Method for selectively capturing chemical elements from a polymetallic sample

Abstract

The present invention relates to a method for selectively capturing chemical elements from a multi-metal liquid sample.

Description

Technical Field

[0001] The present invention relates to a method for selectively capturing chemical elements from a multi-metal liquid sample.

Background Art

[0002] Energy storage has become a global issue and a major challenge. Since 1980, the world's annual consumption of oil has been exceeding the newly discovered reserves. Therefore, it is necessary to turn to other energy sources such as renewable energy and develop technologies for storing these energies in order to manage them better. The efforts to reduce oil consumption are particularly related to the development of electric vehicles and batteries. Lithium-ion batteries are currently widely used in computers and mobile phones, but there are still some limitations for large-scale applications such as electric vehicles. In particular, such applications require large amounts of strategic metals such as cobalt or rare earth metals, which are expensive. Therefore, the development of effective and selective recycling processes in this field is extremely important.

[0003] To date, few methods have been developed for capturing and separating strategic metals, such as those contained in batteries.

[0004] One method is based on a liquid-liquid extraction technique between an aqueous phase and an oil fraction using synthetic surfactants (ACS Sustainable Chem. Eng. 2018, 6, 13611-13627). However, this method is costly, results in low yields, and is not environmentally compliant.

[0005] Another method is based on affinity chromatography. A specific molecule is chemically grafted onto a solid support, and the solid support is determined according to the properties of the metal to be separated. The metal is selectively adsorbed onto the solid support according to the properties of the graft. The separation is carried out by hydrolysis using a strong acidic or basic solution. This process is effective but extremely costly and requires the use of highly reactive effluents.

[0006] WO 2014 / 188115 describes a method suitable for the detection, capture, and / or selective release of chemical elements selected from base metals, alkali metals, alkaline earth metals, actinides, and rare earths. This method uses a molecular assembly, which is formed by contacting at least one amine and at least one aldehyde and / or one imine and / or CO2, or an adduct formed by contacting an amine and CO2, and at least one of these chemical elements. At the end of this process, a precipitate is recovered, and the metal can be recovered from such a precipitate. This process has advantages that cannot be denied from an economic perspective but is not optimized for industrial scale.

[0007] WO 2017 / 191042 describes a similar process optimized for industrial scale. In such a process, when an organic reagent and a metal are contacted under specific conditions, a split stream is generated, thereby enabling the continuous capture of the metal. However, the metal is captured in the form of an amine carbamate complex, so in subsequent steps, it is necessary to convert the complex into a metal salt that can be conveniently and directly marketed. In addition, this process is only applicable to the separation of two chemical elements. This is insufficient for batteries that may contain up to ten different chemical elements.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

[0009] [Non-Patent Document 1] ACS Sustainable Chem. Eng. 2018, 6, 13611-13627 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] Therefore, there remains a need for an effective method capable of selectively capturing chemical elements from a multi-metal sample, wherein the chemical elements are obtained directly in a convenient form. [Means for Solving the Problems]

[0011] In this regard, the present inventors have developed an effective method that enables the capture of chemical elements from a multi-metal liquid sample by selective precipitation. This method uses a simple combination of reaction raw materials such as CO2, amines, or copper ions and can be carried out under mild conditions. In order to optimize the techno-economic characteristics of this method, the latter is preferably carried out at high concentrations. In addition, the chemical elements to be captured are obtained in a convenient and directly marketable form, typically in the form of carbonate, hydroxide salt, or oxide salt.

[0012] Therefore, the present invention is a method for capturing three chemical elements M1, M2, M3 contained in a liquid sample, and optionally a fourth chemical element M4, the method comprising the following steps: a) contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase, solid M1, and optionally solid M2; b) recovering the solid M1 and optionally the solid M2; c) contacting the first liquid phase with copper ions to obtain a second liquid phase; d) contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, solid M3, optionally solid M4, and optionally solid M2; e) recovering the solid M3, optionally the solid M4, and optionally the solid M2; comprising wherein the solid M2 is recovered in step b) and / or step e); M1 is selected from the group consisting of iron, aluminum, titanium, rare earths, actinides, and combinations thereof; M2 is manganese, and M3 and M4 are each independently selected from the group consisting of nickel, cobalt, and combinations thereof; relating to a method.

[0013] In certain embodiments, M1 is iron, aluminum, a rare earth selected from lanthanum and praseodymium, or a combination thereof. In another particular embodiment, M3 is nickel and M4 is cobalt.

[0014] In another particular embodiment, - the solid M1 is a carbonate, hydroxide, oxide, or combination thereof of M1; - the solid M2 is a carbonate, hydroxide, oxide, or combination thereof of M2; - the solid M3 is a carbonate, hydroxide, oxide, or combination thereof of M3, and / or - the solid M4 is a carbonate, hydroxide, oxide, or combination thereof of M4.

[0015] In another specific embodiment, at least one amine to be used in step a) is selected from the group consisting of ethylenediamine (EDA), propanediamine, diethylenetriamine (DETA), triethylenetetramine, tris-(2-aminoethyl)amine, lysine, glycine, 2,3-diaminopropionic acid, 2,4-diaminobutyric acid, and 2,5-diaminopentanoic acid, preferably selected from ethylenediamine and diethylenetriamine.

[0016] In a specific embodiment, the solid M2 is recovered in step b).

[0017] In a more specific embodiment, the method of the present invention is as follows: - Step a) comprises contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase, a solid M1, and a solid M2. - Step b) comprises continuously recovering the solid M1 and the solid M2.

[0018] In a preferred embodiment, the series of steps a) and b) are i) contacting the liquid sample with at least one amine to obtain a liquid phase L0 and a solid M1; ii) recovering the solid M1; iii) contacting the liquid phase L0 with CO2 and optionally at least one amine under an inert atmosphere to obtain the first liquid phase and a solid M2; and iv) recovering the solid M2 including.

[0019] In another preferred embodiment, the series of steps a) and b) are i’) contacting the liquid sample with at least one amine and CO2 under an inert atmosphere to obtain a liquid phase L0’; ii’) heating the liquid phase L0’ to a temperature T1 higher than room temperature under an inert atmosphere to obtain a liquid phase L0” and a solid M1; iii’) recovering the solid M1; iv’) heating the said liquid phase L0” in an oxygen-containing atmosphere to a temperature T2 higher than room temperature to obtain the said first liquid phase and the solid M2 as defined herein, and v’) recovering the solid M2 comprising. Preferably, the temperatures T1 and T2 are each independently included between 70 °C and 110 °C, more preferably about 100 °C.

[0020] Preferably, the series of steps d) and e) are α) contacting the said second liquid phase with a carbonate and optionally a hydroxide to obtain a liquid phase L1 and a solid M3, β) recovering the said solid M3, γ) contacting the said liquid phase L1 with a reducing agent to obtain a third liquid phase and a solid M4, and δ) recovering the said solid M4 comprising.

[0021] In a particular embodiment, the reducing agent is a solid metal such as metallic cobalt, metallic iron, or metallic copper, CO2, or activated carbon.

[0022] In another particular embodiment, the solid M2 and optionally the solid M4 are recovered in step e). In such an embodiment, M2, M3, and optionally M4, which are each solid, are preferably recovered in the form of one single salt, preferably a carbonate, a hydroxide, or a combination thereof.

[0023] In another particular embodiment, the liquid sample further contains a chemical element M5, and the method of the present invention comprises, after step e), the following steps: f) precipitating the solid M5 from the third liquid phase to obtain a solid M5 and a fourth liquid phase; and g) recovering the solid M5, preferably by filtration, centrifugation, or reverse osmosis further comprising, M5 is copper.

[0024] In certain embodiments, prior to step a) of the method of the present invention, - leaching lithium from a solid sample containing lithium, M1, M2, M3, and optionally M4 to obtain a solid sample containing the leached lithium, as well as M1, M2, M3, and optionally M4; - recovering the leached lithium; - converting the solid sample containing M1, M2, M3, and optionally M4 into a liquid sample containing M1, M2, M3, and optionally M4, wherein the liquid sample corresponds to the liquid sample prepared in step a) of the method according to the present invention are further included.

[0025] In another particular embodiment, the liquid sample further contains lithium, and the method of the present invention, after step e) or step g), comprises the following steps: h) concentrating the third or fourth liquid phase to obtain solid lithium; j) recovering the solid lithium, preferably by filtration, centrifugation, or reverse osmosis.

[0026] In certain embodiments, the contacting step of the method of the present invention is carried out in water.

[0027] In another particular embodiment, each of the recovery steps of the method of the present invention is independently carried out by filtration, centrifugation, or reverse osmosis. **DETAILED DESCRIPTION OF THE INVENTION**

[0028] In the present application, the term "about" preceding a value is well known to those skilled in the art and means that the value can vary to a certain extent depending on the context in which the term is used. If the specific use of this term is not clear to those skilled in the art from the context, "about" means ±20% of the value, preferably ±10%. Unless otherwise indicated, when a range is expressed by the phrase "comprised between ~", the limiting values are included within the recited range.

[0029] The method of the present invention enables the capture (or "recovery") and optionally the detection of at least three, preferably at least four, for example four, five, six, or seven chemical elements from a multi-metal liquid sample, typically by selective precipitation. Each of the chemical elements is independently obtained in solid form, in particular in the form of salts such as carbonates, hydroxides, oxides, or combinations thereof. The capture or recovery of the chemical elements by the method according to the invention is typically carried out after observing (or "detecting") the precipitate after bringing different components and / or reactants into contact. Advantageously, the detection additionally comprises comparing the sample obtained with a similar sample that does not contain the chemical element and can be referred to as a reference sample. Similarly, the detection may additionally comprise comparing the sample obtained with a similar sample that contains the chemical element. The duration of each contact step of the method of the present invention can be appropriately adjusted by a person skilled in the art and may in particular be determined by the time required for the precipitate to be fully formed after the contact of the components and / or reactants.

[0030] The liquid sample on which the capture method according to the invention is carried out can be any type of liquid sample containing the chemical elements M1, M2, M3, and optionally M4 as defined herein. It can be a liquid sample of any origin. For example, the liquid sample may be derived from batteries, waste from battery manufacturing, effluents from the steel or dairy industries, red mud, ores, or fly ash. In a particular embodiment, the liquid sample is a sample derived from a battery, for example a nickel-metal hydride battery or a Li-ion battery, or a component thereof (such as a battery cathode). More specifically, the liquid sample may be obtained by solubilizing or leaching a solid sample containing the chemical elements M1, M2, M3, and optionally M4 as defined herein, said solid sample typically being from a battery, for example a nickel-metal hydride battery or a Li-ion battery, or a component thereof (such as a battery cathode). Such a solubilization or leaching step may be carried out by bringing the solid sample into contact with an aqueous solution containing an acid such as nitric acid, hydrochloric acid, or sulfuric acid. The solid sample has the formula: La2Ni9CoMn, Al x Fe y Ni zMnCoO (wherein x and y are each independently 0.1 to 10, and z is an integer from 1 to 8 (preferably 8)), LiAl w CuFeNi k MnCoO (wherein w is 0.1 to 10, and k is an integer from 1 to 8 (preferably 8)), or LiAl 0.1 Ni 0.8 Co 0.1 Mn 0.1 Any one of O may be used. Preferably, the liquid sample is an aqueous solution containing chemical elements M1, M2, M3, and optionally M4 as defined herein. M1, M2, M3, and (if present) M4 in the liquid sample are typically in the form of cations. The concentration of M1 in the liquid sample is preferably 0.5 mol / L or less, for example, between 0.05 and 0.25 mol / L, or between 0.10 and 0.25 mol / L. The concentration of M2 in the liquid sample is preferably 0.5 mol / L or less, for example, between 0.05 and 0.20 mol / L, or between 0.10 and 0.20 mol / L. The concentration of M3 in the liquid sample is preferably 0.75 mol / L or less, for example, between 0.05 and 0.55 mol / L, or between 0.25 and 0.55 mol / L. The concentration of M4 (if present) in the liquid sample is preferably 0.5 mol / L or less, for example, between 0.05 and 0.20 mol / L, or between 0.10 and 0.20 mol / L. The concentration of each chemical element in the liquid sample (i.e., their initial concentration) can be determined by titration ICP (inductively coupled plasma spectrometry).

[0031] M1 is a chemical element selected from the group consisting of iron, aluminum, titanium, rare earth metals, actinides, and combinations thereof. As used herein, "actinide" refers to one or more of the following: actinium 89 Ac, thorium 90 Th, protactinium 91 Pa, uranium 92U, Neptunium 93 Np, Plutonium 94 Pu, Americium 95 Am, Curium 96 Cm, Berkelium 97 Bk, Californium 98 Cf, Einsteinium 99 Es, Fermium 100 Fm, Mendelevium 101 Md, Nobelium 102 No, and Lawrencium 103 Lr.

[0032] As used herein, "rare earth" (or "rare earth metal" in a similar sense) refers to one or more of the following: Scandium 21 Sc, Yttrium 39 Y, and 15 lanthanide metals. The lanthanide metals are Lanthanum 57 La, Cerium 58 Ce, Praseodymium 59 Pr, Neodymium 60 Nd, Promethium 61 Pm, Samarium 62 Sm, Europium 63 Eu, Gadolinium 64 Gd, Terbium 65 Tb, Dysprosium 66 Dy, Holmium 67 Ho, Erbium 68 Er, Thulium 69 Tm, Ytterbium 70 Yb, and Lutetium 71 Lu. In certain embodiments, the rare earth metal is lanthanum or praseodymium. Preferably, M1 is a rare earth selected from iron, aluminum, lanthanum, and praseodymium, or a combination thereof.

[0033] M2 is manganese.

[0034] M3 and M4 are each independently a chemical element selected from the group consisting of nickel, cobalt, and combinations thereof. Preferably, M3 is nickel. Preferably, M4 is cobalt.

[0035] "Solid M1" refers to a solid containing the chemical element M1, particularly a solid salt. Preferably, "solid M1" is a carbonate of M1, a hydroxide of M1, an oxide of M1, or a combination thereof. A specific combination is a carbonate-hydroxide of M1. As used herein, "solid M2" refers to a solid containing the chemical element M2, particularly a solid salt. Preferably, "solid M2" is a carbonate of M2, a hydroxide of M2, an oxide of M2, or a combination thereof. A specific combination is a carbonate-hydroxide of M2. As used herein, "solid M3" refers to a solid containing the chemical element M3, particularly a solid salt. Preferably, "solid M3" is a carbonate of M3, a hydroxide of M3, an oxide of M3, or a combination thereof. A specific combination is a carbonate-hydroxide of M3. As used herein, "solid M4" refers to a solid containing the chemical element M4, particularly a solid salt. Preferably, "solid M4" is a carbonate of M4, a hydroxide of M4, an oxide of M4, or a combination thereof. A specific combination is a carbonate-hydroxide of M4.

[0036] The amine according to the present invention is a compound containing at least one, preferably one or two, primary or secondary amine groups, and optionally at least one tertiary amine group. The amine according to the present invention has the general formula (IV) R2-NH-R3 (wherein R2 is selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl groups, and aromatic groups, and at least one heteroatom selected from N, O, and S may be inserted into their hydrocarbon chains, and they are optionally substituted by at least one substituent, and their substituents preferably do not contain aldehyde CHO; R3 is selected from a hydrogen atom, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl groups, and aromatic groups, and at least one heteroatom selected from N, O, and S may be inserted into their hydrocarbon chains, and they are optionally substituted by at least one substituent). Preferably, the substituents independently do not contain aldehyde CHO. In certain embodiments, the amine contains at least two amine groups, preferably at least three, at least four, or at least five amine groups. In particular, the amine is such that R3 is a hydrogen atom and R2 is an alkyl group, and its hydrocarbon chain is preferably interrupted by at least one nitrogen atom and is optionally substituted by one -COOH group. In such embodiments, R2 may be an alkyl group substituted by at least one NH2 substituent, preferably substituted by a single NH2 substituent, more preferably an alkyl group terminated by a single NH2 substituent. In such embodiments, R2 is preferably interrupted by at least one N atom, preferably by 1, 2, or 3 N atoms.

[0037] Preferably, the amine according to the present invention is selected from the following compounds:

[0038]

Chemical formula

[0039] In certain embodiments, the amine is a basic amino acid (preferably non-proteinogenic), such as 2,3-diaminopropionic acid (i.e., [Chemical formula] ), 2,4-diaminobutyric acid (i.e., [Chemical formula] ), or 2,5-diaminopentanoic acid (i.e., [Chemical formula] ). The basic amino acid may be of the formula (IV) as defined above, wherein R2 is preferably an alkyl group containing 1 to 6 carbon atoms and substituted by at least one NH2 substituent and at least one CO2H substituent, preferably substituted by a single NH2 substituent and a single CO2H substituent.

[0040] The amine may be an amine from a low-moisture solvent, such as N-methylethylenediamine, N,N-dimethylethylenediamine, N,N'-dimethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, or 1,3-propanediamine.

[0041] In one embodiment, the amine is selected from the group consisting of glycine, 2,3-diaminopropionic acid, 2,4-diaminobutyric acid, 2,5-diaminopentanoic acid, lysine, ethylenediamine, 1,5-diaminopentane, diethylenetriamine, N-(3-aminopropyl)1,4-butanediamine, N-methylethylenediamine, N,N-dimethylethylenediamine, N,N'-dimethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, and 1,3-propanediamine.

[0042] More preferably, the amine is ethylenediamine (i.e.,

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[0043] The amine may be water-miscible or non-water-miscible.

[0044] The carbon dioxide used in the method of the present invention (in particular, steps a), i'), and / or iii)) may be a result of human activities, among which waste is representative and may be derived from, for example, combustion flue gas, refinery gas, cement plant gas, or blast furnace gas.

[0045] In step a) of the method of the present invention, a liquid sample is contacted with at least one amine and optionally CO2 to obtain a first liquid phase, solid M1, and optionally solid M2.

[0046] In a specific embodiment, solid M2 is recovered in step b). In such an embodiment, - Step a) includes contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase, solid M1, and solid M2, - Step b) includes recovering the solid M1 and the solid M2.

[0047] The liquid sample, at least one amine, and optionally CO2 may be contacted simultaneously or continuously in step a). Advantageously, the contacting step a) is carried out in water. More specifically, the liquid sample is typically an aqueous solution and no additional solvent is used to carry out the contacting step a). In such an embodiment, the amine is preferably water-miscible. The concentration of the amine in step a) may be included between 0.05 M and 15 M, preferably between 0.5 M and 10 M, more preferably between 2 M and 5 M. The recovery of solid M1 and solid M2 in step b) is preferably carried out continuously and is typically carried out during and / or after the contacting of the liquid sample, at least one amine, and optionally CO2 in step a). Advantageously, the recovery of solid M1 and the recovery of the solid M2 are each independently carried out by filtration, centrifugation, and / or reverse osmosis.

[0048] In certain embodiments, steps a) to b) of the method of the present invention are i) contacting the liquid sample with at least one amine to obtain a liquid phase L0 and a solid M1; ii) recovering the solid M1; iii) contacting the liquid phase L0 with CO2 and optionally at least one amine under an inert atmosphere to obtain the first liquid phase and a solid M2; and iv) recovering the solid M2 and include.

[0049] Advantageously, contacting steps i) and iii) are carried out in water. More particularly, the liquid sample and the liquid phase L0 are typically aqueous solutions and no additional solvent is used to carry out contacting steps i) and iii). The at least one amine in step i) and optionally the at least one amine in step iii) may be the same or different, preferably the same. The concentration of the amine in step i) (and optionally in step iii)) may be between 0.05 M and 15 M, preferably between 0.5 M and 10 M, more preferably between 2 M and 5 M. The amount of amine in step i) may be adjusted to reach a pH favorable for the formation of solid M1 (or "precipitation" in a similar sense). Such a pH is typically about 6. The amount of CO2 (and, if present, the amount of amine added in step iii)) may be adjusted to reach a pH favorable for the formation of solid M2 (or "precipitation" in a similar sense). Such a pH is typically about 8. Contacting step iii) is carried out under an inert atmosphere. As used herein, "inert atmosphere" refers to an atmosphere substantially free of oxygen. The inert atmosphere may in particular be created by substantially replacing the air in the vessel in which the contacting step is carried out with an inert gas. Any suitable inert gas may be used to create the inert atmosphere. Preferably, the inert gas is argon, nitrogen, or a combination thereof, more preferably argon. The contacting step i) may be carried out in an inert atmosphere or in an oxygen-containing atmosphere, preferably in an inert atmosphere. The contacting steps i) and iii) are advantageously carried out at room temperature, especially when carried out in an inert atmosphere. The term "room temperature" is well known to those skilled in the art and typically refers to a temperature included between 15°C and 35°C, preferably between 20°C and 30°C. The recovery of the solid M1 in step ii) and the recovery of said solid M2 in step iv) are typically carried out by filtration, centrifugation, and / or reverse osmosis. In steps i) and ii), the solid M1 is preferably a hydroxide or carbonate of M1. In certain embodiments, M1 in steps i) and ii) is aluminum and the solid M1 is aluminum hydroxide (typically of the formula Al(OH)3). In steps iii) and iv), the solid M2 is preferably a carbonate of M2 (i.e., manganese carbonate, typically of the formula MnCO3), a carbonate-hydroxide of M2, or an oxide of M2, more preferably a carbonate of M2.

[0050] In another specific embodiment, steps a)-b) of the method of the present invention are i') contacting a liquid sample with at least one amine and CO2 in an inert atmosphere to obtain a liquid phase L0'; ii') heating the liquid phase L0' to a temperature T1 higher than room temperature in an inert atmosphere to obtain a liquid phase L0'' and a solid M1; iii') recovering the solid M1; iv') heating the liquid phase L0'' to a temperature T2 higher than room temperature in an oxygen-containing atmosphere to obtain the first liquid phase as defined herein and a solid M2, and v') recovering the solid M2 and comprising.

[0051] A specific "oxygen-containing atmosphere" is oxygen (i.e., O2) or air, preferably air.

[0052] Advantageously, steps i'), ii'), and iv') are carried out in water. More specifically, the liquid sample and the liquid phase L0' are typically aqueous solutions, and no additional solvent is used to carry out steps i'), ii'), and iv'). Preferably, in step i'), the contact is carried out as follows: an aqueous solution of an amine is contacted with CO2, typically by aeration (bubbling), preferably until a pH of about 7 is reached, to form a reaction mixture. Then, the liquid sample is contacted with the reaction mixture. The concentration of the amine in step i') is independently between 0.05 M and 15 M, preferably between 0.5 M and 10 M, more preferably between 2 M and 5 M. Preferably, the temperatures T1 and T2 are each independently between 70 °C and 110 °C, preferably about 100 °C. The recovery of the solid M1 in step iii') and the recovery of the solid M2 in step iv') are typically carried out by filtration, centrifugation, or reverse osmosis. In steps ii') and iii'), the solid M1 is preferably the hydroxide or carbonate of M1. In certain embodiments, in steps ii') and iii'), M1 is aluminum and the solid M1 is preferably aluminum hydroxide. In steps iv') and v'), the solid M2 is preferably the oxide of M2 (i.e., manganese oxide, typically of the formula MnO2).

[0053] In another specific embodiment, steps a)-b) of the method of the present invention are i”) contacting the liquid sample with at least one amine (and optionally CO2) to obtain a liquid phase L and a solid M1, ii”) recovering the solid M1, iii”) precipitating a solid M2 from the liquid phase L to obtain the first liquid phase and the solid M2 as defined herein, and iv”) recovering the solid M2 and include.

[0054] The precipitation process iii”) particularly includes iii”-a) contacting the liquid phase L with CO2 (and optionally at least one amine) in an inert atmosphere, or iii”-b) heating the liquid phase L to a temperature T3 higher than room temperature in an oxygen-containing atmosphere and may include.

[0055] Advantageously, steps i”) and iii”) are carried out in water. More specifically, the liquid sample and the liquid phase L are typically aqueous solutions, and no additional solvent is used to carry out such steps. Step i”) can be carried out either in an oxygen-containing atmosphere or in an inert atmosphere. The amount of amine in step i”) may be adjusted to reach a pH favorable for the formation of solid M1 (or “precipitation” in a similar sense). Such a pH is typically about 6. The concentration of amine in step i”) (and optionally in step iii”-a)) may be included between 0.05M and 15M, preferably between 0.5M and 10M, more preferably between 2M and 5M. Preferably, the temperature T3 is included between 70°C and 110°C, preferably about 100°C. The recovery of solid M1 in step ii”) and the recovery of said solid M2 in step iv”) are typically carried out by filtration, centrifugation, or reverse osmosis. In steps i”) to ii”), the solid M1 is preferably the hydroxide or carbonate of M1. In certain embodiments, M1 is aluminum, and the solid M1 is preferably aluminum hydroxide. In step iii”-a), the solid M2 is preferably obtained as the carbonate of M2 (i.e., manganese carbonate). In step iii”-b), the solid M2 is preferably obtained as the oxide of M2 (i.e., manganese oxide).

[0056] In certain embodiments, at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of the solid M1, preferably at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 98% is recovered in step b) (or step ii), iii'), or ii")). In certain embodiments, when recovered in step b) (or step iv) or step v')), at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of the solid M2, preferably at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 98% is recovered in step b) (or step iv), step v'), or iv")). In certain embodiments, when recovered in step e), at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of the solid M1, preferably at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 98% is recovered in step e).

[0057] Unless otherwise indicated, the percentage of solid Mn (where n is 1, 2, 3, 4, or 5) recovered in a given step corresponds to the ratio of the molar amount of chemical element Mn recovered as "solid Mn" to the total molar amount of chemical element Mn in the original liquid sample (or, in a similar sense, the original solid sample from which the liquid sample was obtained).

[0058] In certain embodiments of the present invention, solid M2 is recovered in step e). In such embodiments, - step a) comprises contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase and solid M1, - step b) comprises recovering the solid M1. In particular, in such embodiments, steps a) to b) may include steps i) to ii) as described above, steps i') to iii') as described above, or steps i") to ii") as described above.

[0059] As used herein, "the first liquid phase" refers to the following liquid phase: - That obtained after recovering solid M1 and optionally solid M2 from a liquid sample, and - That carried out in step c) of the method of the present invention. The content of the first liquid phase may vary depending on the conditions under which steps a) and b) are carried out. In embodiments where solid M2 is recovered in step b) (or step iv), step v'), or step iv")), "the first liquid phase" refers to the following liquid phase: - That obtained after recovering solid M1 and solid M2 from a liquid sample, and - That carried out in step c) of the method of the present invention. In embodiments where solid M2 is recovered in step e), "the first liquid phase" refers to the following liquid phase: - That obtained after recovering solid M1 from a liquid sample, and - That carried out in step c) of the method of the present invention.

[0060] Step c) includes contacting the first liquid phase with copper ions to obtain a second liquid phase. Advantageously, the copper ions in step c) enable the decomplexation between the chemical element M3 already present in the first liquid phase and the amine.

[0061] At least one amine may be used in step c). When the at least one amine is used, the first liquid phase is preferably first contacted with the at least one amine, and then copper ions are added to the mixture containing the first liquid phase and the at least one amine to obtain a second liquid phase. Typically, when at least one amine is already present in the first liquid phase, no additional amine is added in step c). If at least one amine is used in step c), it may be the same as or different from (preferably the same as) at least one amine used in step a) (or step i), iii), i'), or i")). The copper ions may be from any suitable source known to those skilled in the art. Preferably, the copper ions are added in step c) in the form of a copper salt or in the form of an aqueous solution containing such a copper salt. According to the present invention, a copper salt refers to an electrically neutral compound containing cationic copper and one or more monoatomic or polyatomic, monodentate or polydentate, organic or inorganic, anionic ligands. The copper salt has the formula Cu x L y (wherein - L represents a monoatomic or polyatomic, monodentate or polydentate, organic or inorganic, anionic ligand, - x is 1 or 2, preferably 1, - y is 1, 2, or 3, preferably 1 or 2, more preferably 2) can be represented by. Examples of monoatomic or polyatomic, monodentate or polydentate, organic or inorganic, anionic ligands include, but are not limited to, sulfonate ions such as trifluoromethanesulfonate, methanesulfonate, or toluenesulfonate, halides such as chloride ion, bromide ion, or iodide ion, carboxylate ions such as acetate or trifluoroacetate, ketyl - ketonate such as acetylacetonate, tetramethylheptane - dionate, or hexafluoroacetylacetonate, tetrafluoroborate, pentafluorophosphate, hexafluoro - antimonate, nitrite ion, nitrate ion, sulfite ion, sulfate ion, chlorate ion, perchlorate ion, iodate ion, periodate ion, hydroxide ion, and carbonate ion. Preferably, L is chloride ion.

[0062] In certain embodiments, the ligand L is the same as that of the acid used for solubilizing or leaching the solid sample into the liquid sample in the method of the present invention. For example, if the acid is hydrochloric acid, the copper salt is preferably copper chloride.

[0063] The amount of copper ions in step c) is preferably between 1 and 3 molar equivalents, preferably between 1.5 and 2 equivalents, relative to the amount of M3 (or M4).

[0064] Preferably, step c) is carried out in water. More specifically, the first liquid phase is typically an aqueous solution, and no additional solvent is used to carry out step c). Preferably, step c) is carried out at room temperature.

[0065] As used herein, "the second liquid phase" refers to the following liquid phase: - That obtained after contacting the first liquid phase with copper ions (and optionally said at least one amine), and - That carried out in step d) of the present invention.

[0066] Step d) comprises contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, solid M3, and optionally solid M4, and optionally solid M2. Step e) comprises recovering the solid M3, optionally the solid M4, and optionally the solid M2.

[0067] Preferably, step d) is carried out in water. More specifically, the second liquid phase is typically an aqueous solution, and no additional solvent is used to carry out step d). As used herein, "carbonate" refers to "carbonate salt". Preferably, the carbonate is an alkali metal carbonate (such as sodium carbonate, potassium carbonate, or lithium carbonate), or an alkaline earth metal carbonate (such as barium carbonate, calcium carbonate, or magnesium carbonate). More preferably, the carbonate is lithium carbonate (i.e., Li2CO3) or sodium carbonate (i.e., Na2CO3), and even more preferably lithium carbonate. The amount of carbonate in step d) is preferably included between 0.5 and 5 molar equivalents relative to the amount of M3. As used herein, "hydroxide" refers to "hydroxide salt". Preferably, the hydroxide is a hydroxide of an alkali metal (such as sodium hydroxide, potassium hydroxide, or lithium hydroxide), or a hydroxide of an alkaline earth metal (such as barium hydroxide, calcium hydroxide, or magnesium hydroxide). More preferably, the hydroxide is lithium hydroxide or sodium hydroxide, and even more preferably lithium hydroxide. When present, the amount of hydroxide in step d) is preferably included between 0.5 and 1 molar equivalent relative to the amount of M3. In certain embodiments, the amount of carbonate is included between 1 and 5 molar equivalents relative to the amount of M3, and the amount of hydroxide is included between 0.5 and 5 molar equivalents relative to the amount of M3. In certain embodiments, the molar ratio of carbonate to hydroxide in step d) is included between 0.1 and 10, preferably between 0.5 and 2. In certain embodiments, step d) includes contacting the second liquid phase with an aqueous solution containing hydroxide and carbonate of the same metal, such as sodium or lithium, preferably lithium.

[0068] In a specific embodiment, solid M2 is recovered in step b). In such an embodiment, - Step d) includes contacting the second liquid phase with carbonate and optionally hydroxide to obtain a third liquid phase, solid M3, and optionally solid M4, - Step e) includes recovering the solid M3 and optionally the solid M4. Preferably, in such an embodiment, - Step d) includes contacting the second liquid phase with carbonate and optionally hydroxide to obtain a third liquid phase, solid M3, and solid M4, - Step e) includes recovering the solid M3 and the solid M4.

[0069] In a preferred embodiment, the solid M3 and the solid M4 are continuously recovered, typically during and / or after the contact of the second liquid phase, carbonate, and optionally hydroxide in step d).

[0070] In a more specific embodiment, steps d) - e) of the method of the present invention are α) contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a liquid phase L1 and a solid M3, β) recovering the solid M3, γ) contacting the liquid phase L1 with a reducing agent to obtain a third liquid phase and a solid M4, and δ) recovering the solid M4 and include.

[0071] Advantageously, steps α) and γ) are carried out in water. More specifically, the second liquid phase and the liquid phase L1 are typically aqueous solutions, and no additional solvent is used to carry out steps α) and γ). The contacting step α) is advantageously carried out at room temperature. The contacting step γ) is advantageously carried out under heating to room temperature or a temperature T4 higher than room temperature, where T4 is preferably included between 70°C and 110°C, more preferably about 100°C.

[0072] The amount of carbonate in step α) is advantageously included between 0.1 and 10 molar equivalents relative to the amount of M4. If present, the amount of hydroxide in step α) is advantageously included between 0.1 and 10 molar equivalents relative to the amount of M4. In a specific embodiment, the molar ratio of carbonate to hydroxide in step α) is included between 0.1 and 10, preferably between 0.5 and 2.

[0073] As used herein, "reducing agent" refers to any chemical or physical species that can reduce (i.e., lower its oxidation state) the ions of the chemical element M4 contained in the liquid phase L1 in step γ). Advantageously, the use of a reducing agent is favorable for the decomplexation between M4 and the amine. In certain embodiments, the reducing agent is a solid metal (i.e., having an oxidation state of 0), such as metallic cobalt (i.e., Co 0 ), metallic iron (i.e., Fe 0 ), or metallic copper (i.e., Cu 0 ), CO2, or activated carbon. In a preferred embodiment, the reducing agent is metallic cobalt. More specifically, M4 is cobalt and the reducing agent is metallic cobalt. The amount of reducing agent in step γ) is advantageously comprised between 0.5 and 5 molar equivalents relative to the amount of M4. In another specific embodiment, the reducing agent is electrons generated electrochemically.

[0074] In certain embodiments, step γ) comprises contacting the liquid phase L1 with a reducing agent, copper ions, and optionally a carbonate and / or a hydroxide to obtain a third liquid phase and solid M4. Advantageously, combining the reducing agent with the copper ions present in the second liquid phase from step c) and / or those added in step γ) is favorable for the decomplexation between M4 and the amine and for the formation (or "precipitation") of solid M4. The copper ions are preferably added in the form of a copper salt or an aqueous solution containing such a copper salt as described above for step c). Preferably, the copper salt of step c) and the optional copper salt of step γ) are the same.

[0075] In steps α) and β), the solid M3 is preferably a hydroxide, carbonate, or carbonate - hydroxide of M3. In certain embodiments, M3 is nickel and the solid M3 is a carbonate - hydroxide of nickel.

[0076] In steps γ) and δ), the solid M4 is preferably a hydroxide, carbonate, or carbonate - hydroxide of M4. In certain embodiments, M4 is cobalt and the solid M4 is a carbonate - hydroxide of cobalt.

[0077] In another specific embodiment, steps d) - e) of the method of the invention α’) contacting the second liquid phase with a reducing agent, copper ions, and a carbonate (and optionally a hydroxide), preferably in this defined order, to obtain a third liquid phase, solid M3, and solid M4, and β’) recovering the solid M3 and the solid M4 is included.

[0078] In another specific embodiment, solid M2 is recovered in step e). In such an embodiment, - Step d) includes contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, solid M2, solid M3, and optionally solid M4, - Step e) includes recovering the solid M3, the solid M2, and optionally the solid M4. Preferably, in such an embodiment, - Step d) includes contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, solid M2, solid M3, and solid M4, - Step e) includes recovering the solid M3, the solid M2, and the solid M4. In such an embodiment, the conditions (temperature, and the amount of carbonate and optionally hydroxide, etc.) of steps d) and e) are advantageously the same as those above. In particular, step d) is advantageously carried out at room temperature or under heating to a higher temperature T4, where T4 is preferably included between 50 °C and 110 °C. The amount of carbonate in step d) is advantageously included between 0.5 and 5 molar equivalents relative to the amount of M3. If present, the amount of hydroxide in step d) is advantageously included between 0.5 and 1 molar equivalent relative to the amount of M3.

[0079] M2, M3, and optionally M4, which are each solid, are advantageously recovered in step e) in the form of a single salt, preferably a carbonate and / or a hydroxide. When the single salt is both a carbonate and a hydroxide, the carbonate groups (i.e., CO3 2-) the ratio to the hydroxyl group (i.e., HO - ) can vary depending on the method, more specifically the conditions under which step d) or α) is carried out (e.g., pH, the amounts of carbonate and hydroxide introduced in step d) or α)). For example, such a ratio (carbonate / hydroxide) may be included between 0.1 and 2, for example, between 0.1 and 1, or between 0.5 and 2. In certain embodiments, M2 is manganese, M3 is nickel, M4 is cobalt, and M2, M3, and M4, each being solid, are recovered in the form of manganese, nickel, and cobalt carbonate - hydroxide in step e).

[0080] As used herein, the "third liquid phase" refers to the liquid phase obtained after recovering solid M3, and optionally solid M2, and solid M4 (if recovered) from the second liquid phase. It is understood that the content of the third liquid phase can vary depending on the conditions under which steps d) and e) are carried out. In embodiments where solid M2 is recovered in step b) (or step iv) or step v')), the "third liquid phase" refers to the liquid phase obtained after recovering solid M3 and solid M4 (if recovered) from the second liquid phase. In embodiments where solid M2 is recovered in step e), the "third liquid phase" refers to the liquid phase obtained after recovering solid M1, solid M2, and solid M4 (if recovered) from the second liquid phase.

[0081] In certain embodiments, at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of solid M3, preferably at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 98% is recovered in step e) (or step β). In certain embodiments, at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% of the solid M4, preferably at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 98% is recovered in step e) (or step δ).

[0082] In addition to M1, M2, M3, and optionally M4, the liquid sample may further contain copper (hereinafter "M5"). The concentration of M5 (if present) in the liquid sample is advantageously 1 mol / L or less, for example, between 0.01 and 0.5 mol / L. If present, M5 can typically be captured (or "recovered") after step e) of the method of the present invention. In certain embodiments, the method of the present invention, after step e), f) precipitating solid M5 from the third liquid phase to obtain solid M5 and a fourth liquid phase; g) recovering the solid M5, preferably by filtration, centrifugation, or reverse osmosis; and further includes. The precipitation of M5 can be carried out by any suitable method known to those skilled in the art, for example, by contacting the third liquid phase with a sulfide reagent or electrochemically.

[0083] It is understood that the copper ions added in steps c), α), and / or γ) can also be captured (or "recovered") in steps f) and g) above.

[0084] In addition to M1, M2, M3, and optionally M4 and / or M5, the liquid sample may further contain lithium. The concentration of lithium (if present) in the liquid sample is advantageously 1 mol / L or less, for example, between 0.1 and 1 mol / L, or between 0.5 and 1 mol / L.

[0085] Lithium can typically be captured (or "recovered") after step e) or step g) of the method of the present invention. Lithium can be captured, for example, by any suitable method known to those skilled in the art, such as by: - contacting a third liquid phase with a hydroxide (e.g., LiOH) and CO2, - concentrating, - thermally crystallizing, and / or - liquid-solid separation followed by recrystallization by CO2 injection. In certain embodiments, the method of the present invention, after step e) or step g), h) a step of concentrating the third or fourth liquid phase to obtain solid lithium; and j) a step of recovering the solid lithium, preferably by filtration, centrifugation, or reverse osmosis. comprises.

[0086] Preferably, the solid lithium is lithium carbonate.

[0087] Alternatively, if the liquid sample is obtained by solubilizing a solid sample containing lithium and chemical elements M1, M2, M3, and optionally M4 (the solid sample is typically from a battery or its components), lithium may be recovered before the solubilization step of the solid sample. In particular, the method of the present invention, before step a), - leaching lithium from a solid sample containing lithium, M1, M2, M3, and optionally M4 to obtain a leached lithium and a solid sample containing M1, M2, M3, and optionally M4; - recovering the leached lithium; and - converting the solid sample containing M1, M2, M3, and optionally M4 into the liquid sample containing M1, M2, M3, and optionally M4 (typically solubilizing using an aqueous solution containing an acid such as those described above). may comprise.

[0088] The leaching process may typically include contacting a solid sample containing lithium, M1, M2, M3, and optionally M4 with a leaching solution, such as water (e.g., pure water), or an aqueous solution containing at least one amine and CO2. The leaching solution may further contain additives such as a reducing agent (e.g., a solid metal (i.e., having an oxidation state of 0), such as metallic cobalt (i.e., Co 0 ), metallic iron (i.e., Fe 0 ), or metallic copper (i.e., Cu 0 ), CO2, or activated carbon). The leached lithium is typically obtained in the form of lithium carbonate, lithium carbamate, or a mixture thereof.

[0089] The method of the present invention may further include a step for recycling some of the reactants used therein, in particular, - a step of recycling at least one amine from steps a), i), iii), i'), and / or c), and / or - a step of recycling copper ions from steps c), α), and / or γ) may be included.

[0090] As used herein, the term "reactant recycling" typically refers to the recovery and reuse of reactants in subsequent steps of the same method of the present invention or in another method of the present invention. For example, the amine from step a) can be recycled to be reused in step a) of another method of the present invention. Such recycling steps are usually carried out after the step in which the reactant is used or at the end of the method of the present invention, for example, after step e) or g). The at least one amine is usually in its acidic form at the end of the method. The at least one amine can be recycled by using any suitable base (such as a hydroxide) or a basic ion exchange resin. The copper ions can be recycled by stripping or precipitation of the copper salt Cu x L y as defined above.

[0091] In a particular embodiment, the solid M2 is recovered in step b). In such an embodiment, the method of the present invention comprises the following steps: a) contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase, a solid M1, and a solid M2; b) continuously recovering the solid M1 and the solid M2; c) contacting the first liquid phase with copper ions to obtain a second liquid phase; d) contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, a solid M3, and optionally a solid M4; e) continuously recovering the solid M3 and optionally the solid M4. Including. Preferably, in such an embodiment, the method of the present invention comprises the following steps: a) contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase, a solid M1, and a solid M2; b) continuously recovering the solid M1 and the solid M2; c) contacting the first liquid phase with copper ions to obtain a second liquid phase; d) contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, a solid M3, and a solid M4; e) continuously recovering the solid M3 and the solid M4. Including.

[0092] In a preferred embodiment, the method of the present invention comprises the following steps: i) contacting a liquid sample with at least one amine to obtain a liquid phase L0 and a solid M1; ii) recovering the solid M1; iii) contacting the liquid phase L0 with CO2 and optionally at least one amine in an inert atmosphere to obtain a first liquid phase and a solid M2; iv) A step of recovering solid M2; c) A step of bringing the first liquid phase into contact with copper ions to obtain a second liquid phase; α) A step of bringing the second liquid phase into contact with a carbonate and optionally a hydroxide to obtain a liquid phase L1 and solid M3; β) A step of recovering the solid M3; γ) A step of bringing the liquid phase L1 into contact with a reducing agent to obtain a third liquid phase and solid M4; δ) A step of recovering the solid M4 and includes.

[0093] In another preferred embodiment, the method of the present invention comprises the following steps: i’) A step of bringing a liquid sample into contact with at least one amine and CO2 under an inert atmosphere to obtain a liquid phase L0’; ii’) A step of heating the liquid phase L0’ to a temperature T1 higher than room temperature under an inert atmosphere to obtain a liquid phase L0” and solid M1; iii’) A step of recovering the solid M1; iv’) A step of heating the liquid phase L0” to a temperature T2 higher than room temperature under an oxygen-containing atmosphere (such as air) to obtain a first liquid phase and solid M2; v’) A step of recovering the solid M2; c) A step of bringing the first liquid phase into contact with copper ions to obtain a second liquid phase; α) A step of bringing the second liquid phase into contact with a carbonate and optionally a hydroxide to obtain a liquid phase L1 and solid M3; β) A step of recovering the solid M3; γ) A step of bringing the liquid phase L1 into contact with a reducing agent to obtain a third liquid phase and solid M4; δ) A step of recovering the solid M4 and includes.

[0094] In another preferred embodiment, the method of the present invention comprises the following steps: i”) A step of bringing a liquid sample into contact with at least one amine (and optionally CO2) to obtain a liquid phase L and solid M1; ii”) recovering the solid M1 as described above; iii”) precipitating solid M2 from the liquid phase L to obtain the first liquid phase and solid M2 as defined herein; iv”) recovering the solid M2 as described above; c) contacting the first liquid phase with copper ions to obtain a second liquid phase; α) contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a liquid phase L1 and solid M3; β) recovering the solid M3 as described above; γ) contacting the liquid phase L1 with a reducing agent to obtain a third liquid phase and solid M4; δ) recovering the solid M4 as described above and comprising.

[0095] In another specific embodiment, solid M2 is recovered in step e). In such an embodiment, the method of the present invention comprises the following steps: a) contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase and solid M1; b) recovering the solid M1 as described above; c) contacting the first liquid phase with copper ions to obtain a second liquid phase; d) contacting the second liquid phase with a carbonate and optionally a hydroxide to obtain a third liquid phase, solid M2, solid M3, and optionally solid M4; e) recovering the solid M3, the solid M2, and optionally the solid M4 as described above and comprising. Preferably, in such an embodiment, the method of the present invention comprises the following steps: a) contacting the liquid sample with at least one amine and optionally CO2 to obtain a first liquid phase and solid M1; b) recovering the solid M1 as described above; c) contacting the first liquid phase with copper ions to obtain a second liquid phase; d) contacting the second liquid phase with carbonates and optionally hydroxides to obtain a third liquid phase, solid M2, solid M3, and solid M4; e) recovering the solid M2, the solid M3, and the solid M4; and comprising.

[0096] In the above embodiments, the following are preferred: - M1 is aluminum, iron, lanthanum, praseodymium, or a combination thereof, preferably aluminum; - M3 is nickel; - M4 is cobalt.

[0097] The steps of the method according to the invention as described herein can be carried out in a predetermined order or in a different order, preferably in a predetermined order. Intermediate steps may be included between any of the steps of the method of the invention as described herein.

[0098] The invention will be further described in more detail in the following examples, which are not intended to limit the scope of the invention as defined by the appended claims.

Examples

[0099] (Example 1) Demonstration of the concept of nickel / cobalt separation (M3 or M4) Preliminary tests were carried out on nickel and cobalt complexes with ethylenediamine. The solution was prepared according to the following protocol:

[0100] <Nickel carbonate (NiCO3)> Ni(en) 3 2+ Complex solution: 6.480 g of nickel chloride (50 mmol) was placed in a 50 mL volumetric flask. 30 mL of distilled water was added to the flask, and the mixture was shaken until the nickel chloride was completely dissolved, forming a dark green solution. 9.015 g of ethylenediamine (150 mmol, 3 equivalents) was added dropwise to the mixture, forming a dark purple solution. The mixture was returned to room temperature, and the flask was filled with distilled water. CuCl 2 Solution : 13.638 g of copper(II) chloride dihydrate was placed in a 20 mL volumetric flask and filled with distilled water. The mixture was shaken until the copper(II) chloride was completely dissolved, forming a dark green solution. Na 2 CO 3 Solution : 10.599 g of sodium carbonate was placed in a 50 mL volumetric flask and filled with distilled water. The mixture was shaken until the sodium carbonate was completely dissolved, forming a colorless and transparent solution. NiCO 3 Precipitation : 2 mL of Ni(en)3 2+ complex (2 mmol) was added to a 10 mL centrifuge tube. 1.4 mL of distilled water was added to this vial, and the mixture was shaken. 0.6 mL of copper(II) chloride solution (2.4 mmol, 1.2 equivalents per nickel) was added to the mixture. The vial was shaken and left at room temperature for 1 hour. 1 mL of Na2CO3 solution (2 mmol, 1 equivalent per nickel) was added to the vial, and the vial was shaken vigorously. Then the vial was left at room temperature for 1 hour. The solution was centrifuged, and the supernatant was collected. The precipitate was washed three times with 7 mL of distilled water. The solid was dried by freeze-drying for 24 hours. 155.0 mg of fine blue powder was obtained, and analysis by ICP-OES gave a nickel precipitation yield of 52% and a purity of 91%.

[0101] Precipitation of alternative nickel carbonate (NiCO3) Ni(en) 3 2+ Complex solution: 1.2960 g of nickel chloride (10 mmol) was placed in a 20 mL volumetric flask. 10 mL of distilled water was added to the flask, and the mixture was shaken until the nickel chloride was completely dissolved, forming a dark green solution. 1.803 g of ethylenediamine (30 mmol, 3 equivalents) was added dropwise to the mixture, forming a dark purple solution. The mixture was returned to room temperature, and the flask was filled with distilled water. CuCl 2 Solution : 3.4096 g of copper(II) chloride dihydrate (20 mmol) was placed in a 10 mL volumetric flask and filled with distilled water. The mixture was shaken until the copper chloride was completely dissolved, forming a dark green solution. NaOH / Na 2 CO 3 Solution : 0.2 g of sodium hydroxide (5 mmol) and 1.0599 g of sodium carbonate (10 mmol) were placed in a 50 mL volumetric flask and filled with distilled water. The mixture was shaken until the sodium hydroxide and sodium carbonate were completely dissolved, forming a colorless transparent solution. NiCO 3 Precipitation : The NaOH / Na2CO3 solution was placed in a 250 mL beaker, and 20 mL of distilled water was added to the solution. The solutions of Ni(en)3 2+ and copper chloride were combined in a 100 mL beaker and left standing for 2 hours with stirring. After 2 hours, the mixture was filtered through a 0.22 μm membrane and added dropwise to the solution of sodium hydroxide and sodium carbonate with stirring over 20 minutes. The solution was left standing for 16 hours with stirring. Then the solution was filtered and washed three times with 20 mL of distilled water. The obtained solid was dried at 70 °C for 5 hours. 1.35 g of blue powder was obtained, and analysis by ICP-OES gave a nickel precipitation yield of 91% and a purity of 81%.

[0102] Cobalt carbonate (CoCO3) Co(en) 3 3+ Complex solution: 11.897 g of cobalt(II) chloride hexahydrate (50 mmol) was placed in a 50 mL volumetric flask. 30 mL of distilled water was added to the flask and the mixture was shaken until the cobalt(II) chloride was completely dissolved, forming a dark red solution. 9.015 g of ethylenediamine (150 mmol, 3 equivalents) was added dropwise to the mixture, forming an orange solution. The mixture was returned to room temperature and the flask was filled with distilled water. The mixture was placed at 60 °C for 6 hours under an air stream (flow rate: 100 mL / min) and a CO2 stream (100 mL / min). The solution first turned from orange to dark brown (indicating the formation of a peroxo complex), and then from dark brown to dark red (indicating the formation of tris(ethylenediamine)cobalt(III)). CuCl 2 Solution : 13.638 g of copper(II) chloride dihydrate was placed in a 20 mL volumetric flask filled with distilled water. The mixture was shaken until the copper(II) chloride was completely dissolved, obtaining a dark green solution. Na 2 CO 3 Solution : 10.599 g of sodium carbonate was placed in a 50 mL volumetric flask filled with distilled water. The mixture was shaken until the sodium carbonate was completely dissolved, forming a colorless and transparent solution. CoCO 3 Precipitation : 0.75 mL of Co(en)3 3+The solution (0.75 mmol) was placed in a 10 mL centrifuge vial. 3.3 mg of cobalt 0 powder (0.375 mol, 0.5 equivalent per initial cobalt), and 68 mg of ethylenediamine (1.125 mmol, 3 equivalents per cobalt(0)) were added to the vial together with 2.7 mL of distilled water. The vial was placed under an inert atmosphere, stoppered with a septum, and the mixture was left at 60 °C for 24 hours under magnetic stirring. 0.420 mL of CuCl2 solution (1.68 mmol, 1.5 equivalents per total cobalt) was added to the mixture under an inert atmosphere. The vial was shaken and left at room temperature for 1 hour. 1.125 mL of Na2CO3 (2.225 mmol, 2 equivalents per total cobalt) was added to the vial under an inert atmosphere, and then the vial was shaken vigorously. Then, the vial was left at room temperature for 1 hour. The solution was centrifuged, the supernatant was collected, and the precipitate was washed three times with 7 mL of distilled water. The solid was dried by freeze-drying for 24 hours. 41.2 mg of fine purple powder was obtained, and analysis by UV-visible spectroscopy showed a precipitation yield of 87% and a purity of 96.7%. In the following experiment, the solutions were added in the following order: 1 - solution of the metal complex, 2 - solution of sodium carbonate, 3 - solution of copper chloride. Furthermore, the concentrations of the other chemical species were selected to have the following stoichiometric ratios: 3 equivalents of ethylenediamine per 1 mole of metal, 2 equivalents of sodium carbonate per 1 mole of metal, 1.5 equivalents of copper chloride per 1 mole of metal. In this case, the analysis was carried out by UV-visible spectroscopy after calibration.

[0103]

Table 1

[0104] The results obtained are summarized in Table 2. The precipitation yield corresponds to the ratio between the number of moles of metal in the precipitate and the number of moles of metal initially introduced. The purity corresponds to the ratio between the number of moles of the target metal (nickel or cobalt) in the precipitate and the total number of moles of metal (nickel or cobalt and copper).

[0105]

Table 2

[0106] A variety of solutions were prepared that contained nickel ions, copper ions, and ethylenediamine, with the nickel concentration varying from 0.1 M to 0.4 M and the stoichiometric ratio of copper (relative to nickel) in the range of 0.8 to 2 equivalents. Tables 3 and 4 show that good yields and purities were obtained.

[0107]

Table 3

[0108]

Table 4

[0109] From preliminary tests, the following is demonstrated: - Nickel in a solution with an amine can be precipitated with good yield and purity by using a combination of copper ions and carbonate. - Cobalt in a solution with an amine can be precipitated with good yield and purity by using a combination of a reducing agent, copper ions, and carbonate.

[0110] (Example 2) Method according to the invention Step 0. Preparation of Pr2Ni9MnCo polymetallic solution 3.0320 g of Pr2(CO3)3·8H2O was placed in a 50 mL volumetric flask. 2.4731 g of 37% hydrochloric acid was added to the flask together with 15 mL of distilled water. The solution was mixed until the praseodymium carbonate was completely dissolved. 1.1900 g of CoCl2·6H2O, 6.4786 g of NiCl2, and 0.9899 g of MnCl2·4H2O were added to the solution together with 30 mL of distilled water, and the mixture was shaken until the solids were completely dissolved. The flask was filled with distilled water.

[0111] Process 1 (Processes i') - ii') - iii')). Precipitation of praseodymium carbonate Pr2(CO3)3 1.0301 g of diethylenetriamine (DETA) was placed in a 10 mL centrifuge vial containing 1.5 mL of distilled water. CO2 was passed into the solution at a flow rate of 80 mg / min for 1 hour until the pH reached 7. 2.5 mL of the polymetallic solution prepared in the above Process 0) was added dropwise to the vial, leading to important degassing. The solution was placed under an inert atmosphere and heated to 100 °C for 1 hour. The vial was returned to room temperature and then centrifuged, and the supernatant was collected. The obtained solid was washed three times with 8 mL of distilled water and then dried by freeze-drying for 24 hours. 0.1536 g of a bright green solid was obtained, and analysis by ICP showed a precipitation yield of 87.3% and a purity of 67.2%.

[0112] Process 2 (Processes iv') - v')). Precipitation of manganese oxide The supernatant and washing water from the above Process 1) were placed in a 50 mL vial. The vial was placed in a water bath under a stream of air and heated to 100 °C to evaporate the excess water. When the volume in the vial reached approximately 7.5 mL, the vial was centrifuged, washed three times with 3 mL of distilled water, and then the solid was dried by freeze-drying for 24 hours. 13.6 mg of a black solid was collected, and analysis by ICP showed a precipitation yield of 22.2% and a purity of 73.9%.

[0113] Process 3 (Processes c) - α) - β)). Precipitation of nickel carbonate NiCO3 The supernatant and washing water from the above Process 2) were placed in a 50 mL vial to obtain 22.5 mL of a solution with a pH of 10.5. 1.0713 g of CuCl2·2H2O was dissolved in 2.5 mL of distilled water. The solution was added dropwise to the vial under strong magnetic stirring. 1.19 g of Na2CO3 was dissolved in 4 mL of distilled water, and then that solution was added dropwise to the vial. The mixture was centrifuged, and the supernatant was collected. The obtained solid was washed four times with 8 mL of distilled water and then dried by freeze-drying for 24 hours. 0.1437 g of a turquoise-colored powder was obtained, and analysis by ICP showed a precipitation yield of 39% and a purity of 72.6%.

[0114] Step 4 (Step γ to δ)). Precipitation of cobalt carbonate CoCO3 The supernatant and washing water from the above Step 3 were placed in a 50 mL vial. The solution was concentrated in a water bath at 100 °C until the volume reached 20 mL. 11.6 mg of cobalt(0) powder was added to the solution, then the vial was stoppered with a septum and left standing for 48 hours under magnetic stirring. 0.546 g of CuCl2·2H2O was dissolved in 1 mL of distilled water and then added dropwise to the mixture. The mixture was centrifuged and the supernatant was collected. The resulting solid was washed 4 times with 8 mL of distilled water and then dried by freeze-drying for 24 hours. 0.3642 g of blue powder was obtained, and analysis by ICP showed a precipitation yield of 28.6% and a purity of 3.9%.

[0115] The precipitation yield and the proportion of each metal in each precipitate are shown in Tables 5 and 6, respectively.

[0116] [Table 5]

[0117] [Table 6]

[0118] (Example 3) Method according to the present invention The following protocol relates to black masses containing metals in the proportions shown in Table 7.

[0119] [Table 7]

[0120] The protocol was established with a 100 mL solution and a nickel concentration of 0.5 M in the solution. The nickel concentration decreases after each step because the solution is added and dilution is thereby caused. The nickel concentration reaches a minimum of 0.3 M during the step of nickel carbonate precipitation.

[0121] Step 0. Dissolution of the black mass 11.1 g of the black mass was placed in a 250 mL flask. 75 g of distilled water was added to the flask and the solution was placed under stirring. To capture Cl2, the assembled apparatus was equipped with a soda trap. 31.6 g of 37% HCl (2 equivalents per Ni, Mn, and Co + 1 equivalent per Li + 3 equivalents per Al) was added dropwise to the mixture under a nitrogen stream. Once the addition was complete, the mixture was heated at 80 °C for 2 hours. The mixture was returned to room temperature and then filtered through a filter (pore < 2 μm).

[0122] The concentrations of the following metals in the liquid sample obtained after Step 0 were determined by ICP titration to be - Lithium: 0.89 mol / L, - Nickel: 0.5 mol / L, - Manganese: 0.17 mol / L, - Cobalt: 0.17 mol / L, - Aluminum: 0.21 mol / L as follows.

[0123] Step 1 (Steps i) - ii)). Precipitation of aluminum hydroxide Al(OH)3 The filtrate obtained in the above Step 0) was placed in a 250 mL flask, and then a predetermined amount of ethylenediamine was added dropwise until pH 6 was reached. The solution was filtered through a filter (pore < 2 μm), and the precipitate was washed twice with 5 mL of distilled water.

[0124] Step 2 (Steps iii) - iv)). Precipitation of manganese carbonate MnCO3 The filtrate obtained in the above step 1) was placed in a 250 mL flask, and then degassed ethylenediamine (the total amount of ethylenediamine added in steps 1) and 2) was equal to 16.07 g) was added dropwise to the mixture under a nitrogen stream. The formation of a white precipitate (brown if inactivation was not complete) was observed. Then, aeration with CO2 was carried out until the precipitate redissolved (pH was about 7.4). Then the solution was left standing with stirring for 1 hour to form a white precipitate. The mixture was filtered through a filter (pore <2 μm), and the solid was washed twice with 5 mL of distilled water.

[0125] Step 3 (steps c) - α) - β)). Precipitation of nickel carbonate NiCO3 A solution containing 14.6 g of anhydrous CuCl2 in 20 mL of distilled water was prepared. The filtrate obtained in the above step 2) was placed in a 250 mL flask, and the CuCl2 solution was added to the flask. The mixture was left standing with stirring for 10 minutes. A solution containing 5.31 g of Na2CO3 and 1 g of NaOH in 20 mL of distilled water was prepared and added dropwise to the previous mixture. The resulting mixture was left standing with stirring for 3 hours. Then the mixture was filtered through a filter (pore <2 μm), and the solid was washed twice with 5 mL of distilled water.

[0126] Step 4 (steps γ) - δ)). Precipitation of cobalt carbonate CoCO3 The filtrate obtained in the above step 3) was placed in a 250 mL flask, and the flask was inactivated with nitrogen. 0.492 g of metallic cobalt powder was added to the flask, and then the mixture was left standing with stirring at 60 °C for 48 hours. After 48 hours, the residual cobalt powder was filtered under an inert atmosphere, and then a solution containing 5.05 g of anhydrous CuCl2 in 10 mL of distilled water was added to the previous mixture. The solution was left standing with stirring for 15 minutes, and then a solution containing 2.65 g of Na2CO3 and 0.5 g of NaOH in 10 mL of water was added dropwise to the metal solution. The mixture was left standing with stirring for 3 hours, and then the solid was filtered through a filter (pore <2 μm) and washed twice with 5 mL of distilled water.

[0127] (Example 4) Method according to the present invention Process 0. Dissolution of the black mass 11.11 g of the black mass was placed in a 250 mL flask. 40 g of distilled water was added to the flask and the solution was placed under stirring. To trap Cl2, a soda trap was installed in the assembled apparatus. 34.9 g of 37% HCl (2 equivalents per Ni, Mn, and Co + 1 equivalent per Li + 3 equivalents per Al) was added dropwise to the previous mixture under a nitrogen flow. After the addition was complete, the mixture was heated at 80 °C for 8 hours. The mixture was allowed to return to room temperature and then filtered through a 2 μm filter. The flask was rinsed with 10 mL of water. The solid was washed with a dilute sodium hydroxide solution to trap residual Cl2. The results of the dissolution are shown in Table 8.

[0128] [Table 8]

[0129] Process 1 (Process i) - ii)). Precipitation of aluminum hydroxide Al(OH)3 The filtrate obtained during the previous process was placed in a 250 mL flask, 20 mL of water was added, and then 8 mL of EDA (99%) was added until the pH reached 6.1 and a solid (peach / red) was formed. The solid was filtered (slow filtration) and washed with 2 × 5 mL of water. The pH of the filtered solution was 6.2. → 99% of aluminum was recovered in Process 1).

[0130] Process 2 (Process iii) - iv)). Precipitation of manganese carbonate MnCO3 The solution was degassed with argon for 1 hour and then 5 mL of EDA (99%) was added to reach pH 9. The aeration of CO2 was carried out for 2 hours and a brown solid was formed. The solution was filtered (slow filtration), the solid was washed with 200 mL of H2O, and the solution was evaporated to obtain a solution with a mass of 121 g. → Manganese was efficiently recovered in Process 2).

[0131] Process 3 (Process c) - α) - β)). Precipitation of nickel carbonate NiCO3 A solution containing 15.8 g of CuCl₂·2H₂O in 20 mL of distilled water was prepared. The filtrate obtained during the previous step was placed in a 250 mL flask, and the copper chloride solution was added to the flask. A blue solid and a foamy substance were formed. After heating to remove the foamy substance (CO₂), the solution was filtered to remove the formed solid. A solution containing 5.31 g of Na₂CO₃ and 1.050 g of NaOH in 20 mL of distilled water was prepared and added to the metal mixture. Then, the mixture was filtered through a 1 μm filter (slow filtration), and the solid was washed twice with 5 mL of distilled water. → 60% of nickel was recovered in step 3).

[0132] Step 4 (steps γ) - δ)). Precipitation of cobalt carbonate CoCO₃ The filtrate obtained during the previous step was placed in a 250 mL flask, and the flask was inactivated with nitrogen. 0.75 g of metallic cobalt powder was added to the flask after grinding, and then the mixture was left standing at 60 °C for 36 hours with stirring. After 36 hours, the formed solid was filtered under an inert atmosphere (argon ventilation in a funnel on a vacuum flask). A solution containing 6.41 g of CuCl₂·2H₂O in 20 mL of distilled water was added to the vacuum flask to limit the possibility of oxidation of the cobalt complex. The formation of a solid was observed, which was filtered at 1 μm, and then a solution containing 2.67 g of Na₂CO₃ and 0.57 g of NaOH in 20 mL of water was added to the metal solution. The solid was filtered through a filter (pores < 2 μm) and washed twice with 5 mL of distilled water. → 39% of cobalt was recovered in step 4).

[0133] (Example 5) Precipitation of aluminum hydroxide (steps i) - ii) of the method according to the invention) Step 0. Dissolution of the black mass 22.64 g of the black mass (LiAl 0.1 Ni 0.8 Co 0.1 Mn 0.1(O) was placed in a 250 mL flask. 80 mL of distilled water was added to the flask and the solution was placed under stirring. To capture Cl2, a soda trap was equipped in the assembled apparatus. 60 mL of 37% HCl was added dropwise to the mixture under a nitrogen stream. After the addition was complete, the mixture was heated under reflux for 24 hours. The mixture was returned to room temperature and then filtered through a filter (pore <2 μm) and washed with 220 mL of water.

[0134] The results of the dissolution are shown in Table 9.

[0135]

Table 9

[0136] Step 1 (Steps i) to ii)). Precipitation of aluminum hydroxide Al(OH)3 The filtrate obtained during the previous step (concentration: 1.07 M) was placed in a flask and EDA (5 M) was added until a pH of 6 was obtained. The solid was filtered and washed with water.

[0137] No aluminum was detected in the filtrate. The metal composition of the solid is shown in Table 10.

[0138]

Table 10

Claims

1. A method for capturing chemical elements M1, M2, M3, and possibly M4 contained in a liquid sample, wherein the method comprises the following steps: a) A step of contacting the liquid sample with at least one amine to obtain a first liquid phase, solid M1, and possibly solid M2, b) A step of recovering the solid M1, c) A step of bringing the first liquid phase into contact with copper ions to obtain a second liquid phase, d) A step of bringing the second liquid phase into contact with a carbonate to obtain a third liquid phase, solid M3, possibly solid M4, and possibly solid M2. e) A step of recovering the solid M3 and, if applicable, the solid M4. Includes, The solid M2 is recovered in step b) and / or step e), M1 is selected from the group consisting of iron, aluminum, titanium, rare earth elements, actinides, and combinations thereof. M2 is manganese, A method in which M3 and M4 are each independently selected from the group consisting of nickel, cobalt, and combinations thereof.

2. - M1 is a rare earth element selected from iron, aluminum, lanthanum, and praseodymium, or a combination thereof, and / or - The method according to claim 1, wherein M3 is nickel and M4 is cobalt.

3. - The solid M1 is a carbonate, hydroxide, oxide, or combination thereof of M1. - The solid M2 is a carbonate, hydroxide, oxide, or combination thereof of M2. - The solid M3 is a carbonate, hydroxide, oxide, or combination thereof of M3, and / or - The method according to claim 1 or 2, wherein solid M4 is a carbonate, hydroxide, oxide, or combination thereof of M4.

4. The method according to claim 1, wherein the at least one amine is selected from ethylenediamine, propanediamine, diethylenetriamine, triethylenetetraamine, tris-(2-aminoethyl)amine, lysine, glycine, 2,3-diaminopropionic acid, 2,4-diaminobutyric acid, and 2,5-diaminopentanoic acid.

5. The method according to claim 1, wherein solid M2 is recovered in step b).

6. - Step a) includes contacting the liquid sample with at least one amine to obtain a first liquid phase, solid M1, and solid M2, and - The method according to claim 5, wherein step b) includes continuously recovering the solid M1 and the solid M2.

7. Steps a) to b) are i) Contact the liquid sample with at least one amine to obtain a liquid phase L0 and a solid M1. ii) To recover the solid M1, iii) To bring the liquid phase L0 into contact with CO2 in an inert atmosphere to obtain the first liquid phase and the solid M2, and iv) Recover the solid M2. The method according to claim 5, including the method described in claim 5.

8. Steps a) to b) are i') In an inert atmosphere, the liquid sample is subjected to at least one amine and CO ２ By bringing it into contact with the liquid phase L0', ii') The liquid phase L0' is heated in an inert atmosphere at a temperature higher than room temperature T １ To obtain the liquid phase L0'' and the solid M1, iii') To recover the solid M1 mentioned above, iv') The above liquid phase L0'' is heated in an oxygen-containing atmosphere at a temperature higher than room temperature T ２ To heat to obtain the first liquid phase and solid M2, and v') Recover the solid M2. The method according to claim 5, including the method described in claim 5.

9. Temperature T １ and T ２ The method according to claim 8, wherein each of them is independently included in the range of 70°C to 110°C.

10. Steps d) to e) are α) The second liquid phase is brought into contact with a carbonate to obtain the liquid phase L1 and the solid M3. β) To recover the solid M3 mentioned above. γ) To bring the liquid phase L1 into contact with a reducing agent to obtain a third liquid phase and a solid M4, and δ) Recover the solid M4 mentioned above. including, The method according to claim 5.

11. The method according to claim 1, wherein solid M2 and possibly solid M4 are recovered in step e).

12. M2, M3, and possibly M4, which are solids, are recovered in the form of a single salt. The method according to claim 11.

13. The liquid sample further contains the chemical element M5, and the method, after step e), includes the following steps: f) A step of precipitating solid M5 from the third liquid phase to obtain solid M5 and a fourth liquid phase, g) A process for recovering solid M5 and It further includes, M5 is copper. The method according to claim 1.

14. Before step a), - A step of leaching lithium from a solid sample containing lithium, M1, M2, M3, and possibly M4, to obtain a solid sample containing leached lithium and M1, M2, M3, and possibly M4, - A process for recovering the leached lithium, - A step of converting the solid sample containing M1, M2, M3, and optionally M4 into the liquid sample containing M1, M2, M3, and optionally M4. The method according to claim 1, further comprising:

15. The liquid sample further contains lithium, and the method, after step e) or step g), h) A step of concentrating the third or fourth liquid phase to obtain solid lithium, The method according to claim 1 or 13, further comprising the step of recovering solid lithium.

16. The method according to claim 1 or 5, wherein in step a), the liquid sample is brought into contact with at least one amine and CO2.

17. The method according to claim 1 or 10, wherein in step d), the second liquid phase is brought into contact with the carbonate and the hydroxide.

18. The method according to claim 10, wherein the reducing agent is a solid metal.