Metal extraction from lithium ion battery materials

Abstract

To provide a method and equipment for extracting a metal from a black aggregate of a lithium ion battery.SOLUTION: The black agglomerates contain the anode and cathode materials of the battery and some copper, with the cathode materials including lithium and nickel. Furthermore, the invention relates to an installation suitable for use in the method.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a lithium ion battery material, in particular a black aggregate obtained from said battery material. In a method for extracting metals, the black aggregate is a cathode metal and an anode metal. The cathode metal usually contains lithium and nickel, and copper from the battery components. The optional cathode metals include nickel, cobalt, manganese, and aluminum. The present invention also relates to an arrangement suitable for use in this method. Regarding. [Background technology]

[0002] The use of lithium-ion batteries has been growing steadily over the years and even decades. As new electric vehicles are developed, their importance is expected to increase. .

[0003] Such lithium-ion batteries have a cathode that can be reused or recycled within the battery. Some of the materials that could be useful if recovered from these batteries for other purposes Separating the cathode material from other battery components is usually It starts with the mechanical removal of solids such as copper foil from the material, followed by the further removal of electrolyte. The remaining cathode and anode materials are then subjected to a washing step to remove the so-called black aggregates. This black mass can be subjected to a hydrometallurgical separation process to recover the desired individual metals. It is suitable for processing.

[0004] However, mechanical separation is not completely selective and only a fraction of the copper (e.g., from the copper foil) is removed. These eventually become black aggregates, and the hydrometallurgical separation process solubilizes the transition metals in the cathode. When the leaching step to produce copper is involved, copper is also dissolved. This copper fraction is usually It is large enough to generate interest in its recovery as a means of

[0005] Removal of copper from solution is important because copper remaining in solution is used to prepare transition metals. However, copper is effectively removed by the ion exchange reaction. It's difficult.

[0006] The most typical approach for copper (Cu) recovery is solvent extraction, which involves extracting Cu from concentrated sulfuric acid. It can be selectively recovered in an acid Cu solution, and then electrowinning can produce new materials such as Cu cathodes. However, this approach is complex and requires extensive processing materials. This will result in excess chemicals in the fuel supply and significantly increase the investment required.

[0007] A simpler, more cost-effective approach to achieving higher purity metal products is Copper cementation is a well-known method for recovering copper. However, it is possible to form very complex metal mixtures. Therefore, it is rarely used for recovering metals from battery materials.

[0008] Therefore, it is possible to separate and purely select metals from a complex mixture of cathodes and other metals. New technologies are needed to efficiently recover these materials in a form that is safe and reliable. Summary of the Invention [Problem to be solved by the invention]

[0009] The invention is defined by the features of the independent claims. Some specific embodiments are described in the dependent claims. As defined in the claims.

[0010] According to a first aspect of the present invention, a gold alloy is obtained from a black aggregate obtained from a lithium ion battery material. The present invention provides a method for extracting black aggregates from negative and positive electrode materials of a battery, and Contains copper metal. Metals extracted and recovered include copper, lithium, and nickel. and optionally cobalt and manganese may include one or both of the following:

[0011] According to a second aspect of the present invention, there is provided a method for extracting metals from black aggregates, the method comprising: The process proceeds through the solubilization of the desired metals in the black aggregates and then the extraction of such metals from the resulting solution. The solubilized metal fraction is recovered along with a further solubilized metal fraction.

[0012] According to a third aspect of the present invention, a cementation process is carried out with a reagent that can be efficiently separated from the remaining solution. By using the ionization, the copper fraction was extracted from the resulting solution containing the solubilized cathode material. Methods for proceeding through recovery are provided.

[0013] According to a further aspect of the invention, there is provided a method for carrying out the steps of the method of the invention. Suitable facilities will be provided.

[0014] The method of the present invention comprises the following steps: - one or more leaching steps, and - Typically, the copper fraction and fractions containing lithium and nickel ions are extracted from the leach solution. The metal separation step required to recover the desired metal from the a copper recovery step including copper cementation by Equipped with.

[0015] Likewise, an inventive installation suitable for using the above-described method comprises: - one or more leaching units from which the leaching solution containing the dissolved cathode material is collected; the leaching unit, - A metal separation unit from which copper, lithium and nickel ions are separated. a fraction having the metals separated from the copper is recovered, and the recovery of copper comprises a cementation unit. The unit and Equipped with.

[0016] Therefore, the present invention is directed to a method for manufacturing a semiconductor device that contains impurities and at least nickel (Ni) in addition to Cu. The method is based on the recovery of copper (Cu) from a solution containing a mixture of metal ions, including:

[0017] At least part of the copper recovery is achieved by cementation, resulting in the loss of C in solution. The u is replaced by Ni, resulting in a Cu metal product that can be easily separated from the solution components. The reduction potential of the nickel reagent is higher than that of copper (0.34 V). or more negative reduction potential (-0.25V). The selectivity is similar to that of other elements present in the leach solution, e.g., lithium (-3.04V), Or in some cases cobalt (-0.28V), manganese (-1.19V), or aluminum The reduction potential of aluminum (-1.66V) is more negative than that of the nickel reagent. This is due in part to the fact that these other elements are not reduced.

[0018] The present invention offers several advantages. Among other things, the inventors have found that the cementation The essential process configuration is, for example, solvent extraction followed by electrolysis, which is commonly used in battery recycling applications. Compared with decomposition, copper recovery from the leaching solution of black aggregates obtained from Li-ion batteries found to be a significantly simpler and therefore more cost-effective solution to Such a simple process configuration is not suitable for complex material mixtures such as lithium-ion battery materials. This is particularly advantageous when processing materials.

[0019] Furthermore, cementation can be performed without contaminating the leachate with additional chemicals. The procedure for recovering copper by simply increasing the content of a further metal, in this case nickel, in The additional metals can then be recovered separately. Therefore, it may be possible to recover other metals separately from the leach solution.

[0020] Such efficient copper recovery is a promising option for metal recovery from black aggregates. This also leads to a selective overall process, providing individual metal products with high yields and purity. In this way, copper cementation has a synergistic effect that results in high-purity metal products. . [Brief explanation of the drawings]

[0021] [Figure 1] 1 shows a unit of the installation according to the invention; [Figure 2A] 1 shows a unit of a facility according to an embodiment of the present invention; [Figure 2B] 1 shows a unit of a facility according to an embodiment of the present invention; [Figure 3] 1 shows a unit of a facility according to an embodiment of the present invention; [Figure 4] 1 shows a unit of a facility according to an embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0022] [Definition] As used herein, the term "black mass" refers to the macrocomponent of a battery. is intended to represent the mixture of cathode and anode materials obtained after mechanical separation of the cathode and anode materials. The black aggregates also contain, inter alia, copper in metallic form, which comes from the copper foil of the battery, and It also contains organic compounds depending on the pretreatment method of the black aggregate, such as compounds derived from the electrolyte of do.

[0023] "Organic compounds" as used herein is meant to encompass molecules. Figure 1 shows one or more carbon atoms covalently bonded to one or more hydrogen, oxygen, or nitrogen atoms. Thus, for example, graphite or other pure carbon allotropes are Excluded from this class of compounds despite meeting the definition. Other compounds commonly considered to be hydroxyl groups include those in which the only carbon in the compound is a group When based on carbon dioxide, these include carbonates and cyanides, as well as carbon dioxide.

[0024] The "anode" is usually made primarily of graphite or silicon. is not solubilized by the leaching of the present invention, but is present in the black aggregates before leaching.

[0025] "Cathode material" or "cathode metals" Similarly, lithium, nickel, cobalt, and manganese (Li, Ni, Co, Mn) These include metal ions, typically in the form of their oxides. The content of these metals is preferably in the range of 1 to 35% by weight. Other examples of positive electrode components that may be present, but generally in smaller amounts, include tin, zirconium, Zinc, copper, iron, fluoride, phosphorus, aluminum (i.e. Sn, Zr, Zn, Cu, Fe , F, P, and Al).

[0026] The present invention relates to a method for extracting metals from black aggregates of lithium ion battery materials. The method includes the following steps: (a) one or more pre-treatment steps in which a fraction of non-metallic materials is separated from the black mass; The pretreated black mass containing the anode and cathode materials is recovered and preferably leached. the pre-processing step being further processed by (b) one or more leaching steps, in which the cathode material of the pretreated black mass is dissolved; The leach solution containing the dissolved cathode material is recovered and preferably the metal fraction is separated therefrom. the leaching step, which is further processed by (c) Separating one or more initial fractions of metallic material from the leach solution and separating at least nickel and a metal separation step to recover the major fraction containing cadmium and lithium; (i) The metal separation step is performed by cementation of copper using nickel as a reducing agent. and a copper recovery step carried out before the nickel of the leach solution is recovered. Including, (ii) Nickel is recovered after the recovery of copper and before the recovery of lithium; and (iii) Nickel is recovered by solvent extraction; the metal separation step; Equipped with.

[0027] The black mass in lithium-ion batteries typically contains both positive and negative electrode materials, as well as some The electrolyte material includes copper and an organic compound. The organic compound is preferably one of the above-mentioned Each is preferably removed by pre-treating the battery material in water or an organic solvent, Preferably, one or more washing steps are carried out by mixing with water. The material dissolved or dispersed in the solvent, such as the organic compound, is then treated to form a black aggregate. Alternatively, the undissolved components can be separated, typically by a pyrolysis or evaporation step. One or more heating steps, performed as a step, can be used to remove organic compounds. Each heating step is preferably carried out at a temperature of 195 to 470°C. One option is to perform both a washing step and a heating procedure.

[0028] Thus, the pretreatment step preferably removes the lithium and nickel from the battery cathode, and Optionally containing manganese and cobalt in the form of oxides, and residual metallic copper. more preferably <3 wt. %, most preferably <1.5 wt. % of organic compounds , resulting in a pre-treated black mass.

[0029] In a preferred embodiment of the present invention, less of the lithium that is normally lost in the optional washing step is removed. At least in part, the following steps: Used cleaning solution containing the fraction of non-metallic materials separated from the remaining solids reacting the lithium therein with a phosphate reagent to precipitate lithium phosphate; , and The lithium phosphate precipitate is separated from the remaining wash liquid and transported to the next leaching step. combining with a pre-treated black mass; It will be collected by.

[0030] After the pretreatment step, solid-liquid separation is usually performed, whereby the pretreated black aggregates are then leaching step, and optionally either a pretreatment step or a metal recovery step. added metal-containing solids or, such as lithium phosphate precipitates recycled from It can be mixed with the slurry.

[0031] In one embodiment of the present invention, at least one leaching step comprises the addition of an acid and one or more leaching agents. Usually, only one leaching step is used, which is the acid leaching step. The acid leaching step is preferably performed by separating the pretreated black aggregate into a solution containing an acid. This is preferably carried out by dispersing the mixture, adding an optional extractant, and then mixing. do.

[0032] The acid used in the leaching step is preferably hydrochloric acid, nitric acid, methanesulfonic acid, oxalic acid , citric acid, and sulfuric acid to form an acidic leaching solution. Preferably, one or more leaching reagents or extractants, more preferably hydrogen peroxide, carbohydrates and sulfur dioxide, which have the reducing ability to be more effective in dissolving the to provide.

[0033] The temperature during the leaching step is preferably adjustable, whereby most preferably the temperature The temperature is maintained at a high level during the acid leaching, for example at a temperature above 50°C, preferably 50 to 60°C. A temperature of 95°C, and more preferably a temperature of 60-90°C. Similarly, the pressure during acid leaching The pressure is preferably maintained at atmospheric pressure or a slightly higher pressure of 100-200 kPa. Typically, solubilization of the desired transition metal is complete within 2-6 hours.

[0034] After the leaching reaction is complete, i.e., the pretreated black aggregate is left under leaching conditions for a sufficient time. For example, after 2 to 6 hours, the leaching solution containing the cathode metal is recovered. A solid-liquid separation is carried out, which allows the next step of the process to recover the separate metal fractions. It can be transported to the pool.

[0035] In one embodiment of the present invention, the main fraction contains at least nickel ions and lithium ions. The step for recovering the aluminum ions is to separate the initial fraction (or “initial fraction”) of metallic material from the leach solution. One or more steps to separate the “initial metallic fractions” The initial fraction of metallic material is composed of iron, aluminum, calcium ions and fluorine ions. The composition contains at least one of fluoride ions and optionally phosphate. This sequence of steps has the advantage of obtaining a purified solution for recovery of the main fraction of metallic materials. This is because the initial fraction contains substances that are considered to be impurities. Materials may also remain in the leaching solution and impair subsequent recovery of the main fraction, or At the very least, the purity or yield will be reduced.

[0036] Typically, the separation of the initial fraction of metallic material is carried out as a solvent extraction (SX). Both steps involve removing the impurities, such as iron and aluminum, from the leach solution. It is intended to remove impurities already in solid form, optionally preceded by solid separation. This removes the impurities, thus improving the selectivity and performance of the solvent extraction.

[0037] In another alternative, the separation of the initial fraction of metallic material is carried out as a precipitation. step, for example, to remove impurities such as iron and aluminum, and possible phosphoric acid. hydroxide precipitation, which aims to remove salts as a solid fraction from the leach solution.

[0038] In a particularly preferred alternative, the separation of the initial fraction of metallic material comprises precipitation, optionally followed by precipitation. This involves separation of impurities followed by solvent extraction, both steps as described above. The advantage of two-stage impurity separation is that the content of impurities such as iron and aluminum is thus refined. This two-stage separation of the initial metal fraction is then followed by further reduction in the leachate solution. In this case, it is particularly preferred to carry out precipitation before solvent extraction, which allows for the high yield of the solvent extraction. This is because selectivity becomes easier.

[0039] The copper recovery step should be carried out before any other metal separation steps, i.e., after the initial fraction of metallic material. This is preferably done before the separation of the copper, as copper will adversely affect subsequent separation and recovery. Copper itself may be lost during these steps. Cementation, which is used to recover uranium, is a selective reaction that produces pure uranium even in the presence of impurities. Because a copper product is produced, there is no need to purify the leach solution before copper recovery can occur.

[0040] Copper recovery is also favorable since at least one leaching step is carried out under acidic conditions. At least it can withstand the above conditions.

[0041] Recovery of copper from the leach solution is typically achieved by the cementitious method using nickel as the reducing agent. The cementation may be carried out by a cementation step or after solvent extraction. whereby the resulting copper-depleted solution is subjected to the next metal separation step. The nickel used in cementation is usually metallic nickel in powder form. The reaction (1) that occurs during cementation is: (1) Cu 2+ (aq)+Ni 0 (s) → Cu 0 (s)+Ni 2+ (aq) is.

[0042] Thus, the cementation reaction results in copper in solid form, usually recovered as a powder. The resulting copper powder is recovered, separated from the solution, optionally precipitated, and then Preferably, the reaction is followed by filtration, which may include a washing step to remove the mother liquor.

[0043] As mentioned above, cementation contaminates the transition metal-containing solution with additional chemicals. without, but simply increasing the content of the selected metal in the solution, in this case nickel. This has the advantage of introducing a procedure for recovering copper, and this selected metal , which can then be recovered separately. The selected metal, nickel, is already Since it is present in the black aggregate and subsequently in the leaching solution, no further steps are required in the overall method. No topping is added; this procedure simply increases the amount of nickel recovered. .

[0044] Solvent extraction, optionally combined with cementation, is believed to increase the yield of recovered copper. This has the added advantage that there is no significant amount of nitrate in the solution that is taken to subsequent metal recovery. This leaves only insignificant levels of copper impurities, resulting in a higher purity of the subsequently recovered metal. do.

[0045] Further leaching or washing steps, solvent extraction, etc. are required to separate and recover the remaining metals. Various reactions and procedures, such as extraction, precipitation, ion exchange steps, and electrowinning steps, However, as mentioned above, the separation of the initial fraction of metallic material It is preferred to use at least one solvent extraction, since the remaining solvent The purity of the solution is increased, thus facilitating the subsequent recovery of the main fractions, especially the cobalt and nickel fractions. Recovery is also facilitated, which allows for high yields and purity of all metals in the major fractions, typically can be recovered as battery-grade material.

[0046] As mentioned above, recovery of the major fraction of metals includes at least a step of recovering nickel. This is because the cementation step adds more copper to the leach solution. Nickel is added so that it is present in the solution at an increased content. Other metals in the major fraction include lithium, as mentioned above, and possibly cobalt. Contains zinc and manganese.

[0047] Nickel is thus recovered from the copper-depleted leach solution, and nickel recovery is therefore It is carried out at a later stage in the process than the recovery of copper and also at a later stage than the separation of the initial metal fraction. It can be done.

[0048] This nickel recovery is preferably carried out simultaneously with or immediately after the optional recovery of cobalt, more preferably Preferably after the cobalt is recovered, and most preferably before any lithium is recovered. This nickel recovery is usually carried out at a later stage than the optional manganese recovery. It will be held.

[0049] The nickel recovery can be carried out, for example, using solvent extraction (SX), which This produces a fairly pure nickel sulfate solution (NiSO4). This solution can optionally be It may be further purified, for example by ion exchange (IX), followed by crystallization or by conversion to hydroxide or Precipitation into carbonates can be carried out, or sulfate solutions can be used, for example, in the preparation of new cathode materials. It can be used as is without crystallization or precipitation in the process for nickel recovery. The optional solvent extraction is most preferably carried out using an extraction chemical having a carboxylic acid functionality. and one commercially available example of a suitable extraction chemical is Versatic TM 10 is listed, which is It is odecanoic acid.

[0050] In one embodiment of the present invention, the metal separation step involves removing cobalt from the copper-depleted leach solution. Cobalt recovery is thus a later step than copper recovery. It is also carried out at a later stage than the initial separation of the metal fraction.

[0051] Cobalt recovery is preferably carried out simultaneously with or immediately before nickel recovery, more preferably nickel recovery. before any lithium is recovered, and also, most preferably, before any lithium is recovered. Usually, however, this cobalt recovery is a step after the optional manganese recovery. It is held at.

[0052] The preferred option for cobalt recovery is solvent extraction (SX), which is quite A pure cobalt sulfate solution (CoSO4) is produced. This solution can optionally be treated with, for example, ion It is further purified by ion exchange (IX) followed by crystallization or conversion to hydroxide or carbonate. or sulfate solutions can be carried out, for example, in the preparation of new cathode materials, It can be used as is without crystallization or precipitation. Solvent extraction uses extraction chemicals with carboxylic acid functional groups, such as phosphinic acid functional groups. An example of a suitable extraction chemistry is Cyanex TM 272, which is Hexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphine Also known as a 'rut'.

[0053] In a further embodiment of the invention, the metal separation step comprises removing copper from the copper-depleted leach solution. The method includes a step of recovering manganese, and thus recovering manganese is more efficient than recovering copper. and also at a stage later than the separation of the initial metal fraction.

[0054] Manganese recovery is preferably carried out before nickel or cobalt is recovered, and most preferably This is done before any nickel, cobalt and lithium are recovered.

[0055] The manganese recovery options are solvent extraction and precipitation, or solvent extraction followed by precipitation. One particularly preferred option is the use of sulfur dioxide (SO2) and air. The goal is to form manganese oxide (MnO2) using the oxidation precipitates that were present in the slag.

[0056] In a further embodiment of the invention, the metal separation step comprises removing copper from the copper-depleted leach solution. The lithium recovery step is thus performed later in the process than the copper recovery step. and also at a stage subsequent to the separation of the initial metal fraction.

[0057] Preferably, lithium recovery is achieved by removing any of the manganese, cobalt, and nickel present in the leachate. This preferred sequence of steps allows for high purity This will allow lithium to be recovered from lithium-containing solutions.

[0058] Lithium is usually recovered by reacting it with its carbonate or phosphate salts. The product fraction is then collected to produce a product fraction that can be recovered directly, or alternatively, further treated with hydroxypropyl methylcellulose. It can also be converted to lithium and crystallized into pure hydroxide crystals.

[0059] A further option for lithium recovery is to use solvent extraction, followed by further The advantage of this procedure is that it allows for higher lithium is the recovery rate.

[0060] In one embodiment of the present invention, lithium is recovered in its carbonate salt and extracted by solid / liquid separation. The solid product fraction is then recovered or Alternatively, the liquid fraction is further converted to, for example, lithium hydroxide. , which can then be reacted with a phosphate reagent and possibly another precipitating reagent, so that This causes the remaining lithium to precipitate into a lithium phosphate precipitate. , or combined with carbonate or phosphate product fractions for lithium recovery, or Alternatively, it can be mixed with the pre-treated black mass and recycled for the leaching step. A further option is to transfer a portion of the precipitate to each of these steps.

[0061] The phosphate reagent used above is any phosphate of an alkali metal or earth alkali metal. However, sodium phosphate (Na3PO4) is preferred. , because it does not introduce new cations into the reaction mixture and has the appropriate reactivity. This is the case.

[0062] The optional precipitation reagent is preferably selected from alkaline agents such as sodium hydroxide; It functions by increasing the pH of the solution, thereby facilitating the precipitation of the desired lithium phosphate. Make it easy.

[0063] The method of the present invention comprises the units and equipment necessary to carry out the steps of the method, It may be carried out in any suitable device or equipment.

[0064] The invention further relates to an installation suitable for using the above-mentioned method, said installation comprising the following units: knit (see Figure 1), i.e. - Separating the non-metallic fraction from the black aggregate and pre-treating it to contain the anode and cathode materials one or more pre-treatment units 1 for recovering the black aggregates, preferably downstream The pretreatment unit is intended to be led to the leaching unit 2 via a suitable connection. To1 and - dissolving the positive electrode material of the pretreated black mass, and forming a leaching solution containing the dissolved positive electrode material; one or more leaching units 2 for recovering the said brewing unit 2, which is intended to be led to the brewing unit 2 via a suitable connection; - Separating an initial fraction of one or more metallic materials from the leach solution and extracting at least nickel and lithium a metal separation unit 3 for recovering the main fraction containing metals, The metal separation unit 3 further comprises or consists of a cementation unit copper separation unit 31, which is equipped with a nickel inlet 311; Located upstream of Unit 35, all of which are intended for nickel recovery, The nickel recovery unit 35 is located downstream of the copper separation unit 31 and located upstream of the uranium recovery unit 36, and Unit 35 for nickel recovery, including a sub-unit for solvent extraction That is, the metal separation unit 3; Equipped with.

[0065] In one embodiment of the present invention, with various options shown in FIGS. 2A and 2B, The unit 1 is a cleaning unit 1 for removing non-metallic components such as organic compounds from the black aggregate. 1 and / or heating unit 12, with heating unit 12 most preferably The unit is selected from a pyrolysis unit 121 or an evaporation unit 122. An optional cleaning unit The container 11 preferably further includes a water inlet.

[0066] The leaching unit 2 is typically composed of the acid leaching unit 21. 21 includes the necessary inlets 211 for acid and optional extractant, as well as preferably the inlet 212 for the acid and optional extractant. and temperature regulation, which can incorporate either heating or cooling, as shown in Figure 4. The device includes a means 212 for:

[0067] The metal separation unit 3 preferably includes a plurality of subunits, and all of the subunits Typically, they contain additional subunits, inputs, and outputs necessary to carry out the intended reaction. The units are equipped with an inlet and an outlet for recovering copper, nickel, and lithium, respectively. In addition to 31, 35, and 36, other separation and recovery units are also used for metal separation, as shown in Figure 4. Can be included in Unit 3.

[0068] Preferably, at least nickel ions and lithium ions, and optionally is a method for recovering the main fraction of metallic materials containing cobalt and manganese ions. The above units 33, 34, 35, 36 separate the initial fraction of metallic material from the leach solution. It precedes one or more units 32 for.

[0069] Preferably, the copper separation unit 31 is connected to said unit 32 for separating the initial metal fraction. The latter unit 32 is most preferably located upstream of at least one solvent extraction unit. Includes knitwear.

[0070] The copper powder obtained from the copper separation unit 31 is typically separated from the solution after recovery. For this purpose, the installation preferably comprises a sub-unit for settling the powder and a followed by a solid-liquid separation subunit, such as a clarifier, hydrocyclone, decanter or filter. filter, or one or more of these.

[0071] To carry out said separation and recovery, various types of equipment, further leaching or washing unit, solvent extraction unit, precipitation unit, ion exchange unit, and electrowinning unit However, a solvent extraction unit is preferred. For separation of the components, it is preferred to utilize at least one solvent extraction unit. Preferably, the solvent extraction unit is preceded by a solid separation unit, is preceded by a precipitation unit for such impurities.

[0072] Therefore, the units 33, 34, 35, 36 for recovering the main fraction are at least Units 35, 36 for recovering nickel ions and lithium ions, and Optionally, separate sub-units for recovering manganese and cobalt ions are provided. Includes numbers 33 and 34.

[0073] The units 34, 35 for recovering nickel and cobalt are combined or separate, preferably separate, cobalt recovery unit 34 is located upstream of the nickel recovery unit 35, thus providing the individual pure metal products. Provide the necessary equipment.

[0074] The units 34, 35 for recovering nickel and cobalt preferably comprise a solvent It includes an extraction unit, more preferably connected to a crystallization unit, to produce pure product crystals. Complete.

[0075] The unit 36 ​​for recovering lithium, in turn, preferably recovers all other metals. The separation units 31, 32, 33, 34, and 35 are located downstream of the separation units 31, 32, 33, 34, and 35, and typically produce lithium with high yields. It contains one or two subunits for conversion into a recoverable form.

[0076] The optional manganese recovery unit 33 preferably recovers cobalt, nickel, and lithium. It is located upstream of the units 34, 35, 36 for recovering ammonium, and is usually It contains one or both of a unit and a precipitating subunit.

[0077] The equipment of the above-described embodiment is configured to be suitable for use in the method of the present invention. It is particularly preferred that

[0078] The disclosed embodiments of the invention may be modified in any way by the specific structures, process steps, and methods disclosed herein. The present invention is not limited to the above or other materials recognized by those of ordinary skill in the relevant art. It is understood that the term "common" as used herein extends to equivalents thereof, which may be recognized by those skilled in the art. The terminology employed is used only for the purpose of describing particular embodiments and is not intended to be limiting. Please understand that this is not the case.

[0079] Throughout this specification, references to an embodiment or embodiments are made in connection with the embodiment. The particular feature, structure, or characteristic described is included in at least one embodiment of the present invention. Therefore, in various places throughout this specification, the phrase "in one embodiment ( "in one embodiment" or "in an embodiment" Although phrases such as "about" and "about" appear in the same Use terms such as "about" or "substantially" to describe numerical values. If applicable, the exact figures will also be disclosed.

[0080] As used herein, a plurality of items, structural elements, components, and / or materials For convenience, these lists are sometimes presented in a common list. However, Resolves members as if they were individually identified as separate and unique members. In addition, various embodiments and examples of the present invention may be used in various configurations thereof. Alternatives of elements may be mentioned herein. and alternatives are not to be construed as de facto equivalents of each other, but as separate autonomous aspects of the present invention. It is understood that the above statements are to be considered as expressions of a kind.

[0081] As a further feature, the described structure or characteristic may be used in one or more embodiments. , can be combined in any suitable way.

[0082] The above-described embodiments illustrate the principles of the present invention in one or more specific applications. However, numerous changes in form, use and details of implementation may be made without the exercise of inventive faculty. It will be apparent to those skilled in the art that this can be done without departing from the principles and concepts of the present invention. It will be clear. [Industrial Applicability]

[0083] The method, and the equipment suitable for use in said method, is based on the black cellulose obtained from lithium ion batteries. It can replace traditional alternatives for recovering metals from aggregates.

[0084] In particular, the method and apparatus of the present invention allows for the extraction of copper, nickel, and lithium from such battery materials. to recover lithium, and possibly cobalt and manganese, in good yields; To provide an economical and efficient procedure. [Explanation of symbols]

[0085] As shown in the figures (see FIGS. 1-4), in accordance with one or more embodiments of the present invention, Knit and outline shapes can be included in the equipment of the present invention, namely: 1 A pre-treatment unit, including or consisting of: That is, 11 Cleaning unit 12 Heating units, for example of the following types: 121 Pyrolysis Subunit 122 Evaporation Subunit 2. A leaching unit, usually with a solid-liquid separation unit; A leaching unit comprising or consisting of: Wow, 21 Acid leaching units, including: 211 Acid or further leaching reagent injection port 212 Temperature adjustment means 3 Metal separation units, including: 31 Copper ion separation unit 311 Nickel inlet 32 Unit for separating the initial fraction of metallic materials 33 Optional unit for manganese recovery 34 Optional unit for cobalt recovery 35 Nickel Recovery Unit 36 Lithium Recovery Unit

Claims

1. A method for extracting metals from black aggregates of a lithium ion battery, the black aggregates being anode and cathode materials, and some copper, and the cathode material contains lithium and nickel, the method comprising the steps of: a) one or more pre-treatment steps in which a fraction of non-metallic materials is separated from the black mass; The pre-treated black mass containing the anode material and the cathode material is recovered. Top and b) one or more leaching steps in which the cathode material of the pretreated black mass is dissolved and a leaching step in which a leaching solution containing dissolved positive electrode material is recovered; and c) separating an initial fraction of one or more metallic materials from the leach solution and a metal separation step in which a major fraction containing cadmium and lithium is recovered; i) The metal separation step is performed by cementation of copper using nickel as a reducing agent. and a copper recovery step carried out before the nickel of the leach solution is recovered. fruit, ii) nickel is recovered after copper recovery and before lithium recovery; and iii) Nickel is recovered by solvent extraction; the metal separation step; A method comprising:

2. 10. The method of claim 1, wherein the method is used to extract metals from black aggregates. The positive electrode material is composed of lithium and nickel, and optionally one or more of manganese, nickel, and nickel. and aluminum in the form of oxides.

3. The method according to claim 1 or 2, wherein the black aggregate containing copper as a metal is converted into gold. The method used to extract the genera.

4. The method according to any one of claims 1 to 3, wherein the pretreatment step comprises one or more washing and / or a heating step, the heating step preferably being pyrolysis or is carried out to effect evaporation.

5. The method according to any one of claims 1 to 4, wherein the pretreatment step is carried out by removing an organic compound or the like. This is carried out to separate the non-metallic components from the black aggregates, resulting in the separation of the organic compounds in triplicate. % by weight, preferably less than 1.5% by weight.

6. The method according to any one of claims 1 to 5, wherein at least one leaching step , operated with additional acid and one or more leaching reagents, the acids being preferably hydrochloric acid, nitric acid, methyl The acidic leach solution is selected from the group consisting of ethanesulfonic acid, oxalic acid, citric acid, and sulfuric acid. The leaching reagent is preferably selected from hydrogen peroxide, carbohydrates, and sulfur dioxide. 。

7. The method according to any one of claims 1 to 6, wherein the main fraction comprises at least 2 The step for recovering nickel ions and lithium ions comprises removing the metallic material from the leach solution. The method is preceded by one or more steps for isolating an initial fraction of

8. 8. The method according to claim 1, wherein the initial fraction of metallic material contains iron ions. at least one of cations, aluminum ions, calcium ions, and fluoride ions; Optionally, phosphate ions are included.

9. The method according to any one of claims 1 to 8, wherein the separation of the initial fraction of metallic material is carried out by means of a solvent. At least one step is carried out as a solvent extraction, The purpose is to remove impurities from the leach solution, optionally preceded by solids separation, to remove all solids. This method removes organic impurities and also increases the selectivity of solvent extraction.

10. The method according to any one of claims 1 to 9, wherein the separation of the initial fraction of metallic material is carried out by sedimentation. and at least one step carried out as a filter, and impurities such as iron and aluminum are removed. It is intended to remove the leachate, as well as any phosphates that may be present, from the leach solution and is preferred. or a method followed by solvent extraction.

11. The method according to any one of claims 1 to 10, wherein copper is present in the initial fraction of the metallic material. The method of claim 1, wherein the leachate is recovered from the leach solution prior to separation.

12. The method according to any one of claims 1 to 11, wherein copper is reacted with nickel as a reducing agent. The cementation step used, or cementation followed by solvent extraction, The resulting copper-depleted solution is then recovered from the leach solution and used for subsequent metal separation. The method is conveyed in steps.

13. In the method according to any one of claims 1 to 12, the powdered metallic nickel is A method used in cementation.

14. The method according to any one of claims 1 to 13, wherein the leach solution and copper cementation The nickel from both the phosphate and phosphate groups was recovered by solvent extraction and dissolved in a nickel sulfate solution (NiSO 4 ), preferably using extraction chemicals with carboxylic acid functionality, and suitable extraction An example of a commercially available chemical is Versatic TM 10, which is neodecanoic acid ,method.

15. The method according to any one of claims 1 to 14, wherein the leach solution and copper cementation Nickel from both the phosphate and phosphate groups is recovered by solvent extraction to produce a nickel sulfate solution. The solution can be used as is or can be further purified by ion exchange and optionally crystallization. or precipitated to hydroxide or carbonate.

16. The method according to any one of claims 1 to 15, wherein the metal separation step comprises removing copper. and recovering cobalt from the removed leach solution, wherein the recovery of cobalt comprises recovering cobalt from the removed leach solution. The process is carried out simultaneously with or immediately before the recovery of nickel, preferably immediately before the recovery of nickel.

17. The method according to any one of claims 1 to 16, wherein the metal separation step comprises removing copper. and recovering cobalt from the removed leach solution, wherein the recovery of cobalt comprises the step of adding cobalt sulfate. CoSO solution 4 ), preferably by solvent extraction to generate phosphinic acid functional groups An example of a suitable extraction chemical is , trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphonium Cyanex, also known as Finate TM 272, the method.

18. The method according to any one of claims 1 to 17, wherein the metal separation step comprises removing copper. and recovering cobalt from the removed leach solution, wherein the recovery of cobalt comprises the step of recovering cobalt by adding cobalt sulfate. This is done by solvent extraction to produce an ionized solution, which can be used as is or It may be further purified by ion exchange and optionally crystallization, or may be converted to hydroxide or carbonate. The method is as follows:

19. The method according to any one of claims 1 to 18, wherein lithium is present in the leaching solution. The lithium is recovered after all the manganese, cobalt, and nickel that are involved in the recovery are recovered. , for example, by reacting lithium with a carbonate or phosphate reagent, and optionally optionally followed by further conversion, evaporation or crystallization.

20. The method according to any one of claims 1 to 19, wherein the metal separation step comprises removing copper. and recovering manganese from the removed leach solution, said step being carried out after copper separation. preferably before any recovery of nickel or cobalt takes place, more preferably This is carried out before any recovery of cobalt, nickel or lithium takes place, and Recovery may be carried out, for example, by solvent extraction or precipitation, or by solvent extraction followed by precipitation. How to do it.

21. To extract metals from the black aggregates of lithium-ion batteries, the negative and positive electrode materials of the battery The positive electrode material contains lithium and nickel, and the metal is extracted from the black aggregate. The equipment is - Separating a fraction of non-metallic components from the black aggregate and pre-treating it to contain anode and cathode materials. one or more pre-processing units (1) for recovering the processed black aggregates; - dissolving the cathode material of the pretreated black mass and forming a leachate containing the dissolved cathode material; one or more leaching units (2) for recovering the solution; - Separating an initial fraction of one or more metallic materials from the leach solution and extracting at least nickel and lithium a metal separation unit (3) for recovering the main fraction containing lithium, The metal separation unit (3) further comprises or includes a cementation unit The copper separation unit (31) comprises a nickel inlet (3 11) and located upstream of all units (35) intended for nickel recovery. 、 The unit (35) for recovering nickel is located below the copper separation unit (31). a lithium recovery unit (36) upstream of the lithium recovery unit (36); and The unit (35) for recovering nickel is a sub-unit for solvent extraction. The present invention relates to a method for producing a hologram, the metal separation unit (3); Equipped with, facilities.

22. 22. The installation according to claim 21, wherein the pre-treatment unit (1) is adapted to separate organic compounds from black aggregates. A cleaning unit (11) or a heating unit (12) for removing non-metallic components of objects, etc. , or both, and the heating unit (12) preferably comprises a pyrolysis unit or Selected from evaporation units, equipment.

23. 23. The installation according to claim 21 or 22, wherein the metal separation unit (3) comprises at least Units (35, 36) for recovering nickel ions and lithium ions, and optionally further units for recovering manganese ions and cobalt ions ( 33, 34), and all recovery units (33, 34, 35, 36) preferably include , downstream of one or more units (32) for separating an initial fraction of metallic material from the leach solution. and most preferably includes at least one solvent extraction unit.

24. In the installation according to any one of claims 21 to 23, the copper separation unit (31) comprises: An installation located upstream of a unit (32) for separating the initial metal fraction from the leach solution.

25. The method according to any one of claims 1 to 20, further comprising the step of: The method is carried out using the equipment described above.

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