcium, magnesium, copper, iron (II), iron (III), hydrogen and lead.

[0056] In one embodiment, one or more sulfiding agents include gypsum.

[0057] In one embodiment, the gypsum contains CaSO4·2H2O.

[0058] In one embodiment, one or more sulfiding agents are added such that the amount of sulfur in the base metal matte is about 1 to about 28% by weight.

[0059] In one embodiment, one or more sulfiding agents are added such that the amount of sulfur in the base metal mat is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28% by weight.

[0060] In one embodiment, one or more sulfiding agents are added such that the amount of sulfur in the base metal mat is about 1-22, 2-21, 3-20, 4-19, 5-18, 6-17, 7-16, 7.5-15, 8-14, 8.5-13, 9-12, 9.5-11, or about 10% by weight. In a preferred embodiment, the amount of sulfur in the base metal mat is about 10% by weight.

[0061] In one embodiment, one or more sulfiding agents are added such that the amount of sulfur in the base metal matte is about 5 to about 15% by weight.

[0062] In one embodiment, one or more sulfiding agents are added such that the amount of sulfur in the base metal matte is about 10% by weight.

[0063] In another embodiment, the molar excess of sulfur is provided in a ratio of about 0.1:1 to 25:1, preferably about 0.5:1, and the excess sulfur is stoichiometric Me (l) +S (l) →MeS (l) This relates to the reaction (Me is a metal that transitions to the matte phase).

[0064] In various embodiments, the molar excess of elemental sulfur is approximately 0.11:1, 1.1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, or 25:1.

[0065] In one embodiment, the partial pressure of oxygen in a dry metallurgical furnace is approximately 10 -11.5 ~about 10 -6 It's an ATM.

[0066] In one embodiment, the partial pressure of oxygen in a dry metallurgical furnace is approximately 10 -10.5 ~about 10 -7 It's an ATM.

[0067] In one embodiment, the partial pressure of oxygen in a dry metallurgical furnace is approximately 10 -13 , 10 -12.5 , 10 -12 , 10 -11.5 , 10 -11 , 10 -10.5 , 10 -10 , 10 -9.5 , 10 -9 , 10 -8.5 , 10 -8 , 10 -7.5 , 10 -7 , 10 -6.5 , 10 -6 , 10 -5.5 , 10 -5 , 10 -4.5 , or 10 -4 It's an ATM.

[0068] In one embodiment, the partial pressure of oxygen in a dry metallurgical furnace is approximately 10 -12 ~10 -5 , 10 -11 ~10 -6 , 10 -10.5 ~10 -7 , 10 -10 ~10 -7.5 , 10 -9.5 ~10 -8 , or 10 -9 ~10 -8.5 It's an ATM.

[0069] In one embodiment, the partial pressure of oxygen in a dry metallurgical furnace is approximately 10 -9 It's an ATM.

[0070] In one embodiment, further refining includes converting metal sulfides present in the base metal matte into their respective elemental metals or chemical products (e.g., nickel sulfate, nickel hydroxide) by conventional techniques.

[0071] In one embodiment, the dry metallurgical furnace is further defined by a temperature exceeding approximately 1000°C.

[0072] In one embodiment, the dry metallurgical furnace is further defined by a temperature of about 1000 to about 1800°C.

[0073] In one embodiment, the dry metallurgical furnace is further defined by temperatures exceeding approximately 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, or 1800°C.

[0074] In one embodiment, the dry metallurgical furnace is further defined by a temperature of approximately 1000-1800°C, 1100-1750°C, 1200-1700°C, 1250-1650°C, 1300-1600°C, 1350-1550°C, 1400-1500°C, or approximately 1450°C.

[0075] In one embodiment, steps b), c), and d) are carried out in a single container.

[0076] In one embodiment, steps b) and c) are carried out in a separate vessel from step d) and are optionally operably connected to allow for substantially continuous operation. Preferably, step d) is carried out in a sedimentation furnace in which the slag can be separated from the base metal mat.

[0077] In one embodiment, the method includes using a plurality of containers arranged in series or parallel, preferably in series.

[0078] In one embodiment, the method is adaptable to and / or extensible to continuous flow or batch-type scenarios.

[0079] In one embodiment, the method of the present invention is adaptable and / or extensible to continuous flow or batch-type scenarios.

[0080] In one embodiment, the method is carried out continuously or semi-continuously. Semi-continuous operation may include a batch-type process in which each batch is executed in a semi-continuous process. This can be achieved in multiple reactors, each operating independently or in fluid communication with one another.

[0081] In one embodiment, one or more valuable base metals include Li, Au, Ag, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V.

[0082] In one embodiment, one or more valuable base metals include Li, Mn, Cu, Co, Au, Ag, and Ni.

[0083] In one embodiment, one or more valuable base metals include Ni.

[0084] In one embodiment, one or more valuable base metals include Mn.

[0085] In one embodiment, one or more valuable base metals include Cu.

[0086] In one embodiment, one or more valuable base metals include Co.

[0087] In one embodiment, one or more valuable base metals include Au.

[0088] In one embodiment, one or more valuable base metals include Ag.

[0089] In one embodiment, one or more impurities that migrate to the slag are present at a concentration of approximately 0.5% to approximately 40% of the valuable metal concentration on a molar basis.

[0090] In one embodiment, the method of the present invention yields a yield of approximately 1% to approximately 99.99999% (based on extracted valuable metals).

[0091] In preferred embodiments, the method of the present invention yields a yield of about 1% to about 100% (based on extracted valuable metals versus spent battery material). Preferably, the yield is about 10% to about 99.99%. More preferably, the yield is about 25% to about 99%. More preferably, the yield is about 50% to about 99%. More preferably, the yield is about 99%.

[0092] This defined range of approximately 1% to approximately 100% is intended to encompass all yields at the stated endpoints and between them. Therefore, the claimed scope is based on extracted valuable metals versus used battery materials, with respect to the following ranges: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 6 Including 1, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100%, and based on extracted valuable metals versus spent battery materials, including intermediate values ​​such as 70.5, 71.5, 72.5, 73.5, 74.5, 75.5, 76.5, 77.5, 78.5, 79.5, and 80.5%.

[0093] In one embodiment, the dry metallurgical furnace is further defined by the raw material concentration of spent battery material, ranging from about 0.1% to about 99% w / w.

[0094] The raw material concentration of spent battery materials corresponds to the weight / weight percentage of solids in the raw material for dry metallurgy furnaces. The raw material concentration of spent battery materials ranges from approximately 0.1% w / w to approximately 99% w / w. Therefore, the claimed scope includes 0.1, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 99% w / w, and intermediate values ​​such as 21, 23, 25, 27, 29, 31, 33, 35, 37, and 39% w / w.

[0095] In a preferred embodiment, the raw material concentration of the used battery material is about 0.1 to about 99.99% w / w. In another preferred embodiment, the raw material concentration of the used battery material is about 40 to about 98% w / w. In another preferred embodiment, a predetermined raw material concentration of the used battery material is about 50 to about 95% w / w. In another preferred embodiment, a predetermined solid content concentration is about 55 to about 94% w / w. In another preferred embodiment, the raw material concentration of the used battery material is about 75 to about 90% w / w. In another preferred embodiment, the raw material concentration of the used battery material is about 80% w / w.

[0096] In a preferred embodiment, the spent battery material concentration is about 0.1 to about 99.99% w / w. In another preferred embodiment, the spent battery material concentration is about 10 to about 99% w / w. In another preferred embodiment, the spent battery material concentration is about 50 to about 98% w / w. In another preferred embodiment, the spent battery material concentration is about 60 to about 97% w / w. In another preferred embodiment, the spent battery material concentration is about 65 to about 96% w / w.

[0097] In a preferred embodiment, the used battery material concentration is about 0.1 to about 99.9999% w / w. In another preferred embodiment, the used battery material concentration is about 1 to about 98% w / w. In another preferred embodiment, the raw material concentration of the used battery material is about 5 to about 95% w / w. In another preferred embodiment, the raw material concentration of the used battery material is about 60 to about 90% w / w. In another preferred embodiment, the raw material concentration of the used battery material is about 70 to about 85% w / w.

[0098] In one embodiment, used battery material is obtained by destroying or crushing used battery waste to a predetermined average particle size.

[0099] In one embodiment, the used battery material has an average particle size of about 0.1 μm to about 1000 μm.

[0100] In one embodiment, the used battery material is approximately 25 nm to approximately 1000 mm (10 9 It has an average particle size of approximately 25, 50, 75, 100, and 10 3 , 10 4 , 10 5 , 10 6 , 10 7 , 10 8 or 10 9 It has an average particle size between nm. A larger average particle size (e.g., 10 nm) 7 ~10 9 In some embodiments, a complete (i.e., not crushed / shredded) battery can be used in the method of the present invention.

[0101] In one embodiment, the used battery material has an average particle size of about 500 nm to about 500 μm.

[0102] In one embodiment, the used battery material has an average particle size of approximately 2500 μm to approximately 100 μm.

[0103] In one embodiment, the used battery material has an average particle size of approximately 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, or 10,000 nm (i.e., 10 μm). In one embodiment, the used battery material has an average particle size of about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or about 500 μm.

[0104] In one embodiment, the used battery material has an average particle size of about 500 nm to about 500 μm. In a preferred embodiment, the used battery material has an average particle size of about 2000 nm to about 450 μm. In a preferred embodiment, the used battery material has an average particle size of about 4000 nm to about 400 μm. In a preferred embodiment, the used battery material has an average particle size of about 6000 nm to about 350 μm. In a preferred embodiment, the used battery material has an average particle size of about 8000 nm to about 300 μm. In a preferred embodiment, the used battery material has an average particle size of about 10,000 nm to about 250 μm. In a preferred embodiment, the used battery material has an average particle size of about 12,000 nm to about 200 μm. In a preferred embodiment, the used battery material has an average particle size of about 14,000 nm to about 150 μm. In a preferred embodiment, the spent battery material has an average particle size of about 16,000 nm to about 100 μm. In a preferred embodiment, the spent battery material has an average particle size of about 20,000 nm to about 90 μm. In a preferred embodiment, the spent battery material has an average particle size of about 25,000 nm (i.e., 25 μm) to about 80 μm. In a preferred embodiment, the spent battery material has an average particle size of about 30 μm to about 70 μm. In a preferred embodiment, the spent battery material has an average particle size of about 35 μm to about 60 μm.

[0105] The average particle size of the used battery material is approximately 500 nm to approximately 500 μm, more preferably approximately 40 μm to approximately 60 μm, and most preferably approximately 44 μm. This specified range is intended to encompass all average particle sizes at and between the stated endpoints. Accordingly, the claimed range includes 0.5 μm (i.e., 500 nm), 1, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480 and 500 μm, and includes intermediate values ​​such as 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 and 99 μm.

[0106] In one embodiment, the used battery material is not treated (physically, chemically, mechanically, or physically, such as by heating or thermal decomposition) before use.

[0107] In one embodiment, used battery material is treated (chemically, mechanically, and / or physically, such as by heating or thermal decomposition) before use.

[0108] In one embodiment, the electrolyte from the battery is still present in the used battery material.

[0109] In another embodiment, the electrolyte from the battery is still not present in the used battery material.

[0110] In one embodiment, the used battery material may contain one or more of a binder or an electrolyte. Preferably, the electrolyte is lithium hexafluorophosphate (LiPF6). Preferably, the binder is selected from one or more of fluoroethylene carbonate (FEC), 1,3-propanesultone (PS), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), polyvinylidene fluoride (PVDF), and propylene carbonate (PC).

[0111] In one embodiment, the dry metallurgical furnace comprises any suitable dry metallurgical vessel or furnace.

[0112] In one embodiment, the pyrolysis vessel or pyrolysis furnace is a bath furnace or a blast furnace.

[0113] In one embodiment, the pyrolysis vessel or pyrolysis furnace is an ISASMELT® furnace. The ISASMELT® furnace is an upright cylindrical steel vessel lined with refractory bricks. At the bottom of the furnace is a molten bath of slag, matte, or metal (depending on the application). A steel lance is lowered into the bath through a hole in the top of the furnace, and the bath is vigorously agitated by air or oxygen-enriched air injected into the bath through the lance. Mineral concentrate or recycled material is introduced into the bath through another hole in the top of the furnace, or optionally injected through the lance. These raw materials react with the oxygen in the injected gas, producing a powerful reaction in small amounts (compared to other smelting techniques).

[0114] ISASMELT® lances include one or more devices called "swirlers" that swirl the injected gas within the lance, pressing it against the lance walls for cooling. The swirler consists of curved vanes positioned around a central pipe, forming an annular flow. These are designed to minimize pressure loss and generate a powerful vortex by changing the angle from axial to tangential. The vortex helps mix the liquid and solid in the bath with oxygen. The cooling effect creates a "solidified" layer of slag on the outside of the lance. This layer of solid slag protects the lance from the high temperatures inside the furnace. The tip of the lance, immersed in the bath, will eventually wear down, but worn lances can be easily replaced with new ones as needed. The worn tip is then cut off, a new tip is welded to the lance body, and the lance body is then returned to the furnace.

[0115] ISASMELT® furnaces typically operate in a range of 1000–1500°C, depending on the application. Refractory bricks forming the furnace lining protect the steel shell from the heat inside the furnace. The product is removed from the furnace through one or more tap holes in a process called "tapping." This can be done continuously or in batches, and at the end of tapping, the tap holes are sealed with clay and reopened with a drill or thermal lance for the next tapping. Alternatively, slag notches or underflow weirs can be used to continuously remove the molten material from the furnace. The product is separated in a settling vessel such as a rotary holding furnace or electric furnace.

[0116] In the smelting of sulfide concentrates, most of the energy required to heat and melt the raw materials is obtained from the reaction of sulfur and iron in the concentrate with oxygen. However, a small amount of auxiliary energy is required. ISASMELT® furnaces can use a variety of fuels, including coal, coke, petroleum coke, oil, and natural gas. Solid fuels can be added from the top of the furnace along with other raw materials, or injected through a lance. Liquid and gaseous fuels are injected through a lance.

[0117] According to a second aspect of the present invention, one or more valuable metals are provided, extracted from used battery waste by a method defined according to the first aspect of the present invention.

[0118] In one embodiment, one or more valuable metals are selected from the group consisting of Li, Mn, Cu, Co, Au, Ag, and Ni.

[0119] According to a third aspect of the present invention, an apparatus for extracting one or more valuable base metals from used battery waste, a) One or more low-temperature (below 900°C) sulfiding agents, One or more fluxes, By feeding spent battery waste into a dry metallurgical furnace defined by a turbulent bath containing one or more fuels, This results in approximately 10-13 ~about 10 -4 Means for providing the oxygen partial pressure atm, b) A means for forming a base metal mat and slag, wherein the slag contains less than approximately 5% by weight of base metal, and the remainder is transferred to the mat. c) An apparatus is provided, which includes means for separating the mat and the slag.

[0120] In one embodiment, one or more valuable metals include Li, Mn, Cu, Co, Au, Ag, and Ni.

[0121] In one embodiment, the apparatus comprises a plurality of reactors arranged in series with fluid communication between them.

[0122] In one embodiment, the apparatus comprises a plurality of reactors arranged in parallel with fluid communication between them.

[0123] In a preferred embodiment, the apparatus further comprises means for carrying out an initial milling step, thereby milling the used battery material to a predetermined average particle size (as defined above) before it is provided to step a).

[0124] In a preferred embodiment, the apparatus of the present invention further comprises a filtration means for filtering out each of the precipitated metal sulfates after extraction from used battery waste.

[0125] In one embodiment, the apparatus is used to carry out a method defined according to a first aspect of the present invention.

[0126] According to a fourth aspect of the present invention, a metal sulfide extracted in a mat by a method defined according to a first aspect of the present invention is provided.

[0127] In one embodiment, the metal sulfide is Li in the mat. y S x Includes.

[0128] In one embodiment, the metal sulfide is Mn in the mat.y S x Includes.

[0129] In one embodiment, the metal sulfide contains Cu-S within the mat.

[0130] In one embodiment, metal sulfides are placed in the mat. y S x Includes.

[0131] In one embodiment, the metal sulfide is Au in the mat. y S x Includes.

[0132] In one embodiment, the metal sulfide is Ag in the mat. y S x Includes.

[0133] In one embodiment, metal sulfides are present in the mat. y S x Includes.

[0134] In one embodiment, the metal sulfide is Fe in the mat. y S x Includes.

[0135] In preferred embodiments of the second and fourth aspects, the process parameters are as defined above with respect to the first and third aspects of the present invention.

[0136] After the completion of step c), the obtained metal sulfide is solidified from the solution, or optionally, its grade is improved or it is separated before such solidification. The metal sulfide can be converted back to its respective elemental valuable metal by conventional techniques.

[0137] The slag is either discarded or subjected to a secondary recycling process to recover valuable metals that cannot be recovered by the method of the present invention, for example. [Modes for carrying out the invention]

[0138] The present invention relates to a method for dry metallurgical treatment of lithium-ion batteries mixed with a sulfidating agent, which can at least partially overcome the known drawbacks of conventional high-temperature lithium-ion battery treatment methods. Such a treatment method is shown in Figure 1.

[0139] Because lithium-ion batteries lack sufficient sulfur, a sulfur-containing matte phase cannot be produced without adding a sulfidizing agent. Those skilled in the art will understand that various sulfidizing agents can be used to introduce sulfur into the smelting process. However, the selection of an inexpensive and suitable agent is currently unknown even to those skilled in the art.

[0140] The sulfidizing agent currently used in industry is elemental sulfur, which is injected as a liquid into the molten alloy phase or pre-reducing roasted ore. This is done in nickel laterite smelting flowsheets. However, when elemental sulfur is added to bath smelting furnaces that process lithium-ion batteries, such as ISASMELT® furnaces, some of the sulfur may burn before it can react in the bath.

[0141] An alternative sulfiding agent is molten mat from primary base metal smelters. This is done at some primary copper and nickel smelters, where black mass and other materials are added to the converter. However, this requires the smelter to possess a large amount of base metal sulfide concentrate. This means that in places where base metal sulfide concentrate is unavailable, base metal cannot be recovered from lithium-ion batteries.

[0142] An alternative sulfiding agent is pyrite (or pyrite-containing concentrate), which can be supplied to a bath smelting furnace and react with the base metal alloy to form matte. However, when pyrite (or pyrite-containing concentrate) is added to the process, the chemical composition of the slag is altered, making the smelting process more difficult.

[0143] The use of gypsum is currently unknown to those involved in the processing of lithium-ion batteries. This sulfiding agent contains both sulfur (as sulfate) and lime, both of which are necessary in the process to lower the required smelting temperature. The lime in gypsum is used to flux the slag, and the sulfur reacts to form the matte phase. Unlike elemental sulfur, the sulfur in gypsum does not burn when it enters the furnace and is reduced when digested in the bath. Unlike pyrite (or iron sulfide concentrate), gypsum does not contain iron and does not affect the chemical composition of the slag. In contrast to both elemental sulfur and pyrite concentrate, the recovery rate of sulfur (from gypsum) into matte is limited by kinetic constraints and S 2(g) By avoiding the generation process (as an intermediate step), the cost would be significantly higher.

[0144] The ISASMELT® furnace injects oxygen-enriched air, and in some cases fuel, into molten slag and smelts the incoming raw materials in a turbulent bath. Those skilled in the art will know that the oxygen potential of the furnace is 10 -7 ~10 -11 The precise ratio of oxygen-enriched air to fuel can be selected to maintain the temperature within the atm range.

[0145] Those skilled in the art will understand that careful selection of the ratios of raw materials, sulfurizers, and fluxes added to the ISASMELT® furnace is necessary to obtain fluid slag and matte. Furthermore, the matte phase may be sulfur-deficient and contains 1-22% by weight of sulfur when discharged from the ISASMELT® furnace.

[0146] Those skilled in the art will understand that the oxygen-enriched air injected through the ISASMELT lance and the raw materials introduced into the furnace should be added in a ratio that yields partial combustion, resulting in the substantial oxidation of many gaseous compounds while leaving some unburned FeS, ZnS, NiS, Cu2S, CoS, MnS, Fe, Ni, Cu, Zn, Co, and Mn to form a molten mat at the bottom of the furnace.

[0147] The atmosphere suitable for partial combustion of the input material is 10 -13~10 -4 This is the partial pressure of oxygen atm, or more accurately, 10 -11 ~10 -6 This is the partial pressure of oxygen atm, and more precisely, 10 -10.5 ~10 -8.5 This is the partial pressure of oxygen atm. The resulting matte is suitable for addition to base metal refineries for downstream processing. [Examples]

[0148] Examples of the method of the present invention are shown in Tables 1 to 11 below.

[0149] [Table 1]

[0150] As shown above with respect to Table 1, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 243 kg and contained 47.8 wt% nickel, 22.0 wt% copper, 10.6 wt% cobalt, and 10.0 wt% sulfur. In comparison, 189 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.6 wt% Cu, and 0.5 wt% Co.

[0151] [Table 2]

[0152] As shown above with respect to Table 2, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 254 kg and contained 51.6 wt% nickel, 23.8 wt% copper, 13.2 wt% cobalt, and 8.8 wt% sulfur. In comparison, 218 kg of sulfur-containing slag contained only 0.3 wt% Ni, 0.4 wt% Cu, and 0.6 wt% Co.

[0153] As shown below with respect to Table 3a, 120 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 256 kg and contained 51.0 wt% nickel, 23.3 wt% copper, 13.1 wt% cobalt, and 9.9 wt% sulfur. In comparison, 228 kg of sulfur-containing slag contained only 0.3 wt% Ni, 0.7 wt% Cu, and 0.7 wt% Co.

[0154] As shown below with respect to Table 3b, 120 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 253 kg and contained 51.5 wt% nickel, 23.9 wt% copper, 12.4 wt% cobalt, and 10.9 wt% sulfur. In comparison, 235 kg of sulfur-containing slag contained only 0.6 wt% Ni, 0.5 wt% Cu, and 1.5 wt% Co.

[0155] [Table 3]

[0156] [Table 4]

[0157] [Table 5]

[0158] As shown above with respect to Table 3c, 120 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 257 kg and contained 50.9 wt% nickel, 22.9 wt% copper, 13.3 wt% cobalt, and 8.5 wt% sulfur. In comparison, 224 kg of sulfur-containing slag contained only 0.3 wt% Ni, 1.2 wt% Cu, and 0.4 wt% Co.

[0159] As shown in Table 4 below, 80 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 253 kg and contained 51.8 wt% nickel, 24.0 wt% copper, 13.4 wt% cobalt, and 7.1 wt% sulfur. In comparison, 204 kg of sulfur-containing slag contained only 0.1 wt% Ni, 0.3 wt% Cu, and 0.4 wt% Co.

[0160] [Table 6]

[0161] As shown in Table 5 below, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 257 kg and contained 51.1 wt% nickel, 23.2 wt% copper, 13.4 wt% cobalt, and 7.2 wt% sulfur. In comparison, 210 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.9 wt% Cu, and 0.2 wt% Co.

[0162] [Table 7]

[0163] As shown in Table 6 below, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 254 kg and contained 44.7 wt% nickel, 23.7 wt% copper, 20.1 wt% cobalt, and 8.3 wt% sulfur. In comparison, 216 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.6 wt% Cu, and 0.7 wt% Co.

[0164] [Table 8]

[0165] As shown in Table 7 below, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 256 kg and contained 55.8 wt% nickel, 23.6 wt% copper, 8.9 wt% cobalt, and 8.5 wt% sulfur. In comparison, 214 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.5 wt% Cu, and 0.3 wt% Co.

[0166] [Table 9]

[0167] [Table 10]

[0168] As shown in Table 8 above, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 253 kg and contained 39.6 wt% nickel, 35.8 wt% copper, 13.3 wt% cobalt, and 8.3 wt% sulfur. In comparison, 217 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.8 wt% Cu, and 0.6 wt% Co.

[0169] As shown in Table 9 below, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 256 kg and contained 59.1 wt% nickel, 15.7 wt% copper, 13.3 wt% cobalt, and 8.4 wt% sulfur. In comparison, 214 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.4 wt% Cu, and 0.4 wt% Co.

[0170] [Table 11]

[0171] [Table 12]

[0172] As shown in Table 10 above, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 249 kg and contained 49.1 wt% nickel, 24.2 wt% copper, 13.6 wt% cobalt, and 8.5 wt% sulfur. In comparison, 223 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.6 wt% Cu, and 0.5 wt% Co.

[0173] [Table 13]

[0174] Finally, as shown in Table 11 above, 100 kg of gypsum and 20 kg of silica were added to the initial mass of 500 kg of waste nickel-containing batteries. The matte / alloy obtained according to the dry metallurgical extraction method described in claim 1 had a mass of 259 kg and contained 52.8 wt% nickel, 23.3 wt% copper, 13.1 wt% cobalt, and 8.3 wt% sulfur. In comparison, 210 kg of sulfur-containing slag contained only 0.2 wt% Ni, 0.5 wt% Cu, and 0.5 wt% Co.

[0175] The general methods used above fully demonstrate the remarkable effectiveness of improved dry metallurgical conditions that utilize a furnace to extract metal sulfides from spent battery materials.

[0176] This method further demonstrates the effectiveness of improved dry metallurgical conditions that utilize furnaces to recycle other valuable metals from used battery materials. Such metals preferably include Mn, Ni, Co, and / or Li.

[0177] Economic and environmental impacts The above examples demonstrate that, contrary to conventional wisdom, valuable metals such as lithium can be extracted from used battery materials under relatively mild conditions as defined by the present invention, even when using wet or dry metallurgy methods. Such methods offer numerous advantages, including the absence of adverse effects such as metal selectivity, cost, and environmental damage, the elimination of one or more pretreatment or subsequent purification / extraction steps, and the need for a detailed understanding of the chemical composition of the used battery materials.

[0178] The present invention's method for extracting valuable metals from used battery waste offers numerous advantages over conventional methods. The present invention is entirely counterintuitive when using a relatively mild pyrolysis furnace at moderate temperature and pressure for a relatively short reaction time. Furthermore, compared to typical conventional methods, the present invention provides an environmentally friendly approach to what was previously a somewhat harmful and wasteful endeavor.

[0179] More specifically, the use of sulfur to improve the extraction of valuable metals under low-temperature heating conditions represents a more environmentally friendly approach compared to many or most known lithium-ion battery recycling methods. [Industrial applicability]

[0180] The demand for valuable metals such as lithium, manganese, nickel, and cobalt continues to increase globally, but mineral supplies are limited, and conventional extraction methods are difficult to use, making recycling essential. The development and commercialization of inventive technologies could have significant economic implications.

[0181] Although the present invention has been described with reference to specific examples, those skilled in the art will understand that the present invention can be embodied in many other forms.

Claims

1. A method for extracting one or more valuable base metals from used battery waste, a) A step of obtaining used battery waste having a certain amount of one or more valuable base metals, b) One or more low-temperature (below 900°C) sulfiding agents, One or more fluxes, The used battery waste is fed into a dry metallurgical furnace defined by a molten turbulent bath containing one or more fuels and / or coolants. This results in approximately 10 －１３ ~about 10 －４ A process of providing the oxygen partial pressure atm, c) A step of forming a base metal mat and a slag, wherein the slag contains less than approximately 5% by weight of base metal, and the remainder is transferred to the mat. d) A method comprising the step of separating the mat from the slag.

2. e) The method according to claim 1, further comprising the step of separating and purifying one or more valuable base metals by further refining the base metal matte.

3. The method according to claim 1, wherein the one or more sulfiding agents include sulfur, gypsum, metal sulfides and / or metal sulfates, such as sodium, calcium, magnesium, copper, iron(II), iron(III), hydrogen, and lead.

4. The method according to any one of claims 1 to 3, wherein one or more sulfiding agents are added so that the amount of sulfur in the base metal mat is about 1 to about 28% by weight.

5. The oxygen partial pressure is approximately 10 －１０．５ ~about 10 －７ The method according to any one of claims 1 to 4, wherein the ATM is an ATM.

6. The method according to any one of claims 1 to 5, wherein the further refining comprises converting the metal sulfides present in the base metal mat into their respective chemical or metallic products by conventional techniques.

7. The method according to any one of claims 1 to 6, wherein the dry metallurgical furnace is further defined by a temperature exceeding approximately 1000°C.

8. The method according to any one of claims 1 to 7, wherein steps b), c), and d) are performed in a single container.

9. The method according to any one of claims 1 to 8, wherein steps b) and c) are performed in a separate container from step d) and are optionally operably connected to enable substantially continuous operation.

10. The method according to claim 9, wherein a plurality of containers are used, preferably arranged in series or in parallel.

11. The method according to any one of claims 1 to 10, which is adaptable to and / or scalable to continuous flow or batch-type scenarios.

12. The method according to any one of claims 1 to 11, wherein the one or more valuable base metals include Li, Au, Ag, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V.

13. The method according to claim 12, wherein the one or more valuable base metals include Li, Mn, Cu, Co, and / or Ni.

14. The method according to any one of claims 1 to 13, yielding approximately 1% to approximately 100% (based on extracted valuable metals).

15. The method according to any one of claims 1 to 14, wherein the dry metallurgical furnace is further defined by the raw material concentration of spent battery material of about 0.1 to about 90% w / w.

16. The method according to any one of claims 1 to 15, wherein the used battery waste is obtained by destroying or crushing used batteries to a predetermined average particle size.

17. The method according to claim 16, wherein the used battery waste has an average particle size of about 25 nm to about 1000 mm.

18. The method according to any one of claims 1 to 17, wherein the used battery waste has not been treated (physically, such as chemically, mechanically, by heating, or by thermal decomposition) before use.

19. The method according to any one of claims 1 to 17, wherein the used battery waste is treated (chemically, mechanically, and / or physically, such as by heating or thermal decomposition) before use.

20. The method according to any one of claims 1 to 19, wherein the electrolyte from the battery may or may not remain in the used battery waste.

21. The method according to any one of claims 1 to 20, wherein the dry metallurgical furnace comprises any suitable pyrolysis vessel or pyrolysis furnace.

22. The method according to claim 21, wherein the pyrolysis vessel or pyrolysis furnace is a bath furnace or a blast furnace.

23. The method according to claim 21 or 22, wherein the pyrolysis vessel or pyrolysis furnace is an ISASMELT (trademark) furnace.

24. One or more valuable metals extracted from used battery material by the method according to any one of claims 1 to 23.

25. One or more valuable metals selected from the group consisting of Li, Mn, Cu, Co, Au, Ag, and Ni, as described in claim 24.

26. An apparatus for extracting one or more valuable base metals from used battery waste, a) One or more sulfiding agents, One or more fluxes, The used battery waste is fed into a dry metallurgical furnace defined by a turbulent bath containing one or more fuels and / or coolants. This results in approximately 10 －１３ ~about 10 －４ A means for providing the partial pressure of oxygen atm, b) A means for forming a base metal mat and a slag, wherein the slag contains less than about 5% by weight of base metal, and the remainder is transferred to the mat. c) An apparatus comprising means for separating the mat and the slag.

27. The apparatus according to claim 26, wherein the one or more valuable metals include Li, Mn, Cu, Co, Au, Ag, and / or Ni.

28. The apparatus according to claim 26 or 27, comprising a plurality of reactors arranged in series with fluid communication.

29. The apparatus according to any one of claims 26 to 28, used for carrying out the method according to any one of claims 1 to 23.

30. A metal sulfide produced by the method described in any one of claims 1 to 23.

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