Method and system for the purification and recycling of lithium-ion battery waste streams

Abstract

A process and system for recovering metals from lithium-ion battery waste streams includes carrying out a leaching process to form a leachate stream, purifying the leachate stream in a first reactor to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti), and optionally passing the purified filtrate stream through (i) a reactor for carrying out a co-precipitation process by increasing the pH, or (ii) one or more chromatographic columns to separate nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream to produce an intermediate liquid stream comprising lithium (Li) and one or more recovered products comprising one or more of nickel (Ni), manganese (Mn), and cobalt (Co). The intermediate liquid stream can be introduced into a lithium precipitation reactor to precipitate at least one compound comprising lithium (Li).

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 312,978, filed February 23, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] The present disclosure relates to processes and systems for purifying and recycling lithium-ion battery waste streams. [Background technology]

[0003] This section provides background information related to the present disclosure that is not necessarily prior art.

[0004] Electrochemical batteries, such as lithium-ion batteries, are widely used in a variety of applications, including consumer products and automobiles. However, once a battery's lifespan is over, it can be discarded. Consequently, lithium-ion batteries often contain valuable metals, which are then discarded. Efforts to recycle materials from used lithium-ion batteries are ongoing. In some cases, for recycling purposes, used lithium-ion batteries are disassembled, crushed, and / or shredded, forming a lithium-ion battery waste stream known as black mass. Black mass typically contains all battery active materials, and therefore may contain a mixture of negative electrode / anode active materials and positive electrode / cathode active materials, as well as electrolyte components. The presence of multiple complex compounds in black mass makes recycling and recovery of the metals of greatest interest challenging.

[0005] Traditional recycling efforts for such used lithium-ion batteries focus on recovering cobalt and lithium from the lithium cobalt oxide (LiCoO2) cathode material in the black mass due to their high value and their presence as major materials in the waste stream. However, as lithium-ion batteries evolve into new generations, new cathode active materials may reduce the cobalt and nickel content while incorporating additional elements / metals. In some instances, it is estimated that LiCoO2 cathode electroactive material accounts for only about 37% of the total lithium-ion battery market. Other currently popular cathode materials include, for example, lithium nickel manganese cobalt oxide (Li(Ni)), which accounts for about 29% of the current market. x Mn y Co z )O2, where 0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z=1, abbreviated as NMC, LiMn 0.33 Ni 0.33 Co 0.33 O2), lithium manganese oxide (LMO-LiMn2O4 - about 21%), lithium nickel oxide (LNO-LiNiO2 - about 7%), and lithium iron phosphate (LFP-LiFePO4 - about 5%). Thus, black mass waste streams are becoming increasingly complex mixtures of metals, making recycling more difficult.

[0006] Additionally, black mass may contain impurities from the anodes and / or cathodes of spent batteries, which can further complicate conventional recycling efforts. For example, such impurities may include carbon (e.g., graphite), iron, copper, fluorine, phosphorus, titanium, aluminum, etc., depending on the particular type of lithium-ion battery. It is desirable to develop methods and systems that can purify waste streams from lithium-ion batteries, such as black mass, by efficiently separating various impurities while optimizing the recovery of additional metals other than nickel and cobalt. Summary of the Invention

[0007] This section provides a general summary of the disclosure and is not a comprehensive disclosure of its entire scope or all features.

[0008] According to one aspect of the present disclosure, a process for recovering metals from a lithium-ion battery waste stream is provided. The process may include purifying a lithium-ion battery waste stream containing sulfuric acid (HSO) in a first reactor to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). The purification may include removing copper (Cu) and fluorine (F) from the waste stream, and removing fluorine (F) may include adding a source of calcium oxide and an oxidizing agent to produce calcium fluoride (CaF), which precipitates from the waste stream. The purification may also include adding a first inorganic base to increase the pH of the waste stream to produce one or more metal precipitation compounds selected from the group consisting of aluminum hydroxide (Al(OH)), titanium hydroxide (Ti(OH)), iron phosphate (FePO), and one or more iron hydroxides (Fe(OH) and Fe(OH)). The process also includes passing the waste stream from the first reactor through a filter to produce a purified filtrate stream and a second retentate containing one or more metal precipitation compounds, copper (Cu), and calcium fluoride (CaF). The process then includes passing the purified filtrate stream through one or more of a second reactor for carrying out a co-precipitation process by increasing the pH and / or one or more chromatography columns or packed-bed columns / reactors to separate nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream. In this manner, an intermediate liquid stream is produced containing lithium (Li) and one or more recovered products containing one or more of nickel (Ni), manganese (Mn), and cobalt (Co). The one or more recovered products are removed from the intermediate liquid stream. The process also includes introducing the intermediate liquid stream into a lithium precipitation reactor to precipitate at least one compound containing lithium (Li).

[0009] In one embodiment, refining may include precipitating copper (Cu) via a cementation reaction or a sulfidation reaction.

[0010] In one embodiment, removing copper (Cu) from the waste stream includes adding a source of iron (Fe) and a second inorganic base to the waste stream to precipitate copper (Cu), and precipitating copper (Cu) by a cementation reaction.

[0011] In a further embodiment, the source of iron (Fe) comprises iron powder, the first inorganic base and the second inorganic base each comprise sodium hydroxide (NaOH), the source of calcium oxide is selected from the group consisting of lime (CaO), calcium hydroxide (Ca(OH)), and combinations thereof, and the oxidizing agent is selected from the group consisting of hydrogen peroxide (HO), ozone (O), sodium hypochlorite (NaClO), and combinations thereof.

[0012] In a further embodiment, a second inorganic base is added until the pH is about 5, a first organic base is added until the pH is about 10.5, and the oxidizing agent comprises hydrogen peroxide (HO), which is added at a concentration of about 4% to about 6% by volume of the total liquid content (waste stream).

[0013] In a further embodiment, the addition of the source of iron (Fe) and the second inorganic base to the waste stream is carried out at a pH of about 1 to about 2, with mixing at a temperature of about 55° C. to about 65° C. for a period of about 15 minutes or more.

[0014] In a further embodiment, about 2.5 g of iron powder is added per liter (L) of waste stream.

[0015] In one embodiment, removing copper (Cu) from the waste stream comprises precipitating copper (Cu) by adding a source of sodium sulfide (NaS) to the waste stream, precipitating copper (Cu) by a sulfidation reaction.

[0016] In one embodiment, removing copper (Cu) from the waste stream comprises subjecting the waste stream to a solvent extraction process in which the waste stream is mixed with an extractant and an organic phase to remove the copper (Cu).

[0017] In a further embodiment, the extractant comprises 2-hydroxy-5-nonylbenzaldehyde oxime and the organic phase comprises kerosene.

[0018] In a further embodiment, the solvent extraction process further removes iron (Fe) from the waste stream.

[0019] In one embodiment, the purification further comprises (iii) introducing a phosphate source into the waste stream prior to adding a first inorganic base to increase the pH of the waste stream to produce an aluminum phosphate (AlPO) precipitate.

[0020] In a further embodiment, the phosphate source comprises sodium phosphate (Na3PO4).

[0021] In one embodiment, the addition of a calcium oxide source and an oxidizing agent to produce calcium fluoride (CaF) is carried out at a temperature of about 55° C. to about 65° C. with mixing for a period of about 30 minutes or more, at a pH of about 1 to about 2.

[0022] In one embodiment, the addition of the first inorganic base increases the pH of the waste stream to between about 4 and about 5, inclusive.

[0023] In one embodiment, the addition of the first inorganic base to increase the pH is conducted with mixing at a temperature of about 55° C. to about 65° C. for a period of about 60 minutes or more.

[0024] In one embodiment, the purified filtrate stream comprises nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO), and separation of the nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream is performed by passing the purified filtrate stream through a second reactor, where a co-precipitation process is performed that includes raising the pH of the purified filtrate stream to about 11 or greater in an inert environment to form nickel hydroxide hydrate (Ni(OH) 6H O), manganese hydroxide hydrate (Mn(OH) H O), and cobalt hydroxide hydrate (Co(OH) 7H O), which are simultaneously precipitated from the purified filtrate stream to produce one or more recovered products.

[0025] In a further embodiment, increasing the pH of the purified filtrate stream further comprises initially adding ammonia to the purified filtrate stream comprising nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO).

[0026] In one embodiment, the one or more recovered products are Ni x Mn y Co 1-x-y It is an electroactive material precursor with a stoichiometry of (OH)2.

[0027] In one embodiment, the one or more recovered products are stoichiometrically approximately

number

[0028] In one embodiment, the process further comprises determining a first ratio of Ni:Mn:Co in the purified filtrate stream prior to the co-precipitation process, which first ratio is then compared to a target stoichiometric ratio of Ni:Mn:Co for one or more recovered products. ThereforeThe process may include adding one or more of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO) to the purified filtrate stream prior to adjusting the pH to adjust the amount of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO). In this way, the one or more recovered products have a second ratio corresponding to the target stoichiometric ratio.

[0029] In one embodiment, the separation is carried out by passing the purified filtrate stream in a first direction through a chromatography column or packed-bed column / reactor containing a chelating resin, performing a chromatographic separation process at a pH of about 4.5 or less, and producing a raffinate stream containing at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exiting the packed-bed column / reactor, while nickel (Ni) ions and cobalt (Co) ions are retained on the chelating resin in the packed-bed column / reactor. The process further includes regenerating the packed-bed column / reactor by passing a regenerant having a pH of about 1.5 or less through the packed-bed column / reactor to form an extract stream containing nickel (Ni) ions and cobalt (Co) ions. The process also includes precipitating nickel hydroxide (Ni(OH)2) and cobalt hydroxide (Co(OH)2) from the extract.

[0030] In one embodiment, the method further includes combining nickel hydroxide (Ni(OH)) and cobalt hydroxide (Co(OH)) with at least one compound comprising lithium (Li) and aluminum hydroxide (Al(OH)) to form a precursor of the LiNiCoAlO electroactive material.

[0031] In certain embodiments, manganese in the raffinate stream / purified filtrate stream can be precipitated, for example, as manganese oxide (e.g., manganese dioxide, MnO) or manganese hydroxide (Mn(OH)). In one variation, manganese removal via precipitation to form manganese oxide (e.g., manganese dioxide (MnO)) can be achieved by implementing one or more of the following processes: adding sodium permanganate, potassium permanganate, or subjecting the raffinate to ozonation. In certain embodiments, combining these manganese removal processes maximizes manganese precipitation levels.

[0032] In another variation, the process may further include adjusting the pH of the purified filtrate stream as it enters the packed bed column / reactor to between about 4 and about 5. The process further includes precipitating manganese hydroxide (Mn(OH)2) by adjusting the pH to between about 8 and about 10, and separating the manganese hydroxide (Mn(OH)2).

[0033] In one embodiment, at least one compound comprising lithium (Li) is water It contains lithium carbonate (Li2CO3) which combines with manganese oxide (Mn(OH)2) to form LiMnO4 electroactive material.

[0034] In one embodiment, adjusting the pH comprises adding sodium hydroxide (NaOH) to the purified filtrate stream.

[0035] In one embodiment, the stationary phase of the packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0036] In one embodiment, the separation is carried out by passing the purified filtrate stream in a first direction through a first packed bed column / reactor containing a first chelating resin and conducting a chromatographic separation process at a pH of about 1.5 or less, thereby producing a first raffinate stream that contains at least one manganese (Mn)-containing species, at least one cobalt (Co)-containing species, and at least one lithium (Li)-containing species and exits the first packed bed column / reactor, while nickel (Ni) ions are retained on the first chelating resin in the first packed bed column / reactor. The process also includes passing the first raffinate stream in a first direction through a second packed-bed column / reactor containing a second chelating resin and conducting a chromatographic separation process at a pH of about 2.5 or less, thereby producing a second raffinate stream containing at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species, which exits the second packed-bed column / reactor, while cobalt (Co) ions are retained on the second chelating resin in the second packed-bed column / reactor. The process further includes regenerating the first packed-bed column / reactor by passing a first regenerant having a pH of about 1.5 or less through the first packed-bed column / reactor to form a first extract stream containing nickel (Ni) ions. Nickel hydroxide (Ni(OH)2) may then be precipitated from the first extract stream. The process also includes regenerating the second packed bed column / reactor by passing a second regenerant solution having a pH of about 2.5 or less through the second packed bed column / reactor to form a second extract stream comprising cobalt (Co) ions, followed by precipitating cobalt hydroxide (Co(OH)2) from the second extract stream.

[0037] In one embodiment, the process further includes combining nickel hydroxide (Ni(OH)) and cobalt hydroxide (Co(OH)) with at least one compound comprising lithium (Li) and aluminum hydroxide (Al(OH)) to form a precursor of the LiNiCoAlO electroactive material.

[0038] In one embodiment, the process further comprises precipitating manganese hydroxide (Mn(OH)2) from the second raffinate stream by adjusting the pH to about 8 or greater to about 10 or less to form an intermediate liquor stream. The manganese hydroxide (Mn(OH)2) is then separated from the intermediate liquor stream.

[0039] In one embodiment, at least one compound comprising lithium (Li) is water It contains lithium carbonate (Li2CO3) which combines with manganese oxide (Mn(OH)2) to form LiMnO4 electroactive material.

[0040] In one embodiment, the process further includes adding sodium hydroxide (NaOH) to the purified filtrate stream to adjust the pH of the purified filtrate stream to about 2.5, and adding sodium hydroxide (NaOH) to the first raffinate stream to adjust the pH of the first raffinate stream to about 3.5.

[0041] In one embodiment, the stationary phase of the first packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid, and the stationary phase of the second packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0042] In one embodiment, the lithium-ion battery effluent stream is black mass. Prior to purification, the method further includes subjecting the black mass to a leaching process comprising mixing an inorganic acid with the black mass to form an acidic mixture, thereby producing a lithium-ion battery effluent stream. An oxidizing agent may be mixed with the acidic mixture. The process further includes adding deionized water to the acidic mixture. The leachate stream is then passed through a second filter to produce a filtrate stream comprising one or more metal sulfates and a first retentate comprising graphite.

[0043] In a further embodiment, the combining of the inorganic acid and the combining of the oxidizing agent are both carried out at a temperature of about 100° C. or less.

[0044] In a further embodiment, the inorganic acid comprises sulfuric acid (H2SO4), the oxidizing agent comprises hydrogen peroxide (H2O2), and the pH of the acidic mixture is about 2.5 or less.

[0045] In a further embodiment, the mixing of the inorganic acid comprises adding the black mass to sulfuric acid (H2SO4) having a molar concentration of about 4 M, the mixing of the oxidizing agent comprises adding about 30% by weight of hydrogen peroxide (H2O2) to the acid mixture such that the acid mixture has a solid / liquid ratio of 100 g / L, followed by mixing for about 2 hours or more, and the mixing of the deionized water comprises adding about 30% by weight of hydrogen peroxide (H2O2) to the acid mixture such that the acid mixture has a solid / liquid ratio of 100 g / L, followed by mixing for about 2 hours or more. water The method involves diluting sulfuric acid (H2SO4) to a molar concentration of about 2M by HCl followed by mixing for about 30 minutes or more.

[0046] In one embodiment, the one or more recovered products have a purity level of about 95% or greater and contain a total cumulative amount of impurities including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F) of about 5% or less by weight.

[0047] In one embodiment, the one or more recovered products have a purity level of about 98% or greater and contain a total cumulative amount of impurities including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F) of about 2% or less by weight.

[0048] In one embodiment, the separation recovers greater than about 80 wt. % each of nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream.

[0049] In one embodiment, prior to separating the nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream, the method further includes passing the purified filtrate stream through a solvent extraction reactor and combining it with an extractant and an organic phase to further remove impurities (e.g., copper (Cu), iron (Fe), and optionally aluminum (Al)) from the intermediate liquid stream.

[0050] In a further embodiment, the total cumulative concentration of impurities comprising metals selected from the group consisting of copper (Cu), iron (Fe), aluminum (Al), and combinations thereof is less than or equal to about 20 ppm.

[0051] In a further embodiment, the extractant comprises bis-(2-ethylhexyl) phosphoric acid and the organic phase comprises kerosene.

[0052] In one embodiment, introducing the intermediate liquid stream into the lithium precipitation reactor includes adding sodium carbonate (NaCO) and a second inorganic base to the lithium precipitation reactor, wherein the intermediate liquid stream has a temperature of at least about 80° C. and at most about 90° C. for at least about 90 minutes to produce a lithium carbonate (LiCO) precipitate.

[0053] In one embodiment, the intermediate liquid stream comprises lithium sulfate (LiSO) and sodium sulfate (NaSO). Prior to introduction, the intermediate liquid stream is subjected to a thermal shock process to bring the temperature to between about 0° C. and about 30° C., and then ionized in an electrode ionization unit to facilitate precipitation of sodium sulfate (NaSO) from the intermediate liquid process, and then sodium carbonate (NaCO) is added to a lithium precipitation reactor to produce lithium carbonate (LiCO) precipitate.

[0054] In one embodiment, the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is individually about 95% or greater, and the separation efficiency of fluorine is about 80% or greater.

[0055] In a further embodiment, the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is individually about 99.5% or greater, and the separation efficiency of fluorine is about 99% or greater.

[0056] According to another aspect of the present disclosure, a process for recovering metals from a lithium-ion battery waste stream is provided. The process may include purifying a lithium-ion battery waste stream containing sulfuric acid (HSO) in a first reactor to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). The purification may include adding a source of iron (Fe) and a first inorganic base to the waste stream to precipitate copper (Cu) by a cementation reaction, and then adding a source of calcium oxide and an oxidizing agent to produce calcium fluoride (CaF), which precipitates from the waste stream. The purification may also include adding a second inorganic base to raise the pH of the waste stream to produce one or more metal precipitation compounds selected from the group consisting of aluminum hydroxide (Al(OH)), titanium hydroxide (Ti(OH)), iron phosphate (FePO), and one or more iron hydroxides (Fe(OH) and Fe(OH)). The process also includes passing the waste stream from the first reactor through a filter to produce a purified filtrate stream and a second retentate comprising one or more metal precipitation compounds, copper (Cu), and calcium fluoride (CaF). The process then includes separating nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream by passing the purified filtrate stream through either a second reactor to perform a co-precipitation process by raising the pH, or through one or more chromatography columns or packed-bed column / reactors. In this manner, an intermediate liquid stream is produced that includes lithium (Li) and one or more recovered products including one or more of nickel (Ni), manganese (Mn), and cobalt (Co). The one or more recovered products are removed from the intermediate liquid stream. The process also includes introducing the intermediate liquid stream into a lithium precipitation reactor to precipitate at least one compound that includes lithium (Li).

[0057] In one embodiment, the source of iron (Fe) comprises iron powder, the first inorganic base and the second inorganic base each comprise sodium hydroxide (NaOH), the source of calcium oxide is selected from the group consisting of lime (CaO), calcium hydroxide (Ca(OH)), and combinations thereof, and the oxidizing agent is selected from the group consisting of hydrogen peroxide (HO), ozone (O), sodium hypochlorite (NaClO), and combinations thereof.

[0058] In one embodiment, a first base is added until the pH is about 5, a second base is added until the pH is about 10.5, and the oxidizing agent comprises hydrogen peroxide (HO), which is added at a concentration of about 4% to about 6% by volume of the total liquid content (waste stream).

[0059] In one embodiment, the addition of the source of iron (Fe) and the first inorganic base to the waste stream is carried out at a pH of about 1 to about 2, with mixing at a temperature of about 55° C. to about 65° C. for a period of about 15 minutes or more.

[0060] In one embodiment, about 2.5 g of iron powder is added per liter (L) of waste stream.

[0061] In one embodiment, the addition of a source of calcium oxide and an oxidizing agent to produce calcium fluoride (CaF) is carried out at a temperature of about 55° C. to about 65° C. with mixing for a period of about 30 minutes or more, at a pH of about 1 to about 2.

[0062] In one embodiment, the addition of the second inorganic base raises the pH of the waste stream to between about 4 and about 5, inclusive.

[0063] In one embodiment, the addition of the second inorganic base to increase the pH is conducted at a temperature of about 55° C. to about 65° C. with mixing for a period of about 60 minutes or more.

[0064] In one embodiment, the purified filtrate stream comprises nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO), and separation of the nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream is performed by passing the purified filtrate stream through a second reactor, where a co-precipitation process is performed, including increasing the pH of the purified filtrate stream to about 11 or greater in an inert environment to form and simultaneously precipitate nickel hydroxide hydrate (Ni(OH) 6H O), manganese hydroxide hydrate (Mn(OH) H O), and cobalt hydroxide hydrate (Co(OH) 7H O) from the purified filtrate stream to produce one or more recovered products.

[0065] In a further embodiment, increasing the pH of the purified filtrate stream further comprises initially adding ammonia to the purified filtrate stream comprising nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO).

[0066] In one embodiment, the one or more recovered products are Ni x Mn y Co 1-x-y It is an electroactive material precursor with a stoichiometry of (OH)2.

[0067] In one embodiment, the one or more recovered products comprise approximately

number

[0068] In one embodiment, the process further comprises determining a first ratio of Ni:Mn:Co in the purified filtrate stream prior to the co-precipitation process, which first ratio is then compared to a target stoichiometric ratio of Ni:Mn:Co for one or more recovered products. ThereforeThe process may include adding one or more of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO) to the purified filtrate stream prior to adjusting the pH to adjust the amount of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO). In this way, the one or more recovered products have a second ratio corresponding to the target stoichiometric ratio.

[0069] In one embodiment, the separation is carried out by passing the purified filtrate stream in a first direction through a packed-bed column / reactor containing a chelating resin, performing a chromatographic separation process at a pH of about 4.5 or less, and producing a raffinate stream containing at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exiting the packed-bed column / reactor, while nickel (Ni) ions and cobalt (Co) ions are retained on the chelating resin in the packed-bed column / reactor. The process further includes regenerating the packed-bed column / reactor by passing a regenerant having a pH of about 1.5 or less through the packed-bed column / reactor to form an extract stream containing nickel (Ni) ions and cobalt (Co) ions. The process also includes precipitating nickel hydroxide (Ni(OH)2) and cobalt hydroxide (Co(OH)2) from the extract.

[0070] In one embodiment, the method further includes combining nickel hydroxide (Ni(OH)) and cobalt hydroxide (Co(OH)) with at least one compound including aluminum hydroxide (Al(OH)) and lithium (Li) to form a precursor of the LiNiCoAlO electroactive material.

[0071] In one embodiment, the process further comprises adjusting the pH of the purified filtrate stream as it enters the packed bed column / reactor to between about 4 and about 5. The process further comprises adjusting the pH to between about 8 and about 10, thereby precipitating manganese hydroxide (Mn(OH)2) and isolating the manganese hydroxide (Mn(OH)2).

[0072] In one embodiment, the at least one compound comprising lithium (Li) comprises lithium carbonate (Li2CO3), water It combines with manganese oxide (Mn(OH)2) to form LiMnO4 electroactive material.

[0073] In one embodiment, adjusting the pH comprises adding sodium hydroxide (NaOH) to the purified filtrate stream.

[0074] In one embodiment, the stationary phase of the packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0075] In one embodiment, the separation is carried out by passing the purified filtrate stream in a first direction through a first packed bed column / reactor containing a first chelating resin and conducting a chromatographic separation process at a pH of about 1.5 or less, thereby producing a first raffinate stream comprising at least one manganese (Mn)-containing species, at least one cobalt (Co)-containing species, and at least one lithium (Li)-containing species that exits the first packed bed column / reactor, while nickel (Ni) ions are retained on the first chelating resin in the first packed bed column / reactor. The process also includes passing the first raffinate stream in a first direction through a second packed-bed column / reactor containing a second chelating resin, performing a chromatographic separation process at a pH of about 2.5 or less, and producing a second raffinate stream comprising at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exiting the second packed-bed column / reactor, while cobalt (Co) ions are retained on the second chelating resin in the second packed-bed column / reactor. The process further includes regenerating the first packed-bed column / reactor by passing a first regenerant having a pH of about 1.5 or less through the first packed-bed column / reactor to form a first extract stream comprising nickel (Ni) ions. Nickel hydroxide (Ni(OH)) may then be precipitated from the first extract stream. The process also includes regenerating the second packed bed column / reactor by passing a second regenerant having a pH of about 2.5 or less through the second packed bed column / reactor to form a second extract stream containing cobalt (Co) ions, followed by precipitating cobalt hydroxide (Co(OH)2) from the second extract stream.

[0076] In one embodiment, the process further includes forming a precursor of the LiNiCoAlO electroactive material by combining nickel hydroxide (Ni(OH)) and cobalt hydroxide (Co(OH)) with at least one compound including aluminum hydroxide (Al(OH)) and lithium (Li).

[0077] In one embodiment, the process further comprises precipitating manganese hydroxide (Mn(OH)2) from the second raffinate stream by adjusting the pH to about 8 or greater to about 10 or less to form an intermediate liquor stream. The manganese hydroxide (Mn(OH)2) is then separated from the intermediate liquor stream.

[0078] In one embodiment, the at least one compound comprising lithium (Li) comprises lithium carbonate (Li2CO3), water It combines with manganese oxide (Mn(OH)2) to form LiMnO4 electroactive material.

[0079] In one embodiment, the process further includes adding sodium hydroxide (NaOH) to the purified filtrate stream to adjust the pH of the purified filtrate stream to about 2.5, and adding sodium hydroxide (NaOH) to the first raffinate stream to adjust the pH of the first raffinate stream to about 3.5.

[0080] In one embodiment, the stationary phase of the first packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid, and the stationary phase of the second packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0081] In one embodiment, the lithium-ion battery waste stream is black mass. Prior to purification, the method further includes subjecting the black mass to a leaching process, which includes mixing an inorganic acid with the black mass to form an acidic mixture, thereby producing a lithium-ion battery effluent stream. An oxidizing agent may be mixed with the acidic mixture. The process may further include adding deionized water to the acidic mixture. The leachate stream is then passed through a second filter to produce a filtrate stream comprising one or more metal sulfates and a first retentate comprising graphite.

[0082] In a further embodiment, the combining of the inorganic acid and the combining of the oxidizing agent are both carried out at a temperature of about 100° C. or less.

[0083] In a further embodiment, the inorganic acid comprises sulfuric acid (H2SO4), the oxidizing agent comprises hydrogen peroxide (H2O2), and the pH of the acidic mixture is about 2.5 or less.

[0084] In a further embodiment, the mixing of the inorganic acid comprises adding black mass to sulfuric acid (H2SO4) having a molar concentration of about 4 M, and the mixing of the oxidizing agent comprises adding about 30% by weight of hydrogen peroxide (H2O2) to the acidic mixture such that the acidic mixture has a solid / liquid ratio of 100 g / L, followed by mixing for about 2 hours or more, and then adding deionized water to dilute the sulfuric acid (H2SO4) to a molar concentration of about 2 M, followed by mixing for about 30 minutes or more.

[0085] In one embodiment, the one or more recovered products have a purity level of about 95% or greater and contain a total cumulative amount of about 5% by weight or less of impurities, including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F).

[0086] In one embodiment, the one or more recovered products have a purity level of about 98% or greater and contain a total cumulative amount of about 2% by weight or less of impurities, including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F).

[0087] In one embodiment, the separation recovers greater than about 80 wt. % each of nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream.

[0088] In one embodiment, introducing the intermediate liquid stream into the lithium precipitation reactor includes adding sodium carbonate (NaCO) and a second inorganic base to the lithium precipitation reactor, wherein the intermediate liquid stream has a temperature of from about 80° C. to about 90° C. for about 90 minutes or more to produce a lithium carbonate (LiCO) precipitate.

[0089] In one embodiment, the intermediate liquid stream comprises lithium sulfate (LiSO) and sodium sulfate (NaSO). Prior to introduction, the intermediate liquid stream is subjected to a thermal shock process to bring the temperature to between about 0° C. and about 30° C., and then ionized in an electrode ionization unit to promote the precipitation of sodium sulfate (NaSO) from the intermediate liquid stream, and then sodium carbonate (NaCO) is added to a lithium precipitation reactor to produce a lithium carbonate (LiCO) precipitate.

[0090] In one embodiment, the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is individually about 95% or greater, and the separation efficiency of fluorine is about 80% or greater.

[0091] In a further embodiment, the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is individually about 99.5% or greater, and the separation efficiency of fluorine is about 99% or greater.

[0092] According to yet another aspect of the present disclosure, a system for recovering metals from a lithium-ion battery waste stream is provided. The system may include a leaching reactor unit including a first heated reaction vessel having an agitator, a source of sulfuric acid (H2SO4), a source of hydrogen peroxide (H2O2), and a source of deionized water (H2O), and a first filter downstream of the first heated reaction vessel. The first heated reaction vessel has multiple inlets for receiving a lithium-ion battery waste stream including black mass, sulfuric acid (H2SO4), hydrogen peroxide (H2O2), and deionized water (H2O), and an outlet for the leachate stream to exit and enter the first filter for separation into a first filtrate stream and a first retentate including graphite. The system also includes an impurity reactor removal unit including a second heated reaction vessel having an agitator, a source of hydrogen peroxide (H2O2), and a source of calcium oxide, and a second filter downstream of the second heated reaction vessel. The second heated reactor has multiple inlets for receiving the first filtrate stream, iron (Fe) powder, sodium hydroxide (NaOH), hydrogen peroxide (HO), and calcium oxide, and an outlet through which the first intermediate liquid exits the second reactor and enters a second filter for separation into a purified filtrate stream and a second retentate containing multiple precipitate compounds, including fluorine (F), phosphate (P), copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). The system also includes a metal recovery unit for separating nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream in the separation unit. The separation unit may be comprised of one or more of a coprecipitation unit and / or one or more chromatography columns or packed-bed column / reactors.When the separation unit is a coprecipitation unit, it includes a third heated reaction vessel for carrying out a coprecipitation process by increasing the pH, a source of nickel sulfate (NiSO), a source of manganese sulfate (MnSO), a source of cobalt sulfate (CoSO), a source of sodium hydroxide (NaOH), an agitator, and a third heated reaction vessel having multiple inlets for receiving the purified filtrate stream, the source of nickel sulfate (NiSO), the source of manganese sulfate (MnSO), the source of cobalt sulfate (CoSO), and the source of sodium hydroxide (NaOH), and an outlet through which the second intermediate liquid stream exits the third heated reaction vessel and enters a third filter downstream of the separation unit for separation. Alternatively, the separation unit may be one or more chromatography columns or packed bed columns / reactors, producing a second intermediate liquid stream that enters a third filter downstream of the one or more chromatography columns or packed bed columns / reactors. Also downstream of the separation unit is a third filter through which the second intermediate liquid stream passes to separate the third intermediate liquid stream and a third retentate comprising one or more recovered products, including nickel (Ni), manganese (Mn), and cobalt (Co). Finally, the system includes a lithium recovery unit including a lithium precipitation reactor for precipitating at least one compound comprising lithium (Li) and a fourth filter downstream of the fourth heated reactor. The lithium precipitation reactor has an outlet through which the fourth intermediate stream exits and enters the fourth filter for separation into a waste stream and a fourth retentate comprising at least one compound comprising lithium (Li). In one embodiment, the impurity reactor removal unit further includes a source of iron (Fe) powder and a source of sodium hydroxide (NaOH), wherein the multiple inlets of the second heated reactor further receive iron (Fe) powder and sodium hydroxide (NaOH).

[0093] In one embodiment, the impurity reactor removal unit further comprises a source of sodium phosphate (Na3PO4).

[0094] In one embodiment, the lithium precipitation reactor is a fourth heated reaction vessel having an agitator, and the lithium recovery unit further includes a source of sodium hydroxide (NaOH), a source of sodium carbonate (NaCO), and the fourth heated reaction vessel has a plurality of inlets for receiving the third intermediate liquid stream, the sodium hydroxide (NaOH), and the sodium carbonate (NaCO), and an outlet through which the fourth intermediate stream exits and enters a fourth filter.

[0095] In one embodiment, the lithium recovery unit further comprises a thermal shock unit and an electrode ionization unit upstream of the lithium precipitation reactor.

[0096] In one embodiment, the metal recovery unit is a co-precipitation unit further including an analyzer for determining the content of nickel (Ni), manganese (Mn), and cobalt (Co) in the purified filtrate stream upstream of the third heated reactor. The co-precipitation unit also includes a controller and one or more metering pumps that regulate the flow of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO) to the multiple inlets of the third heated reactor. The controller receives input from the analyzer and controls the one or more metering pumps.

[0097] In one embodiment, the metal recovery unit includes one chromatographic column or packed bed column / reactor containing a chelating resin for carrying out a chromatographic separation process at a pH of about 4.5 or less. The metal recovery unit also includes one or more precipitation reactors for precipitating compounds including nickel (Ni), manganese (Mn), and cobalt (Co).

[0098] In one embodiment, the stationary phase of the packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0099] In one embodiment, the metal recovery unit includes a first chromatography column or packed bed column / reactor containing a first chelating resin for performing a chromatographic separation process at a pH of about 2.5 or less, a second chromatography column or packed bed column / reactor containing a second chelating resin for performing a chromatographic separation process at a pH of about 3.5 or less, and one or more precipitation reactors for precipitating compounds including nickel (Ni), manganese (Mn), and cobalt (Co).

[0100] In one embodiment, the system further comprises an evaporator downstream of the metal recovery unit and upstream of the lithium recovery unit.

[0101] According to another aspect of the present disclosure, a system for recovering metals from a lithium-ion battery waste stream is provided. The system may include a leaching reactor unit including a first heated reaction vessel having an agitator, a source of sulfuric acid (H2SO4), a source of hydrogen peroxide (H2O2), and a source of deionized water (H2O), and a first filter downstream of the first heated reaction vessel. The first heated reaction vessel has a plurality of inlets for receiving a lithium-ion battery waste stream including black mass, sulfuric acid (H2SO4), hydrogen peroxide (H2O2), and deionized water (H2O), and an outlet for the leachate stream to exit and enter the first filter for separation into a first filtrate stream and a first retentate including graphite. The system also includes an impurity reactor removal unit including a second heated reactor having an agitator, a source of iron (Fe) powder, a source of sodium hydroxide (NaOH), a source of hydrogen peroxide (HO), and a source of calcium oxide, and a second filter downstream of the second heated reactor. The second heated reactor has a plurality of inlets for receiving the first filtrate stream, the iron (Fe) powder, the sodium hydroxide (NaOH), the hydrogen peroxide (HO), and the calcium oxide (e.g., CaO, Ca(OH)), and an outlet for the first intermediate liquid to exit the second reactor and enter the second filter for separation into a purified filtrate stream and a second retentate containing a plurality of precipitated compounds, including fluorine (F), phosphate (P), copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). The system also includes a metal recovery unit for separating nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream in a separation unit, which may consist of either a co-precipitation unit or one or more chromatography columns or packed bed columns / reactors.When the separation unit is a coprecipitation unit, it includes a third heated reaction vessel for carrying out a coprecipitation process by increasing the pH, a source of nickel sulfate (NiSO), a source of manganese sulfate (MnSO), a source of cobalt sulfate (CoSO), a source of sodium hydroxide (NaOH), an agitator, and a third heated reaction vessel having multiple inlets for receiving the purified filtrate stream, the source of nickel sulfate (NiSO), the source of manganese sulfate (MnSO), the source of cobalt sulfate (CoSO), and the source of sodium hydroxide (NaOH), and an outlet through which the second intermediate liquid stream exits the third heated reaction vessel and enters a third filter downstream of the separation unit for separation. Alternatively, the separation unit may be one or more chromatography columns or packed bed columns / reactors, producing a second intermediate liquid stream that enters a third filter downstream of the one or more chromatography columns or packed bed columns / reactors. Also downstream of the separation unit is a third filter through which the second intermediate liquid stream passes to separate the second intermediate liquid stream into a third intermediate liquid stream and a third retentate comprising one or more recovered products including nickel (Ni), manganese (Mn), and cobalt (Co). Finally, the system includes a lithium recovery unit including a lithium precipitation reactor for precipitating at least one compound comprising lithium (Li), and a fourth filter downstream of the fourth heated reactor. The lithium precipitation reactor has an outlet through which the fourth intermediate stream exits and enters the fourth filter for separation into a waste stream and a fourth retentate comprising at least one compound comprising lithium (Li).

[0102] In one embodiment, the lithium precipitation reactor is a fourth heated reaction vessel having an agitator, and the lithium recovery unit further includes a source of sodium hydroxide (NaOH), a source of sodium carbonate (NaCO), and the fourth heated reaction vessel has a plurality of inlets for receiving the third intermediate liquid stream, the sodium hydroxide (NaOH), and the sodium carbonate (NaCO), and an outlet for the fourth intermediate stream to exit and enter a fourth filter.

[0103] In one embodiment, the lithium recovery unit further comprises a thermal shock unit and an electrode ionization unit upstream of the lithium precipitation reactor.

[0104] In one embodiment, the metal recovery unit is a co-precipitation unit further including an analyzer for determining the content of nickel (Ni), manganese (Mn), and cobalt (Co) in the purified filtrate stream upstream of the third heated reactor. The co-precipitation unit also includes a controller and one or more metering pumps for regulating the flow of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO) to multiple inlets of the third heated reactor. The controller receives input from the analyzer and controls the one or more metering pumps.

[0105] In one embodiment, the metal recovery unit includes one chromatographic column or packed bed column / reactor containing a chelating resin for carrying out a chromatographic separation process at a pH of about 4.5 or less. The metal recovery unit also includes one or more precipitation reactors for precipitating compounds including nickel (Ni), manganese (Mn), and cobalt (Co).

[0106] In one embodiment, the stationary phase of the packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0107] In one embodiment, the metal recovery unit includes a first chromatography column or packed bed column / reactor containing a first chelating resin for performing a chromatographic separation process at a pH of about 2.5 or less, a second chromatography column or packed bed column / reactor containing a second chelating resin for performing a chromatographic separation process at a pH of about 3.5 or less, and one or more precipitation reactors for precipitating compounds including nickel (Ni), manganese (Mn), and cobalt (Co).

[0108] In one embodiment, the system further comprises an evaporator downstream of the metal recovery unit and upstream of the lithium recovery unit.

[0109] According to yet another aspect of the present disclosure, a system for recovering metals from a lithium-ion battery waste stream is provided. The system includes a leaching reactor. The leaching reactor includes multiple inlets for receiving a lithium-ion battery waste stream containing black mass, sulfuric acid (H2SO4), hydrogen peroxide (H2O2), and deionized water (H2O). The leaching reactor also has at least one outlet and an agitator. The leaching reactor is further configured to thermally communicate with a first heat source and to subject the lithium-ion battery waste stream to a leaching reaction that produces a leachate stream. The system also includes a first pneumatic filter in fluid communication with the outlet of the leaching reactor, through which the leachate stream passes and is separated into a first filtrate stream and a first retentate containing graphite. The system also includes an impurity removal reactor in fluid communication with the first pneumatic filter. The impurity removal reactor includes a plurality of inlets for receiving the first filtrate stream from the first pneumatic filter, hydrogen peroxide (HO), and calcium oxide (e.g., CaO, Ca(OH)). The impurity removal reactor also includes an outlet and an agitator. The impurity removal reactor is in thermal communication with a second heat source and is configured to purify the first filtrate stream to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti) and produce a first intermediate liquid stream. The system also includes a second pneumatic filter in fluid communication with the outlet of the impurity removal reactor and through which the first intermediate liquid stream passes to separate the purified filtrate stream and a second retentate comprising a plurality of precipitated compounds, including fluorine (F), phosphate (P), copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). The system further includes a co-precipitation reactor in fluid communication with the second pneumatic filter. The co-precipitation reactor includes multiple inlets for receiving the purified filtrate stream from the second pneumatic filter, nickel sulfate (NiSO), manganese sulfate (MnSO), cobalt sulfate (CoSO), and sodium hydroxide (NaOH). The co-precipitation reactor also includes at least one outlet and an agitator.The co-precipitation reactor is in thermal communication with a third heat source and configured to produce a second intermediate liquid stream. The system further includes a third pneumatic filter in fluid communication with the outlet of the impurity removal reactor, through which the second intermediate liquid stream passes to separate a third intermediate liquid stream containing lithium (Li) and a third retentate containing multiple precipitation products, nickel (Ni), manganese (Mn), and cobalt (Co). An evaporator in the system includes an inlet, a distillate outlet, and a concentrate outlet, and is in fluid communication with the third pneumatic filter. The evaporator separates the third intermediate stream into a concentrate stream and a distillate stream. The system further includes a lithium precipitation reactor in fluid communication with the concentrate outlet of the evaporator. The lithium precipitation reactor includes multiple inlets for receiving the concentrate stream from the evaporator, sodium hydroxide (NaOH), and sodium carbonate (NaCO). The lithium precipitation reactor also includes an outlet and an agitator. The lithium precipitation reactor is in thermal communication with a fourth heat source and is configured to generate a product stream. The fourth pneumatic filter is in fluid communication with an outlet of the lithium precipitation reactor through which the product stream passes and is separated into a fourth retentate containing lithium carbonate (Li2CO3) product and a waste stream. The system also includes fluid conduits for establishing fluid communication among the leaching reactor, the first pneumatic filter, the impurities removal reactor, the second pneumatic filter, the co-precipitation reactor, the third pneumatic filter, the evaporator, the lithium precipitation reactor, and the fourth pneumatic filter. The system also includes at least one pump for circulating fluid within the fluid conduits.

[0110] In one embodiment, the multiple inlets of the impurity removal reactor further receive iron (Fe) powder and sodium hydroxide (NaOH).

[0111] In one embodiment, the multiple inlets of the impurity removal reactor further receive sodium phosphate (Na3PO4).

[0112] In one embodiment, the leaching reactor includes a first outlet through which the leachate stream flows and a second outlet through which the first gas effluent flows. The co-precipitation reactor includes a third outlet through which the second intermediate liquid stream flows and a fourth outlet through which the second gas effluent flows. The system further includes a scrubber in fluid communication with the second outlet of the leaching reactor and the fourth outlet of the co-precipitation reactor, such that the scrubber receives the first gas effluent and the second gas effluent for processing.

[0113] According to yet another aspect of the present disclosure, a system for recovering metals from a lithium-ion battery waste stream is provided. The system includes a leaching reactor. The leaching reactor includes multiple inlets for receiving a lithium-ion battery waste stream containing black mass, sulfuric acid (H2SO4), hydrogen peroxide (H2O2), and deionized water (H2O). The leaching reactor also has at least one outlet and an agitator. The leaching reactor is further configured to thermally communicate with a first heat source and to subject the lithium-ion battery waste stream to a leaching reaction that produces a leachate stream. The system also includes a first pneumatic filter in fluid communication with the outlet of the leaching reactor, through which the leachate stream passes and is separated into a first filtrate stream and a first retentate containing graphite. The system also includes an impurity removal reactor in fluid communication with the first pneumatic filter. The impurity removal reactor includes a plurality of inlets for receiving the first filtrate stream from the first pneumatic filter, iron (Fe) powder, sodium hydroxide (NaOH), hydrogen peroxide (HO), and calcium oxide (e.g., CaO, Ca(OH)). The impurity removal reactor also includes an outlet and an agitator. The impurity removal reactor is in thermal communication with a second heat source and is configured to purify the first filtrate stream to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti) and produce a first intermediate liquid stream. The system also includes a second pneumatic filter in fluid communication with the outlet of the impurity removal reactor, through which the first intermediate liquid stream passes to separate the purified filtrate stream and a second retentate containing a plurality of precipitated compounds, including fluorine (F), phosphate (P), copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). The system further includes a co-precipitation reactor in fluid communication with the second pneumatic filter. The co-precipitation reactor includes multiple inlets for receiving the purified filtrate stream from the second pneumatic filter, nickel sulfate (NiSO), manganese sulfate (MnSO), cobalt sulfate (CoSO), and sodium hydroxide (NaOH). The co-precipitation reactor also includes at least one outlet and an agitator.The co-precipitation reactor is in thermal communication with a third heat source and configured to produce a second intermediate liquid stream. The system further includes a third pneumatic filter in fluid communication with the outlet of the impurity removal reactor, through which the second intermediate liquid stream passes to separate a third intermediate liquid stream containing lithium (Li) and a third retentate containing multiple precipitation products, nickel (Ni), manganese (Mn), and cobalt (Co). An evaporator in the system includes an inlet, a distillate outlet, and a concentrate outlet, and is in fluid communication with the third pneumatic filter. The evaporator separates the third intermediate stream into a concentrate stream and a distillate stream. The system further includes a lithium crystallization or lithium precipitation reactor in fluid communication with the concentrate outlet of the evaporator. The lithium precipitation reactor includes multiple inlets for receiving the concentrate stream from the evaporator, sodium hydroxide (NaOH), and sodium carbonate (NaCO). The lithium precipitation reactor also includes an outlet and an agitator. The lithium precipitation reactor is in thermal communication with a fourth heat source and is configured to generate a product stream. The fourth pneumatic filter is in fluid communication with an outlet of the lithium precipitation reactor through which the product stream passes and is separated into a fourth retentate containing lithium carbonate (Li2CO3) product and a waste stream. The system also includes fluid conduits for establishing fluid communication among the leaching reactor, the first pneumatic filter, the impurities removal reactor, the second pneumatic filter, the co-precipitation reactor, the third pneumatic filter, the evaporator, the lithium precipitation reactor, and the fourth pneumatic filter. The system also includes at least one pump for circulating fluid within the fluid conduits.

[0114] In one embodiment, the leaching reactor includes a first outlet through which the leachate stream flows and a second outlet through which the first gas effluent flows. The co-precipitation reactor includes a third outlet through which the second intermediate liquid stream flows and a fourth outlet through which the second gas effluent flows. The system further includes a scrubber in fluid communication with the second outlet of the leaching reactor and the fourth outlet of the co-precipitation reactor, such that the scrubber receives the first gas effluent and the second gas effluent for processing.

[0115] Further aspects and areas of applicability will become apparent from the description provided herein. It is to be understood that the various aspects of the present disclosure may be implemented individually or in combination with one or more other aspects. It is also to be understood that the description and specific examples herein are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The drawings described herein are for purposes of illustrating selected embodiments only, not all possible embodiments, and are not intended to limit the scope of the present disclosure.

[0116] Corresponding reference numerals may indicate corresponding parts throughout the several views of the drawings. [Brief explanation of the drawings]

[0117] [Figure 1] FIG. 1 is a process flow diagram including various steps for removing impurities and recovering precious metals contained in spent lithium ion batteries according to one exemplary embodiment of the present disclosure. [Figure 2] FIG. 2 is a process flow diagram of the co-precipitation stage of FIG. 1 including an automated control system according to another exemplary embodiment. [Figure 3] FIG. 1 is a process flow diagram including a thermal shock process according to another exemplary embodiment. [Figure 4] FIG. 1 is a process flow diagram comprising a chromatographic separation process carried out using one chromatographic column or packed bed column / reactor containing a chelating resin stationary phase, according to another illustrative embodiment. [Figure 5] FIG. 1 is a process flow diagram comprising a chromatographic separation process carried out using two chromatographic columns or a packed bed column / reactor containing a chelating resin, according to another illustrative embodiment. [Figure 6]FIG. 5 is an additional process flow diagram according to another exemplary embodiment, comprising a chromatographic separation process carried out using a single chromatographic column or packed bed column / reactor containing a chelating resin stationary phase as shown in FIG. [Figure 7] FIG. 5 is an additional process flow diagram according to another exemplary embodiment, comprising a chromatographic separation process carried out using a single chromatographic column or packed bed column / reactor containing a chelating resin stationary phase as shown in FIG. [Figure 8] FIG. 6 is an additional process flow diagram according to another exemplary embodiment, comprising a chromatographic separation process carried out using two chromatographic columns or a packed bed column / reactor containing a chelating resin as shown in FIG. 5. [Figure 9] FIG. 6 is an additional process flow diagram according to another exemplary embodiment, comprising a chromatographic separation process carried out using two chromatographic columns or a packed bed column / reactor containing a chelating resin as shown in FIG. 5. [Figure 10] 2A-2D are various diagrams of a system used to implement the process of FIG. 1 according to another exemplary embodiment. [Figure 11] 2A-2D are various diagrams of a system used to implement the process of FIG. 1 according to another exemplary embodiment. [Figure 12] 2A-2D are various diagrams of a system used to implement the process of FIG. 1 according to another exemplary embodiment. [Figure 13] 2A-2D are various diagrams of a system used to implement the process of FIG. 1 according to another exemplary embodiment. [Figure 14] 2A-2D are various diagrams of a system used to implement the process of FIG. 1 according to another exemplary embodiment. [Figure 15] FIG. 3 is a top view of a system including a controller for implementing the process of FIG. 2 according to another exemplary embodiment. [Figure 16]FIG. 4 is a top view of a system including a thermal shock module and an electrode ionization module for carrying out the process of FIG. 3 according to another exemplary embodiment. [Figure 17] FIG. 8 is a top view of a system including a chelating resin column for carrying out the process of FIGS. 4 and 6-7, according to another exemplary embodiment. [Figure 18] FIG. 10 is a top view of a system including two chelating resin columns for carrying out the process of FIGS. 5 and 8-9, according to another exemplary embodiment. [Figure 19] 1 is a chart comparing the recovery of desired metals (Li, Co, Mn, Ni) from two embodiments for removing copper by precipitation (cementation and sulfidation) from spent lithium ion battery streams (copper-rich black mass) in accordance with various aspects of the present disclosure. [Figure 20] 1 is a chart comparing the recovery of desired precipitated metals (Li, Co, Mn, Ni) for an embodiment employing a phosphate additive to remove aluminum from a spent lithium ion battery stream (aluminum-rich black mass) in accordance with various aspects of the present disclosure, compared to a precipitation process lacking a phosphate additive for the same aluminum-rich black mass stream. DETAILED DESCRIPTION OF THE INVENTION

[0118] Exemplary embodiments will now be described in more detail with reference to the accompanying drawings.

[0119] The exemplary embodiments are provided so that the present disclosure will be thorough and will fully convey its scope to those skilled in the art. Numerous specific details are described, such as examples of specific compositions, components, devices, and methods, to provide a thorough understanding of the embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that the exemplary embodiments can be embodied in many different forms, and that neither should be construed to limit the scope of the present disclosure. In some exemplary embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.

[0120] The terms used herein are for the purpose of describing particular exemplary embodiments only and are not intended to be limiting. As used herein, the singular forms "a," "an," and "the" may be intended to include the plural forms unless the context clearly dictates otherwise. The terms "comprises," "comprising," "including," and "having" are inclusive and thus specify the presence of stated features, elements, compositions, steps, integers, operations, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. The open-ended term "comprising" should be understood as an open-ended term used to describe and claim various embodiments defined herein, although in certain aspects, the term may instead be understood as a more restrictive and limiting term such as "consisting of" or "consisting essentially of." Thus, for any given embodiment that recites compositions, materials, components, elements, features, integers, operations, and / or process steps, the present disclosure also specifically includes embodiments that consist of or consist essentially of such recited compositions, materials, components, elements, features, integers, operations, and / or process steps. When "consisting of," alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operations, and / or process steps; when "consisting essentially of," any additional compositions, materials, components, elements, features, integers, operations, and / or process steps that materially affect the basic and novel properties are excluded from such embodiments, but any compositions, materials, components, elements, features, integers, operations, and / or process steps that do not materially affect the basic and novel properties may be included in the embodiments.

[0121] The method steps, processes, and operations described herein should not be construed as necessarily requiring performance in the particular order discussed or illustrated, unless specifically identified as such, and it should also be understood that additional or alternative steps may be employed unless otherwise indicated.

[0122] When a component, element, or layer is referred to as being "on," "engaged to," "connected to," or "coupled to" another element or layer, it may be directly on, engaged with, connected to, or coupled to the other component, element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on," "directly engaged," "directly connected," or "directly coupled" to another element or layer, there may be no intervening elements or layers present. Other words used to describe relationships between elements should be interpreted similarly (e.g., "between" vs. "directly between," "adjacent" vs. "directly adjacent," etc.). As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0123] Terms such as "first," "second," and "third" may be used herein to describe various steps, elements, components, regions, layers, and / or sections; however, these steps, elements, components, regions, layers, and / or sections should not be limited by these terms unless otherwise indicated. These terms may be used only to distinguish one step, element, component, region, layer, or section from another step, element, component, region, layer, or section. As used herein, terms such as "first," "second," and other numerical terms do not imply an order or sequence unless clearly indicated by context. Thus, a first step, element, component, region, layer, or section described below could be referred to as a second step, element, component, region, layer, or section without departing from the teachings of the exemplary embodiments.

[0124] Spatial or temporal relative terms such as "before," "after," "inner," "outer," "beneath," "below," "lower," "above," "upper," and the like are used herein for ease of description and to describe the relationship of one element or feature to another, as shown in the figures. Spatial or temporal relative terms may be intended to encompass different orientations of a device or system in use or operation in addition to the orientation depicted in the figures.

[0125] Throughout this disclosure, numerical values ​​represent approximate scales or range limits to encompass slight deviations from the given value and embodiments having about the stated value, as well as embodiments having the exact stated value. Except for the examples set forth at the end of the detailed description, all numerical values ​​of parameters (e.g., amounts or conditions) in this specification, including the appended claims, are understood to be modified in all instances by the term "about," regardless of whether "about" actually appears before the numerical value. "About" indicates that the stated numerical value allows for some imprecision (some approximation to the exact numerical value; approximately the numerical value, or reasonably close to the numerical value; approximately). Unless the imprecision provided by "about" is otherwise understood in this art in its ordinary sense, "about," as used herein, at least accounts for the variation that can result from ordinary methods of measuring and using such parameters. For example, "about" can include variations of 5% or less, optionally 4% or less, optionally 3% or less, optionally 2% or less, optionally 1% or less, optionally 0.5% or less, and in some embodiments, optionally 0.1% or less.

[0126] Additionally, the disclosure of a range includes the disclosure of all values ​​and further divided ranges throughout the range, including the endpoints and subranges given therein. Thus, a range includes the disclosure of all different values ​​and further divided ranges throughout the range, including the endpoints unless otherwise specified. The disclosure of a value and range of values ​​for a particular parameter (temperature, molecular weight, weight %, etc.) does not exclude other values ​​and ranges of values ​​useful herein. It is contemplated that two or more specific exemplified values ​​for a given parameter may define the endpoints of a range of values ​​that may be claimed for that parameter. Similarly, the disclosure of two or more ranges of values ​​for a parameter (whether such ranges are nested, overlapping, or separate) is contemplated to encompass all possible combinations of value ranges that may be claimed using the endpoints of the disclosed ranges. For example, if a parameter X is exemplified herein as having a value in the range of 1 to 10, or 2 to 9, or 3 to 8, it is also contemplated that the parameter X may have values ​​in other ranges, including 1 to 9, 1 to 8, 1 to 3, 1 to 2, 2 to 10, 2 to 8, 2 to 3, 3 to 10, and 3 to 9.

[0127] Unless otherwise specified, composition amounts are by weight. Additionally, when an amount is expressed as weight, it can be used interchangeably with mass, but should be understood to reflect the mass of a given ingredient.

[0128] As used herein, the terms "composition" and "material" are used interchangeably to refer broadly to a substance that contains at least the preferred chemical constituent, element, or compound, but may contain additional elements, compounds, or substances, including trace amounts of impurities, unless otherwise specified.

[0129] In diagrams, the direction of the arrows generally indicates the flow of matter or information (such as data or instructions) relevant to the diagram. For example, if element A and element B exchange various information, but the information sent from element A to element B is relevant to the diagram, the arrow may point from element A to element B. This unidirectional arrow does not imply that other information is not sent from element B to element A. Furthermore, in response to the information sent from element A to element B, element B may send a request for information or an acknowledgment of receipt to element A.

[0130] As used herein, including in the definitions below, the term "module" or "controller" may be interchangeable with the term "circuitry" when used in the context of, for example, a computing device or module. The terms "module" and / or "controller" may refer to, be a part of, or include: an application-specific integrated circuit (ASIC); a digital, analog, or mixed analog / digital discrete circuit; a digital, analog, or mixed analog / digital integrated circuit; a combinational logic circuit; a field-programmable gate array (FPGA); a processor circuit (shared, dedicated, or group) that executes code; a memory circuit (shared, dedicated, or group) that stores code to be executed by the processor circuit; other suitable hardware components that provide the described functionality; or a combination of some or all of the above, such as a system-on-chip.

[0131] The modules and / or controllers may include one or more interface circuits. In some examples, the interface circuit may include a wired or wireless interface connected to a local area network (LAN), the Internet, a wide area network (WAN), or a combination thereof. The functionality of any given module and / or controller of the present disclosure may be distributed among multiple modules and / or controllers connected via interface circuits. For example, multiple modules and / or controllers may enable load balancing. In further examples, a server (also known as remote, or cloud) module and / or controller may perform some functions on behalf of a client module and / or controller.

[0132] As used above, the term code includes software, firmware, and / or microcode and may refer to programs, routines, functions, classes, data structures, and / or objects. The term shared processor circuit encompasses a single processor circuit that executes some or all code from multiple modules and / or controllers. The term group processor circuit encompasses a processor circuit that executes some or all code from one or more modules and / or controllers in combination with additional processor circuits. References to multiple processor circuits encompass multiple processor circuits on separate dies, multiple processor circuits on a single die, multiple cores of a single processor circuit, multiple threads of a single processor circuit, or combinations thereof. The term shared memory circuit encompasses a single memory circuit that stores some or all code from multiple modules and / or controllers. The term group memory circuit encompasses a memory circuit that stores some or all code from one or more modules and / or controllers in combination with additional memory.

[0133] The term memory circuit is a subset of the term computer-readable medium. As used herein, the term computer-readable medium does not encompass transient electrical or electromagnetic signals propagating through a medium (such as on a carrier wave); therefore, the term computer-readable medium may be considered tangible and non-transitory. Non-limiting examples of non-transitory tangible computer-readable media include non-volatile memory circuits (such as flash memory circuits, erasable programmable read-only memory circuits, mask read-only memory circuits), volatile memory circuits (such as static random access memory circuits, dynamic random access memory circuits), magnetic storage media (such as analog or digital magnetic tape, hard disk drives), and optical storage media (such as CDs, DVDs, and Blu-ray discs).

[0134] The apparatus and methods described in this application may be implemented in part or entirely by a special-purpose computer created by configuring a general-purpose computer to perform one or more specific functions embodied in a computer program. The functional blocks, flowchart components, and other elements described above function as software specifications and can be converted into a computer program by the routine work of a skilled engineer or programmer.

[0135] A computer program includes processor-executable instructions stored on at least one non-transitory, tangible computer-readable medium. A computer program may also include or rely on stored data. A computer program may include a basic input / output system (BIOS) that interacts with hardware in a special-purpose computer, device drivers that interact with specific devices in a special-purpose computer, one or more operating systems, user applications, background services, background applications, etc.

[0136] Computer programs include: (i) written text that is parsed, such as HTML (Hypertext Markup Language), XML (Extensible Markup Language), or JSON (JavaScript Object Notation); (ii) assembly code; (iii) object code generated from source code by a compiler; (iv) source code for execution by an interpreter; (v) source code for compilation and execution by a just-in-time compiler; etc. By way of example only, the source code may be written using syntax from languages ​​including C, C++, C#, Objective-C, Swift, Haskell, Go, SQL, R, Lisp, Java®, Fortran, Perl, Pascal, Curl, OCaml, Javascript®, HTML5 (Hypertext Markup Language 5th revision), Ada, ASP (Active Server Pages), PHP (PHP: Hypertext Preprocessor), Scala, Eiffel, Smalltalk, Erlang, Ruby, Flash®, Visual Basic®, Lua, MATLAB, SIMULINK, and Python®.

[0137] No element recited in a claim is intended to be a mean-plus-function element within the meaning of 35 U.S.C. §112(f) unless the element is expressly recited using the phrase "means for," or, in the case of a method claim, using the phrase "operation for" or "step for."

[0138] As mentioned above, lithium-ion battery waste streams are formed from lithium-ion batteries after they are dismantled, crushed, and / or shredded. Such waste streams may be a material known as black mass for recycling purposes. Black mass may collectively include portions of one or more used lithium-ion batteries, including portions from different types of lithium-ion batteries (e.g., having different active materials). Black mass typically includes all active materials, and therefore may include electrolytic components mixed with anode and cathode active materials. In some examples, used lithium-ion secondary batteries may include positive electrodes / cathodes made from lithium cobalt oxide (LCO), lithium manganese oxide (LMO), lithium nickel manganese cobalt oxide (NMC), lithium iron phosphate (LFP), lithium nickel aluminum cobalt oxide (NCA), lithium titanate (LTO), etc. See, for example, Table 1, which lists common commercially available battery active material combinations. Spent lithium-ion batteries may contain negative electrodes / anodes made from graphite, lithium titanate oxide (Li2TiO3-LTO), lithium metal, and the like. [Table 1]

[0139] Additionally, black mass may contain fluorine, such as in lithium hexafluorophosphate (LiPF). As a result, black mass may contain metals of interest (e.g., precious metals) such as nickel (Ni), manganese (Mn), cobalt (Co), and lithium (Li), as well as impurities such as iron (Fe), copper (Cu), fluorine (F), phosphorus (P), titanium (Ti), and aluminum (Al). It should be understood that the composition of black mass will vary from batch to batch depending on the type of lithium-ion battery. As an example, a batch of black mass may contain the components shown in Table 2 below. [Table 2]

[0140] As lithium-ion batteries evolve, new active materials include more complex materials containing multiple metals (e.g., lithium nickel manganese cobalt oxide Li(Ni)). x Mn y Co z )O2, where 0≦x≦1, 0≦y≦1, 0≦z≦1, x+y+z=1, abbreviated as NMC, for example, LiMn 0.33 Ni 0.33 Co 0.33 As mentioned above, recycling processes have generally focused on recovering cobalt and lithium from lithium cobalt oxide cathodes. However, used lithium-ion batteries often contain many other types of cathode materials, such as nickel and manganese, that also contain valuable metals that are desirable for recovery. Furthermore, black mass typically contains many types of impurities. This is especially true when black mass is obtained from a collection of different types of lithium-ion batteries. Such impurities can adversely affect the purity of the valuable metals recovered from recycling.

[0141] In various embodiments, the systems and processes disclosed herein enable the recycling of spent lithium-ion batteries by removing impurities contained in the black mass and recovering various precious metals of interest. As an example, the disclosed methods and systems provide the ability to process lithium-ion battery waste streams to separate impurities including elements selected from the group consisting of fluorine (F), phosphate (P), copper (Cu), aluminum (Al), iron (Fe), carbon (C) (e.g., in the form of graphite), titanium (Ti), and combinations thereof from recovered metals selected from the group consisting of nickel (Ni), manganese (Mn), cobalt (Co), and lithium (Li).

[0142] In certain embodiments, when a lithium ion battery waste stream initially contains impurities including elements selected from the group consisting of fluorine (F), phosphate (P), copper (Cu), aluminum (Al), iron (Fe), carbon (C) (e.g., in the form of graphite), and titanium (Ti), these impurities can be removed individually or cumulatively (including all removed elements) to a separation efficiency of about 75% or greater, or any of the values ​​defined below. Separation efficiency can be calculated by comparing the initial amount of a given element present in the stream before treatment with the final amount of the given element present in the product after treatment or separation. In certain embodiments, the separation efficiency (η) of a given component can be calculated by:

number

[0143] In some variations, the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is individually about 95% or greater, optionally about 97% or greater, optionally about 98% or greater, optionally about 99% or greater, optionally about 99.5% or greater, optionally about 99.8% or greater, and in some embodiments, optionally about 99.9% or greater.

[0144] In some embodiments, the efficiency of fluorine separation is about 85% or greater, optionally about 90% or greater, optionally about 95% or greater, optionally about 97% or greater, optionally about 98% or greater, and in some embodiments, optionally about 99% or greater.

[0145] In a further embodiment, the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is individually about 95% or greater, and the separation efficiency of fluorine is about 80% or greater.

[0146] In a further embodiment, the separation efficiency for each of copper (Cu), aluminum (Al), titanium (Ti), and iron (Fe) is about 99.5% or more and about 100% or less, and the separation efficiency for fluorine is about 99% or more.

[0147] In other embodiments, the disclosed processes may produce one or more recovered products (including nickel (Ni), cobalt (Co), and manganese (Mn)) having a purity level of about 95% or greater and containing about 5% by weight or less of the total cumulative amount of impurities, including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F). For example, the purity level of the one or more recovered products (including nickel (Ni), cobalt (Co), and manganese (Mn)) may be about 95% by weight or greater and about 99% by weight or less, and may contain about 1% by weight or greater and about 5% by weight or less of the total cumulative amount of impurities, including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F). In one variation, the one or more recovered products have a purity level of about 98% by weight or greater, with a total cumulative amount of impurities including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F) of about 2% by weight or less. Additionally, the separation processes described herein are capable of recovering about 80% by weight or greater of each of nickel (Ni), manganese (Mn), and cobalt (Co) from the waste stream.

[0148] This can be achieved by treating the lithium-ion battery waste stream as a feedstock in various stages of a system for batch processing, where the contents undergo sequential reactions with various reagents to selectively precipitate and remove components of interest, such as nickel (Ni), manganese (Mn), cobalt (Co), and lithium (Li), if present, to form nickel-manganese-cobalt oxide (NMC), lithium carbonate (LiCO). The various stages or units are arranged in series to provide intermediate treatment streams to the next stage unit. Such stages may include, for example, a leaching stage or unit, an impurity removal stage or unit, a metal recovery stage or unit, a lithium recovery stage or unit, and / or one or more precipitation stages, as further described below.

[0149] In certain embodiments, the present disclosure contemplates a process for recovering metals from lithium-ion battery waste streams. The optional first leaching step may involve, for example, recovering black mass from the waste stream by subjecting the black mass to a leaching process. (2)The process may be performed on a lithium-ion battery waste stream containing lithium ion batteries, or the waste stream may be pretreated and received, as described further below. For example, a process for removing impurities and recovering various precious metals from one or more spent lithium-ion batteries according to one exemplary embodiment of the present disclosure is shown in FIG. 1 and generally designated by reference numeral 100. As shown, the process may be performed in system 100 including various sequentially arranged stages, including a leaching unit or stage 102, an impurity removal unit or stage 104, and two precipitation units or stages 106 and 108. In stages 102, 104, 106, and 108, the contents are collected and processed in reactors or vessels 110, 122, 132, and 142. Reactors 110, 122, 132, and 142 may each be a jacketed stirred tank internally coated with a corrosion-resistant lining to withstand the high temperature and acidic conditions that may occur in system 100. For example, reactors 110, 122, 132, 142 may each include an agitator 112, 124, 134, 148 for stirring the contents, and a jacket 116, 126, 136, 150 for circulating a heating / cooling medium (e.g., steam, etc.) surrounding the respective reactor to maintain a desired temperature.

[0150] The process of system 100 begins with a leaching stage 102. In the example of Figure 1, various components are fed to a reactor (e.g., leaching reactor) 110, identified as V-001. (1) Black Mass (2) to form an acidic mixture, and then an oxidizing agent (3) Mix with the acid mixture and deionized water (4) The black mass is subjected to a leaching process which involves adding (2) After this process, the leachate stream produced in reactor 110 may include: (5) is then passed through a second filter to produce a filtrate stream containing one or more metal sulfates. (7) and a first retentate containing graphite. (6)and

[0151] Therefore, during the leaching step 102, inorganic acid from the source or container (1) is fed to the leaching reactor 110 during the first phase. The inorganic acid may be sulfuric acid (H2SO4) or another suitable inorganic acid, as shown in FIG. 1. Notably, hydrochloric acid may be avoided in some embodiments because chlorine may cause electrochemical cell contamination if the recycled material contains high levels of chlorine. In some examples, the inorganic acid may include about 4 M sulfuric acid (H2SO4). During this time, the agitator 112 may be activated to agitate the acid solution in the leaching reactor 110. In some embodiments, the mixing of the inorganic acid and the oxidizing agent is performed at a temperature of about 100°C or less, optionally about 95°C or less, and in some embodiments, about 90°C or less. The oxidizing agent may be hydrogen peroxide (H2O2), ozone (O3), sodium hypochlorite (NaClO), or a combination thereof. In some variations, the oxidizing agent is hydrogen peroxide (H2O2). In particular, since the addition of black mass and dilution with sulfuric acid is an exothermic process, the temperature may be monitored to ensure that it does not exceed the boiling point of water, for example by introducing cold water or via a heat exchanger. During the first phase, black mass from a source or vessel may be gradually added to the stirred acid solution in the leaching reactor 110.

[0152] In one variation, the inorganic acid includes sulfuric acid (H2SO4), the oxidizing agent includes hydrogen peroxide (H2O2), and the pH of the acid mixture in the leaching reactor 110 is about 2.5 or less. The hydrogen peroxide (H2O2) may be added at a concentration of about 4% to about 6% by volume, based on the total volume of the liquid contents. In a further variation, mixing the inorganic acid includes adding black mass to sulfuric acid (H2SO4) having a molar concentration of about 4 M, and mixing the oxidizing agent includes adding about 30% by weight of hydrogen peroxide (H2O2) to the acid mixture so that the acid mixture has a solid / liquid ratio of 100 g / L, followed by mixing for about 2 hours or more in the leaching reactor 110, then diluting the sulfuric acid (H2SO4) to a molar concentration of about 2 M by adding deionized water, followed by mixing for about 30 minutes or more.

[0153] Black Mass(2) After the acid solution is introduced, the metals in the black mass begin to react with the metals, which react to form their respective sulfates. In some instances, the fluorine (F) in the black mass is converted to hydrogen fluoride (HF). Some of the HF remains in solution contained in the leaching reactor 110, while the remainder is converted to gas. (80) and discharged to the scrubber 114.

[0154] During the first phase, an oxidizing agent may be supplied to the leaching reactor 110 from a source or vessel. The oxidizing agent may be hydrogen peroxide (H2O2) or other suitable oxidizing agent, as shown in Figure 1. In some examples, the oxidizing agent is 30% hydrogen peroxide (H2O2). The oxidizing agent may be supplied to the reactor 110 before, simultaneously with, or after the inorganic acid and / or black mass are added. The mixture of acid solution, oxidizing agent, and black mass may be stirred for a defined period of time (e.g., 1 hour, 2 hours, 3 hours, etc.).

[0155] In some examples, it may be desirable to maintain the temperature of the liquid in the leaching reactor 110 at a specified level, desirably below 100°C, as described above. For example, the specified temperature level may range from about 60°C (140°F) to about 80°C (176°F). In some embodiments, the minimum required temperature level may be about 60°C (140°F), and the desired temperature level may be about 80°C (176°F). However, in some cases, the temperature of the liquid may rise above the desired level and / or fall below the minimum required temperature level. For example, as described above, heat from the reaction of the acid solution with the metals in the black mass may cause the temperature of the liquid in the leaching reactor 110 to rise above the desired temperature (e.g., 80°C). In other examples, the liquid temperature may not rise to the required level (e.g., 60°C). In such examples, the liquid temperature may be controlled in a different manner. For example, the liquid temperature may be reduced by adjusting the rate of black mass addition to the acid solution. In another example, the liquid temperature may be lowered or raised by circulating a heating / cooling medium (eg, steam, etc.) through a jacket 116 surrounding the leaching reactor 110.

[0156] Once the stirring period is complete, add deionized water from the source or container. (4) is added to the reactor 110 in a second phase. For example, deionized (DI) water may be added to dilute the sulfuric acid. For example, adding water may reduce the molarity of the liquid in the leaching reactor 110 from about 4 M to about 2 M. Furthermore, as noted above, because the addition of black mass and dilution of sulfuric acid are exothermic processes, the water may be added to cool the contents of the reactor 110 so that the temperature does not exceed 90-100°C. In some examples, the temperature may be cooled to about 60°C (140°F). After the addition of the DI water, the mixture in the leaching reactor 110 is stirred for a specified period of time (e.g., about 30 minutes). At this point, the pH of the solution may be acidic, e.g., between about 0.1 and about 1. In some embodiments, the pH of the solution may be about 0.1. The leachate stream may contain various metal sulfates, such as nickel sulfate (NiSO4), manganese sulfate (MnSO4), cobalt sulfate (CoSO4), etc.

[0157] The vessel contents within reactor 110 are then pumped via pump 118 through filter 120, which may be a pneumatic filter. After the leachate stream has passed through the filter, a filtrate stream containing one or more metal sulfates is generated. (7) and a first particle containing solid matter such as carbon (graphite) particles. Retentate (6)Graphite is thus removed from the leachate stream. Pump 118 and filter 120 are identified in FIG. 1 as P-001 and F-001, respectively. The remaining contents that pass through filter 120 (e.g., first filtrate) are fed to impurity removal reactor 122, which is used in impurity removal stage 104. In some examples, substantially all of the carbon (graphite) particles in the vessel contents may be captured in filter 120 as filtrate. Such carbon (graphite) particles may be passed or conveyed to a vessel for further processing (e.g., drying). In some examples, pump 118 may be a centrifugal pump as shown in FIG. 1 or other suitable pump, and filter 120 may be a pressure filter, hydraulic filter, gravity filter, or other suitable type of filter.

[0158] After filtration, reactor 110 may be washed with an internal spray ball to remove acid residues and all leaching reaction products may be sent to reactor 122.

[0159] Additionally, acid residues in the filter cake / return may be neutralized by rinsing the residue to reduce operator exposure during cake collection. In some examples, a separate water stream may be lined with pump 118 and dilute caustic added upstream of filter 120 to remove residual filtrate, which may be sent to wastewater treatment. At the end of this stage 102, the graphite cake (e.g., in a container, on filter 120, etc.) may be collected for disposal.

[0160] In the impurity removal step 104, impurities are removed. This may be done simultaneously in a collective batch process, or individual steps for removing specific impurities may be performed sequentially. As explained below, if the impurity removal steps are not performed in a chronological or sequential manner, high efficiency of impurity removal may not be achieved. In the impurity removal step 104, the leachate produced from step 102 is (7)Impurities (e.g., certain metals) therein may be removed, e.g., converted to their hydroxides or other forms and precipitated. In some embodiments, there may be a minimal compromise of no more than 2% precious metal concentration while removing impurities.

[0161] In one embodiment, the method of the present disclosure comprises removing a lithium ion battery waste stream containing sulfuric acid (H2SO4) in the impurity removal reactor 122. (7) to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti). Initially, the contents from reactor 110 (e.g., a first filtrate or leachate) (7) is provided to an impurity removal reactor 122, identified in FIG. 1 as V-002. Purification may include removing copper (Cu) from the liquid stream. In some variations, purification may include precipitating a product containing the copper (Cu) removed (e.g., separated) from the liquid stream, which may occur, for example, via a cementation reaction or a sulfidation reaction. In other embodiments, removing copper (Cu) from the waste stream includes subjecting the waste stream to solvent extraction. Removal of copper (Cu) may include one or more of these removal processes (e.g., one or more of sulfidation, cementation, and solvent extraction).

[0162] As an example, in one variation, copper removal from a liquid stream may be achieved by a sulfidation reaction, which produces a precipitate that can be removed. As further described herein, copper sulfide precipitation is useful for recovering more of the desired metal downstream in the process, since many such metals are poorly soluble as sulfides. Generally, the logarithmic solubility product (K) of a metal sulfide is sp ) is higher than that of metal hydroxides (i.e., the higher the logarithmic solubility product, the lower the solubility product). For example, for copper (Cu), the first K of copper sulfide (CuS) is sp is 10 -35.9 and the second K sp is 10 -19.8When lithium-ion battery effluent, e.g., black mass, is relatively rich in copper (Cu), e.g., about 6% copper by weight or more, other copper removal processes, such as cementation, may be less desirable because iron (Fe), released during the process when impurities such as copper are removed, can cause the desired precious metal to precipitate prematurely from the process stream, thus reducing recovery of the desired metal downstream of the process.

[0163] In the sulfidation reaction and removal process, a sulfur (S) source, such as sodium sulfide (NaS), may be added to the liquid stream to provide sulfur compounds / ions as a reagent to promote the precipitation of copper (Cu) via the sulfidation reaction. Copper precipitation as sulfide typically occurs at lower pH values ​​than precipitation of the target / desired metal as a hydroxide. As those skilled in the art will appreciate, the pH should not be too low, e.g., about 0.5 or less, because some sulfide precipitates are acid-soluble. Furthermore, it is understood that at higher pH ranges, e.g., from about 4 to about 8, the metal salts will not precipitate as sulfides because they have already formed hydroxide salts. In one variation, the sulfur (S) source can be sodium sulfide (NaS). Therefore, sodium sulfide (NaS) can be administered to the leach solution in an amount greater than the required stoichiometric ratio of sodium sulfide (NaS) to copper, e.g., at a pH of about 1.1 to about 1.5 to remove copper. The pH of the liquid can optionally be around 1, for example, in some variations, from about 0.9 to about 1.1.

[0164] The pH of the liquor may then be raised to an acidic pH, for example, from about 4.5 to about 5. The addition and subsequent reaction of sodium sulfide (NaS) to the liquor stream may serve to raise the pH to a target range. In some embodiments, the amount of sodium sulfide (NaS) introduced / dosed into the stream is controlled to avoid an undesirably large increase in pH. For example, dissolution of sodium sulfide forms aqueous hydrogen sulfide and NaOH (which causes a pH increase) according to the following reaction scheme: Na2S + H2O → H2S + 2NaOH. In another variation, a first inorganic base may be added to further raise the pH to the desired pH range.

[0165] In order for copper ions to form copper sulfide, they must react with hydrogen sulfide ions, and therefore protonation of hydrogen sulfide occurs in alkaline media based on speciation, as shown in the following reaction scheme: CuSO4+HS - +OH - →Cu(s)+SO4 2- +H2O.

[0166] Another sulfurization reaction that can occur when sodium sulfide is added is: Na2S(s)+Cu 2+ (aq) → CuS(s) + 2Na + (aq). Therefore, in one embodiment, the overall sulfurization reaction in the effluent is expressed as: Na2S(aq)+CuSO4(aq)→Na2SO4+CuS(s).

[0167] In some variations, the pH during the sulfurization reaction may be from about 0.7 to about 2, and in some variations, optionally from about 1.5 to about 2. The sulfurization reaction may be carried out for about 30 minutes in some variations.

[0168] The copper precipitate formed by the sulfidation reaction can then be removed from the liquid stream. The precipitated copper (Cu) can be removed in a solid-liquid separation process downstream from the first reactor, such as filtration, as described further below. After sulfidation removal, in some variations, about 90% or more of the original copper (Cu) present in the liquid stream is removed.

[0169] In another variation, copper removal may be achieved via a cementation reaction. In another variation, iron (Fe) provided from an iron (Fe) source is used for the cementation reaction and removal process. (9) and a first inorganic base(8) may be added to the liquid stream to precipitate copper (Cu) via a cementation reaction. In some variations, the first base may be added until the pH of the mixture is about 5, and in some other variations, about 5.5. Without limiting the disclosure, it is believed that a spontaneous reaction occurs between the copper ions and the iron, oxidizing the iron and reducing the copper ions by electron transfer, resulting in the precipitation of copper as follows: Cu 2+ (aq) + Fe(s) → Cu(s) + Fe 2+ (aq). The precipitated copper (Cu) can be removed in a solid-liquid separation process downstream from the first reactor, such as filtration, as further described below. The source of iron (Fe) can be iron powder.

[0170] The first inorganic base (as well as the second inorganic base described below) may be selected from relatively strong inorganic bases such as sodium hydroxide (NaOH), potassium hydroxide (KOH), and / or lithium hydroxide (LiOH). In one variation, the base comprises sodium hydroxide (NaOH).

[0171] A comparison of the recovery of desired (e.g., precious) metals (e.g., Li, Co, Mn, Ni) by precipitation for two alternative copper removal processes (cementation and sulfidation) on copper-rich black mass (e.g., 6 wt. % copper (Cu)) is shown in Figure 19. As can be seen, sulfidation performed better on such lithium-ion battery waste streams, e.g., containing copper-rich black mass, with less undesired precipitation of desired / precious metals, indicating that greater amounts of desired metals are available for recovery downstream in the disclosed processes.

[0172] In other variations, where lithium-ion battery waste streams, such as black mass, are relatively rich in copper (Cu), e.g., having about 3% or more by weight of copper, alternative copper removal processes, such as solvent extraction processes, may be used. For example, the waste stream containing the copper to be removed can be contacted (e.g., mixed) with an extractant and an organic phase. In such a process, the extractant forms a complex with the target impurity, here copper (Cu), and transfers the complex from the liquid aqueous phase in the waste stream to the organic phase. In this way, the extractant / organic phase forms a raffinate, which can be further separated by gravity or centrifugation processes. In some variations, the solvent extraction process for removing copper (Cu) can also advantageously simultaneously remove impurities, including iron (Fe), when the waste stream is mixed with the extractant and organic phase.

[0173] In one variation, a suitable extractant for removing copper and, optionally, iron includes an oxime such as 5-nonyl-salicylaldoxime, also known as 2-hydroxy-5-nonylbenzaldehyde oxime (NSAO, commercially available as ACORGA™ P50 oxime solvent extraction reagent). A suitable organic phase for copper solvent extraction is a liquid hydrocarbon such as kerosene. The kerosene may be sulfonated kerosene. The aqueous-to-organic ratio (A / O ratio) may be set to 1:1. In one variation, the pH may be about 1 to maximize copper (Cu) extraction while minimizing coextraction of precious metals. The concentration of the extractant (e.g., 5-nonyl-salicylaldoxime) may be between 0% and about 20% by volume of the total organic phase. In one variation, solvent extraction may be carried out in a reactor with three separate stages, which may provide greater effectiveness than a single-stage column / reactor separation. Further stages may be added, but solvent extraction beyond the fourth stage appears to only marginally increase copper (Cu) extraction efficiency.

[0174] After performing the solvent extraction process, in some variations, about 95% or more of the initial copper (Cu) present in the waste stream and about 95% or more of the initial iron (Fe) present in the waste stream may be removed from the waste stream.

[0175] The method may then include fluoride removal. The fluoride removal process comprises the addition of a calcium source and an oxygen source to produce calcium fluoride (CaF), which precipitates from the liquid waste stream. (11) , for example calcium oxide, and optionally an oxidizing agent (10) The calcium oxide source may further comprise adding (11) is selected from the group consisting of lime (CaO), calcium hydroxide (Ca(OH)), and combinations thereof, and the oxidizing agent may include hydrogen peroxide (HO), ozone (O), sodium hypochlorite (NaClO), and combinations thereof. In some variations, solid-phase calcium oxide (CaO) or solid-phase calcium hydroxide (Ca(OH)) may be mixed or reacted (e.g., slaked) with water in a reactor or tank to form a liquid-phase calcium hydroxide source (Ca(OH)), which may then be introduced into and / or mixed with a liquid stream for fluoride removal. The pH during fluoride removal is from about 1 to about 2.

[0176] In some embodiments, an oxidizing agent (10) is hydrogen peroxide (H2O2). Again, after the reaction, precipitated calcium fluoride (CaF2) can be removed in a downstream solid-liquid separation process, such as filtration, as further described below. Of note, in some variations, if iron is added to the process (as in the reaction above, where copper precipitates), it may be added to the process before the lime addition (CaO) to remove fluoride. If unreacted CaO is present in the solution, zero-valent iron acts as an adsorbent to remove copper, and Cu 2+ It does not act as a reducing agent to convert HCl to Cu and may therefore detrimentally interfere with copper removal.

[0177] An alternative fluorine removal process may be a selective adsorption process in which the liquid stream can be treated in one or more columns (e.g., chromatography columns or packed bed columns / reactors) with a resin process that uses a stationary phase of a polymeric adsorbent highly selective for fluorine to remove fluorine. As a non-limiting example, a suitable fluorine removal process is described in PCT International Application PCT / SG2022 / 050014, entitled "PROCESS FOR RECYCLING LITHIUM IRON PHOSPHATE BATTERIES," relevant portions of which are incorporated herein by reference. Fluorine removal is advantageous because, if fluorine remains in significant concentrations in the recycled active material, it can form harmful impurity compounds (e.g., as hydrogen fluoride (HF)) that can cause capacity fade in the battery and degradation of the recycled cathode electroactive material.

[0178] In variations where the lithium-ion battery effluent stream, e.g., black mass, is relatively rich in aluminum (Al), e.g., having about 3% or more by weight of aluminum, the present disclosure may further include additional purification steps for the lithium-ion battery effluent stream after copper and fluoride removal. More specifically, additional processes for removing aluminum may be implemented as described herein. In such embodiments, a phosphate source, e.g., sodium phosphate (Na3PO4), may be added to the liquid stream to the impurity removal reactor 122 to facilitate aluminum (Al) removal. The addition of phosphate to the leach solution is advantageous in that aluminum phosphate (AlPO4) precipitates from the aluminum-rich black mass (in addition to aluminum hydroxide, as described below). When treating aluminum-rich black mass streams, the presence of aluminum (Al) can lead to the premature precipitation of significant amounts of desired (e.g., precious) metals (e.g., Li, Co, Ni) in the impurity removal phase. Most phosphates have products with lower solubility compared to their hydroxide counterparts, and forming metal phosphates serves to remove them from the leach solution as solid products. In one variation of the present disclosure, a phosphate source such as sodium phosphate (NaPO) is added to provide phosphate anions and promote the formation of aluminum phosphate as a desired by-product, as shown in the following reaction scheme: Al2(SO4)3+2Na3PO4→2AlPO4+3Na2SO4.

[0179] After adding a phosphate source, e.g., sodium phosphate (NaPO), the pH of the liquid stream / liquid can be increased from above 4 to below about 5, and then to around 4 but below 5, prior to liquid-solid separation (e.g., filtration) of the precipitated phosphate. The results are shown in Figure 20, which illustrates precipitation with and without phosphate additives. Thus, in an aluminum-rich leachate, simply changing the pH results in aluminum precipitation, with significant precipitation rates of desired precious metals (e.g., Li, Mn, Co, Ni). When phosphate additives are used in a comparative precipitation involving the formation of aluminum phosphate, the precipitation rates of the desired precious metals are lower. Iron (Fe) and aluminum (Al) removal rates may be as high as 100%.

[0180] In some embodiments, after copper and fluoride removal, the liquid waste stream is treated with a base such as, for example, sodium hydroxide (NaOH). (12) The pH may be adjusted to have a pH of about 4.5 or greater to about 5 or less by adding HCl. The pH shift aids in the removal of remaining impurities, including one or more of iron (Fe), titanium (Ti), aluminum (Al), phosphate (P), and combinations thereof. The temperature during this process is about 60°C, and the mixing is carried out for about 60 minutes in some variations.

[0181] The purification may also optionally include the addition of a second inorganic base to raise the pH of the liquid waste stream to produce one or more metal precipitation compounds, including metals selected from the group consisting of aluminum (Al), titanium (Ti), iron (Fe), and combinations thereof. (12) More specifically, in some variations, the refining also includes adding a second inorganic base to raise the pH of the liquid waste stream to produce one or more metal hydroxide precipitate compounds selected from the group consisting of aluminum hydroxide (Al(OH)), titanium hydroxide (Ti(OH)), iron phosphate (FePO), iron hydroxide (either Fe(OH) and / or Fe(OH)), and combinations thereof. (12)In some embodiments, the second inorganic base can be added until the pH of the mixture is optionally about 10.2 or greater, optionally about 10.3 or greater, optionally about 10.4 or greater, and in some embodiments, optionally about 10.5 or greater. In some further variations, the second inorganic base can be added until the pH of the mixture is about 10.5 or greater and about 11.5 or less, optionally about 10.5 or greater and about 11 or less, which can depend on the stoichiometry of the metal in the final product formed.

[0182] Adding sulfuric acid upstream during metal leaching produces sulfate ions (SO4 2- An oxidizing agent such as H2O2 added upstream of the leaching reactor promotes the presence of ferrous iron. 2+ Ferric ions 3+ ions, iron will be present in the effluent as Fe2(SO4)3 in the matrix. Therefore, during the impurity removal process, iron and phosphorus will precipitate as FePO4. Similarly, oxidizing agents (e.g., H2O2) can change the oxidation states of titanium(II) and aluminum(III) metals individually, resulting in the precipitation of titanium and aluminum hydroxides (e.g., Ti(OH)2 or Ti(OH)4 and Al(OH)3).

[0183] A second inorganic base, such as NaOH, used to adjust the pH may also further promote the precipitation of excess copper (Cu) and iron (Fe) during this impurity removal process, such that residual copper (Cu) and iron (Fe) are removed as impurities.

[0184] In some variations, further processing to deeply remove impurities may be advantageous. For example, a solvent extraction process may be used to further remove impurities from the solution, including metals selected from the group consisting of iron (Fe), copper (Cu), aluminum (Al), and combinations thereof. After adjusting the pH of the solution, e.g., to about 2 to about 2.5, and performing liquid-solid separation / filtration to remove precipitated impurities, the solution may be sent to a solvent extraction tank (although not shown, such a solvent extraction tank may be placed in fluid communication with the impurity removal reactor / tank and the product precipitation reactor / tank). In some embodiments, solvent extraction may be carried out in a tank or reactor having multiple stages.

[0185] A solution containing one or more impurities to be removed, including copper (Cu), iron (Fe), and optionally aluminum (Al), can be contacted (e.g., mixed) with an extractant and an organic phase. In such a process, the extractant can form complexes with the target impurities, here copper (Cu), iron (Fe), and / or aluminum (Al), and transfer the complexes from the liquid aqueous phase to the organic phase in the solution. In this way, the extractant / organic phase forms a raffinate, which can be further separated by gravity or centrifugation processes.

[0186] In one variation, an extractant suitable for deep impurity removal includes bis-(2-ethylhexyl)phosphoric acid, also known as di-(2-ethylhexyl)phosphoric acid (DEHPA or HDEHP). An organic phase suitable for use in solvent extraction of impurity metals may be a liquid hydrocarbon, such as kerosene. In one variation, the kerosene may be sulfonated kerosene. The water-to-organic ratio (A / O ratio) may be set at 2 to 1. In one variation, the pH may be about 2 to about 2.5. The concentration of the extractant (e.g., bis-(2-ethylhexyl)phosphoric acid) may be greater than 0% by volume and less than or equal to about 15% by volume of the total organic phase volume, e.g., about 10% by volume in one variation and about 15% by volume in another variation, and the hydrocarbon (e.g., kerosene) may be present at greater than 85% by volume and less than about 100% by volume of the total organic phase volume, e.g., about 90% by volume, or about 85% by volume. The duration of the deep impurity removal solvent extraction process is, for example, about 20 minutes.

[0187] Therefore, the extractant and organic phase / hydrocarbon may be mixed with the process stream solution in a solvent extraction tank / reactor to reduce the cumulative level of all metal impurities of interest (e.g., the combined amounts of copper (Cu), iron (Fe), and aluminum (Al)) to about 20 ppm or less. For example, the impurity level in the solution entering the tank may be 100-200 ppm, and may be reduced to less than about 20 ppm in the purified product stream exiting the solvent extraction tank.

[0188] As shown in FIG. 1, one variation of the present technology is to provide a source or container of sodium hydroxide (NaOH). (8、12) Iron (Fe) powder was introduced from (9) is introduced into reactor 122 from another source or vessel to initiate the removal of impurities such as copper (Cu) via cementation, including the removal of copper (Cu) as an impurity via precipitation, which involves a cementation reaction. As will be appreciated by those skilled in the art, a source of sodium hydroxide (NaOH), not shown in FIG. (8、12) and iron (Fe) powder source (9)can be easily replaced with a single source of sodium sulfide (NaS, e.g., in water) introduced into reactor 122 if the desired copper (Cu) precipitation reaction is alternatively sulfidation.

[0189] This is considered the first phase of the impurity removal stage 104. This mixture may be agitated with an agitator 124 for a defined period of time (e.g., 15 minutes, 30 minutes, etc.). In some examples, 19.125 M NaOH and iron (Fe) powder may be added. As noted above, the pH of the leachate exiting the leaching reactor 110 and entering the reactor 122 may be acidic, e.g., having a pH of about 0.1 or greater and about 1 or less. In one example, the pH may be adjusted to between about 1 and about 2 or less in the reactor 122 using an inorganic base, such as sodium hydroxide (NaOH), to initiate copper removal via cementation. For example, adding sodium hydroxide (NaOH) and iron (Fe) powder to the leachate for cementation may produce copper (Cu) precipitate and ferric sulfate (FeSO). In another variation, adding sodium sulfide (NaS) to the leachate for sulfidation may produce copper (Cu) precipitate in the form of CuS and sulfuric acid (HSO). In some instances, the fluorine in the mixture may be converted to hydrogen fluoride (HF). Some of the HF may remain in solution contained in reactor 122, while the remainder may be converted to a gas. (81) and may be discharged to a scrubber 114.

[0190] For example, Cu cementation with zero-valent iron (Fe) can be applied for at least 15 minutes with stirring. During this time, the temperature can be maintained at approximately 60°C by circulating a heating / cooling medium (e.g., steam) through the jacket 126 surrounding the reactor 122. Ignoble metals can reduce precious metal ions according to the electromotive force series. The larger the voltage gap between one half-cell reaction, the more likely the reaction will occur from a thermodynamic and electrochemical standpoint. Therefore, among all the metals contained in the leachate, iron and copper have the potential to react favorably due to their high cell potential (E_cell). When cementing Cu with Fe powder, as in the example of Figure 1, Fe is reduced by Fe 2+ is oxidized to Cu 2+ is reduced to Cu. The reaction is shown below: Fe+Cu 2+ →Fe 2+ +Cu

[0191] Next, the oxidizer from the source or container (10) and lime content from the source or container (source of calcium oxide). (11) is fed to reactor 122 to begin removing further impurities, such as fluoride, from the leachate. This may be considered the second phase of the impurity removal stage 104. For example, an oxidizing agent (10) may be hydrogen peroxide (H2O2) or other suitable oxidizer as shown in Figure 1, and the lime component may be calcium oxide (CaO) or Calcium hydroxide (Ca(OH) 2 )(11) As noted above, although not shown, the calcium oxide component may be supplied as a liquid phase from an upstream tank where the calcium oxide component is mixed with water or other solvent. In some examples, the oxidizer is 30% hydrogen peroxide (HO). This mixture may be stirred in the reactor 122 using the agitator 124 for another defined period of time (e.g., 15 minutes, 30 minutes, etc.).

[0192] For example, lithium hexafluorophosphate (LiPF6) is one of the most commonly used ionically conductive salts in organic carbonate-based electrolytes for lithium-ion batteries. Dissolution of LiPF6 in black mass can induce the formation of highly toxic HF when water reacts with phosphorus pentafluoride (PF5). This HF formation is shown below: LiPF6 → LiF+PF5 PF5+H2O→POF3+2HF

[0193] Conventional lithium battery recycling processes do not remove fluoride. However, failure to remove fluoride / hydrofluoric acid (HF) can lead to capacity fade in batteries, including those incorporating NMCs made from recycled or recovered metals. For example, as shown below, HF can destroy available Li + Reduce the concentration and make Li a useful resource + Instead of precipitating LiF, LiF can be formed. Li + +HF → LiF+H +

[0194] To alleviate this problem, HF that is not removed from the system may be removed via added calcium oxide (CaO). For example, a mixture of CaO and HF will produce calcium fluoride (CaF2) and water, as shown below: CaO+2HF→CaF2+H2O

[0195] During the second phase, the pH remains the same, between about 1 and about 2, wherein the mixture may be stirred with an agitator 124 for another defined period of time (e.g., 15 minutes, 30 minutes, etc.), and the temperature may be maintained at about 60° C. by thermal communication with a heat source. For example, a heating / cooling medium (e.g., steam, etc.) may be circulated through a jacket 126 surrounding the reactor 122.

[0196] In some embodiments, a particular order of removal of certain types of impurities, as described above, is desired. For example, it may be advantageous to remove copper from the leachate before removing fluoride. If fluoride is removed before copper (by adding CaO), zero-valent iron acts as an adsorbent to remove copper, and Cu 2+ Since CaO does not act as a reducing agent for Cu to Cu, any unreacted CaO remaining in solution may interfere with copper removal. For example, reduction results in a decrease in charge / oxidation state, while oxidation results in an increase in charge.

[0197] After removing copper and fluoride, the method contemplates adding a second inorganic base to raise the pH of the effluent and produce one or more metal precipitation compounds. In certain embodiments, the one or more metal precipitating compounds may be selected from the group consisting of aluminum hydroxide (Al(OH)), titanium hydroxide (Ti(OH)), iron phosphate (FePO), iron hydroxide (Fe(OH) and Fe(OH)), and combinations thereof. As shown in FIG. 1 , sodium hydroxide (NaOH) is fed to the impurity removal reactor 122 to begin removing additional impurities, such as residual iron (Fe), phosphate (P), titanium (Ti), and aluminum (Al), from the intermediate liquid / vessel contents. This may be considered the third phase of the impurity removal stage 104. As the NaOH is added, the pH of the overall solution may be adjusted from about 4 or greater to about 5 or less, the solution may be stirred with the agitator 124 for another defined period of time (e.g., about 60 minutes), and the temperature may be maintained at about 60° C., as described above. This pH transition may aid in the removal of residual iron, phosphate, titanium, and aluminum. In some embodiments, 19.125M NaOH is added to the impurity removal reactor 122. NaOH is added in small increments (e.g., in 0.5 increments) to gradually raise the pH to 5.5. The NaOH added in phase 3 may be supplied from the same source or container of NaOH used in phase 1 in step 104, or may be supplied from a different source or container.

[0198] For example, to remove iron and phosphate, sulfuric acid (H2SO4) is added to leach out the metals.2- The hydrogen peroxide (H2O2) added earlier upstream of the leaching reactor 110 enhances the presence of ferrous iron (Fe 2+ ) to ferric iron (Fe 3+ ) ion, so that the iron exists in the matrix as Fe2(SO4)3. In such instances, the iron and phosphorus precipitate as iron phosphate (FePO4).

[0199] Furthermore, the iron previously administered (as iron powder) for copper removal simultaneously reacts with PO4 3- If copper is first precipitated by cementation, copper(II) cations are reduced to metallic copper (Fe + Cu). 2+ →Fe 2+ +Cu), iron oxidizes to ferrous iron Fe 2+ The hydrogen peroxide (H2O2) used in the leaching reactor 110 forms ferrous ions, Fe 2+ Ferric Fe 3+ ions, oxidized to PO4 3- is removed as FePO4. In some embodiments, NaOH may be used to adjust the pH to promote precipitation of excess Fe and remove impurities.

[0200] For the removal of titanium and aluminum, H2O2 acting as an oxidizing agent pushes the oxidation states of the metals to the titanium(II) and aluminum(III) valence states, respectively, and hydroxides can precipitate (Ti(OH)4 and Al(OH)3).

[0201] After treatment, the impurity removal reactor 122 generates a waste stream (13) exits reactor 122 through filter 130 and produces a purified filtrate stream (15) and a second retentate comprising one or more metal precipitating compounds and calcium fluoride (CaF), which can be further processed in the system as described below. (14)Thus, the vessel contents in reactor 122 are pumped via pump 128 (e.g., a centrifugal pump, etc.) through filter 130 (e.g., a pressure filter, hydraulic filter, gravity filter, etc.), and the second filtrate stream enters reactor 132 for use in metal recovery stage 106 (sometimes referred to as co-precipitation stage 106). Pump 128 and filter 130 are identified in FIG. 1 as P-002 and F-002, respectively. In some embodiments, substantially all of the impurities (e.g., metal hydroxides) precipitated in reactor 122 are captured in filter 130.

[0202] After filtration, the impurity removal reactor 122 may be washed with an internal spray ball to remove any acid residue within the vessel and send all reaction products to a reactor (e.g., receiving reactor) 132. Additionally, any chemical residues in the filter cake may be rinsed to reduce operator exposure during cake collection. Additionally, a separate water stream may be lined with pump 128 and dilute caustic may be added upstream of filter 130 to remove residual filtrate, which may be sent to wastewater treatment. At the end of this batch cycle (e.g., stage 104), the retentate / hydroxide cake may be collected for disposal.

[0203] After leaching of metals and removal of impurities in the reactors 110, 122, the method may include processing the purified liquid stream to separate and recover nickel (Ni), manganese (Mn), and cobalt (Co) by passing the purified filtrate stream through a metal recovery unit. The metal recovery unit may include a second reactor for performing a co-precipitation process by increasing the pH, or one or more chromatography columns. In an alternative variation, metal recovery may include both processing in one or more second reactors and processing in one or more chromatography columns. In this manner, an intermediate liquid stream containing lithium (Li) and one or more recovered products including one or more of nickel (Ni), manganese (Mn), and cobalt (Co) are produced. The one or more recovered products may be electroactive material precursors, more specifically, Ni. x Mny Co 1-x-y The positive electrode / cathode active material precursor may have a stoichiometry of (OH)2, where x is <1 and y is <1. To convert this precursor material to the electroactive material (oxide form), it can be mixed with other reagents, such as lithium carbonate for lithiation. After mixing, the electroactive material precursor can be subjected to a heat treatment, such as calcination, at a temperature of about 700°C or higher to form the electroactive material. In one variation, one or more recovered products have a stoichiometry of about

number

[0204] In some embodiments, after metal leaching and impurity removal as described above, one or more recovered products, including one or more of nickel (Ni), manganese (Mn), and cobalt (Co), are extracted from the intermediate liquid stream. In some variations, the reaction between stoichiometric amounts of transition metal salts, such as nickel sulfate hydrate (NiSO4·6H2O), manganese sulfate hydrate (MnSO4·H2O), and cobalt sulfate hydrate, is carried out. occurs As an optional variation, a complexing agent (chelating agent) and a base can be used in the process. For example, ammonia (NH3) can be used as the complexing agent (chelating agent) and added first before particle precipitation to form [M(NH3)] 2+A concentration gradient sufficient to promote the formation of a complex (where M is a transition metal such as nickel (Ni), manganese (Mn), or cobalt (Co)) may be provided. Sodium hydroxide or potassium hydroxide may be selected as the base to maintain a high pH and provide hydroxide ions for precipitation of the metal product. In such a variation, the reaction that occurs is shown below: where "n" represents the number of coordinated ammonia molecules, M represents nickel (Ni), manganese (Mn), or cobalt (Co), and is 6 or less. Reaction (1) shows the complexation / chelation of the metal to a complex. Reaction (2) shows the addition of a base such as NaOH to form the metal hydroxide. M 2+ +nNH3 → [M(NH3)n] 2+ (1) [M(NH3)n] 2+ +2OH - →M(OH)2+nNH3(2) In this manner, the liquid stream can be further processed to separate and recover the hydroxides of nickel (Ni), manganese (Mn), and cobalt (Co), as further described below.

[0205] In another variation shown in Figure 1, the NMC electroactive material precursor can be extracted from the system in reactor 132 of the co-precipitation step 106. Reactor 132 is identified as V-003 in Figure 1. Stated differently, the purified liquid stream (15) is processed in reactor 132 to separate and recover nickel (Ni), manganese (Mn), and cobalt (Co). (15) may be received directly from filter 130 after exiting impurity removal reactor 122, may be pretreated as described above with a complexing or chelating agent such as ammonia, or may simply be treated as described herein in reactor 132 to promote co-precipitation.

[0206] Regarding the electroactive material precursor of interest, Ni x Mn y Co 1-x-yO2 (NMC) layered oxide may exist primarily as sulfate in reactor 132 where the liquid stream is not treated with ammonia. The following is an example of the formation of NMC sulfate in reactor 132 by using sulfuric acid (leaching) and hydrogen peroxide as a reducing agent in stages 102, 104. 6LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O2(s)+9H2SO4(aq)+H2O2(aq)→2NiSO4(aq)+2MnSO4(aq)+2CoSO4(aq)+3Li2SO4(aq)+10H2O(g)+2O2(g)

[0207] Thus, the purified filtrate stream includes nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO), and a method according to an embodiment of the present disclosure may include separating the nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream by passing the purified filtrate stream through a second reactor for performing a co-precipitation process.

[0208] The co-precipitation process may involve raising the pH of the purified filtrate stream to about 11 or higher in an inert environment (e.g., nitrogen blanket) to form nickel hydroxide hydrate (Ni(OH)2·6H2O), manganese hydroxide hydrate (Mn(OH)2·H2O), and cobalt hydroxide hydrate (Co(OH)2·7H2O), which are simultaneously precipitated from the purified filtrate stream to produce one or more recovered products.

[0209] Therefore, in the co-precipitation step 106, sodium hydroxide (NaOH) is added to raise the pH level, as shown in FIG. (19)may be fed to reactor 132. For example, 19.125 M NaOH may be added to raise the pH to about 10.5, 11, or the like. During this time, the solution in reactor 132 may be stirred with agitator 134 for a defined period of time (e.g., about 30 minutes), and the temperature may be maintained at about 80°C (176°F) by circulating a heating / cooling medium through jacket 136 surrounding reactor 132. After the stirring period is complete, NiMnCo(OH)6 precipitate, sodium sulfate, and lithium sulfate are produced.

[0210] For example, NaOH (19) After being added to reactor 132, the metal sulfates NiSO4, MnSO4, and CoSO4 are converted to their hydroxides, forming nickel hydroxide hydrate (Ni(OH)2·6H2O), manganese hydroxide hydrate (Mn(OH)2·H2O), and cobalt hydroxide hydrate (Co(OH)2·7H2O), respectively. Alternatively, in processes where the purified liquid stream is pretreated with a complexing or chelating agent (e.g., ammonia), NaOH can be added to reactor 132 to achieve the pH levels described above and form the same metal hydroxide hydrates, i.e., nickel hydroxide hydrate (Ni(OH)2·6H2O), manganese hydroxide hydrate (Mn(OH)2·H2O), and cobalt hydroxide hydrate (Co(OH)2·7H2O).

[0211] As mentioned above, an inert environment can be provided, for example using a nitrogen blanket, to maintain the oxidative integrity of the hydroxide. NiSO4(aq)+2NaOH+6H2O→Ni(OH)2·6H2O+Na2SO4 MnSO4(aq)+2NaOH+H2O→Mn(OH)2·H2O+Na2SO4 CoSO4(aq)+2NaOH+7H2O→Co(OH)2·7H2O+Na2SO4

[0212] In some embodiments, a nitrogen purge system may be used with reactor 132 to generate a nitrogen blanket. For example, nitrogen (e.g., a nitrogen source providing N gas) may be connected to a push-pull (e.g., pad-de-pad) valve to keep reactor 132 oxygen-free during pump-in and pump-out steps. Additionally, reactor 132 may be equipped with a valve (e.g., a pressure relief valve) designed for 45 PSIG and set at 45 PSIG for the possibility of future high-pressure operation.

[0213] In some embodiments, the concentration of one or more recovered components, such as NMC components, is analyzed for all liquids from the impurity removal stage 104 collected in reactor 132 and adjusted accordingly. For example, the hydroxide precipitates may each share similar crystalline and microspheroidal structures and therefore may behave similarly in mechanism, appearing as a mixed salt rather than three distinct phases, regardless of the Ni / Mn / Co ratio.

[0214] The method may further include determining a first ratio of Ni:Mn:Co in the purified filtrate stream prior to the co-precipitation process. The method may include comparing the first ratio to a target stoichiometric ratio of Ni:Mn:Co for one or more recovered products. The method may then include adding nickel sulfate (NiSO4) to the purified filtrate stream prior to adjusting the pH. (16) , manganese sulfate (MnSO4) (17) , and cobalt sulfate (CoSO4) (18) to the purified filtrate stream to adjust the amount of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO). In this way, the one or more recovered products have a second ratio corresponding to the target stoichiometric ratio.

[0215] Therefore, if the Ni:Mn:Co ratio is insufficient for the intended recycled electroactive material precursor, or if the desired product requires a different NMC permutation / stoichiometry, sulfate salts can be added to reactor 132 as needed, as shown in FIG. 1. This can achieve, for example, molar equivalence between nickel, manganese, and cobalt in reactor 132. The following is an example of one such form of NMC sulfate addition. In certain embodiments, the system can include an analytical unit that can sample the purified liquid stream and determine the nickel (Ni), manganese (Mn), and cobalt (Co) content upstream of the reactor. The co-precipitation apparatus can also include a controller and one or more metering pumps to regulate the flow of nickel sulfate (NiSO), manganese sulfate (MnSO), and cobalt sulfate (CoSO) to multiple inlets of the third heated reactor. The controller receives input from the analyzer and controls one or more metering pumps to adjust the amount of each sulfate salt fed to the stream or reactor.

[0216] In various embodiments, NMC sulfates can be dosed appropriately through the use of an automated process implemented with a controller, such as a programmable logic controller (PLC). For example, Figure 2 shows an example of a piping and instrumentation design for precipitation stage 106 in which nickel, manganese, and cobalt sulfates are added to reactor 132 using a PLC 202. In Figure 2, a real-time control system for managing the Ni-Mn-Co molar balance for customization of the NMC(OH)2 product can be implemented by using an inductively coupled plasma (ICP) analyzer 204 with an algorithm implemented in the PLC.

[0217] In the example of FIG. 2, the concentrations of nickel, manganese, and cobalt in the solution flowing into reactor 132 can be measured using an ICP analyzer 204. The measurements are relayed to PLC 202 for further calculations. For example, an algorithm stored in PLC 202 can determine the amounts of nickel sulfate (NiSO4), manganese sulfate (MnSO4), and cobalt sulfate (CoSO4) needed to co-precipitate the final NiMnCo(OH)6 product based on metal concentration data (e.g., represented by one or more feedback signals) from ICP analyzer 204. In some examples, the algorithm can incorporate any form of desired NiMnCo(OH)6 output and calculate the desired dosage by balancing the molar concentrations to a setpoint. Once the desired dosage is determined, PLC 202 can provide control signals to metering pumps 206, 208, and 210 for the following precise dosages: NiSO4, MnSO4, and CoSO4. After the desired levels of NiSO4, MnSO4, and CoSO4 sulfates are achieved, the pH of the solution can be increased by adding NaOH, as described above. In the example of FIG. 2, a controller 212 (e.g., implementing proportional-integral-derivative (PID) control) can control a metering pump 214 to add a desired amount of NaOH based on a pH sensor 216 attached to the reactor 132.

[0218] Thus, for example, instead of manually precipitating NiMnCo(OH) hydroxide (also known as NMC111), the entire process of step 106 can be automated. This provides convenience to the end user and management by dosing the appropriate nickel sulfate (NiSO4), manganese sulfate (MnSO4), cobalt sulfate (CoSO4) to replenish the required concentrations of Ni, Mn, and Co in solution to produce the appropriate NMC hydroxide permutation (and / or other permutations such as NMC622, NMC811, NMC532, etc., as non-limiting examples).

[0219] With continued reference to Figure 1 and / or Figure 2, an appropriate amount of NaOH (19) and an appropriate amount of NMC sulfate (as needed) 16, 17, 18 derivedAfter the addition of NMC, reactor 132 contains all of the NMC product as a precipitate, as well as sodium sulfate and lithium sulfate, which dissolve under process conditions as described above. In some embodiments, the residual HF in the solution contained in reactor 132 is converted into gas (82) and may be vented to scrubber 114. The contents within reactor 132 are then pumped via pump 138 (e.g., a centrifugal pump, etc.) through filter 140 (e.g., a pressure filter, a hydraulic filter, a gravity filter, etc.) to produce a third filtrate (e.g., containing sodium sulfate and lithium sulfate). (20) is collected in a reactor (e.g., a receiving reactor) 142 used in the precipitation step 108. Retentate (21) contains one or more recovered products including nickel (Ni), manganese (Mn), and cobalt (Co). Pump 138 and filter 140 are identified in Figure 1 as P-003 and F-003, respectively. In some embodiments, substantially all of the one or more recovered products (e.g., NMC product) that precipitate in reactor 132 are captured as retentate in filter 140.

[0220] After filtration, reactor 132 may be washed with an internal spray ball to remove process fluid residue within reactor 132, and all reaction products are sent to reactor 142. At the end of this batch cycle (stage 106), the product NMC cake may be collected for further drying and packaging.

[0221] In some embodiments, the contents that pass through filter 140 (e.g., the third filtrate) (22) At least some of the water therein may be removed before being collected in reactor 142. This may be accomplished by heating and distillation / evaporation processes. In various embodiments, the process of removing water from the third filtrate may be considered part of co-precipitation stage 106 and / or precipitation stage 108. In other embodiments, the process of removing water from the third filtrate may be considered a separate stage, such as a water removal stage.

[0222] For example, in FIG. 1, the third filtrate containing sodium sulfate and lithium sulfate (22) The filtrate is passed through an evaporator 144. The evaporator separates the intermediate third filtrate stream into a concentrate stream. (26) and the distillate stream (25) In such an example, about 50% of the water in the filtrate is evaporated to form a distillate stream, and the resulting concentrated vapor may be collected in a storage tank. (25) can be used in upstream processes if desired. The remaining contents (e.g., concentrate stream) (26) may be pumped to reactor 142 via pump 146. Pump 146 is identified in FIG. 1 as P-301. In some embodiments, the concentrated stream may be collected in a separate storage tank before being pumped to reactor 142. In certain aspects, the lithium concentration is increased for the next process step; by way of example only, after being processed in an evaporator, the concentration of lithium (Li) in the stream may be greater than about 12 g / L.

[0223] The disclosed method also includes precipitation of an intermediate liquid stream, e.g., a concentrate stream, to precipitate at least one compound comprising lithium (Li). (26) It is also contemplated that the concentrate stream may be introduced into the lithium precipitation reactor. For example, the concentrate stream may be introduced into the lithium precipitation reactor. Then, sodium carbonate (Na2CO3) (28) with an inorganic base (e.g., NaOH) (27) The liquid stream may be added to a lithium precipitation reactor together with the lithium carbonate (LiCO). The liquid stream is maintained at a temperature of about 80° C. to about 90° C. for about 90 minutes or more in the lithium precipitation reactor to produce a precipitate of lithium carbonate (LiCO).

[0224] In the precipitation step 108, sodium carbonate (Na2CO3) (28)is optionally fed to a lithium precipitation reactor 142 to convert lithium sulfate (LiSO) to lithium carbonate (LiCO). Reactor 142 is designated V-004 in FIG. 1. During (or before) this, the temperature of the contents (e.g., concentrate stream, third filtrate, etc.) in reactor 142 can be adjusted to a desired temperature (e.g., about 80°C-90°C) by circulating a heating / cooling medium through jacket 150, which functions as a heat exchanger. In one variation, sodium carbonate (NaCO) solution can be added to the lithium-bearing liquid stream in the lithium precipitation reactor at a feed rate of 20 L / min.

[0225] Next, as shown in Figure 1, sodium hydroxide (NaOH) (27) to reactor 142 to raise the pH level. For example, 19.125 M NaOH may be added to raise the pH to about 13. During this time, the solution in reactor 142 may be stirred with agitator 134 for a defined period of time (e.g., about 30 minutes, 1 hour, 1.5 hours, etc.), and the temperature may be maintained at a desired temperature with jacket 150. Once the stirring period is over, the lithium sulfate precipitates as lithium carbonate. Li2CO3 ... Li2SO4(aq)+Na2CO3→Li2CO3(s)+Na2SO4(aq) (3) Li2SO4 + 2NaOH → 2LiOH + Na2SO4 (coprecipitation) (4) 2LiOH+Na2CO3→Li2CO3+2NaOH (5)

[0226] The contents of the vessel in the reactor 142 are then (29) is pumped via pump 152 (e.g., a centrifugal pump, etc.) through filter 154 (e.g., a pressure filter, a hydraulic filter, a gravity filter, etc.). Pump 152 and filter 154 are identified in FIG. 1 as P-004 and F-004, respectively. In some embodiments, substantially all of the lithium carbonate product (30)may be trapped in filter 154. After filtration, reactor 142 may be washed with an internal spray ball to remove process fluid residue within reactor 142. At the end of this batch cycle (e.g., step 108), the product Li2CO3 cake (30) The effluent that passes through the filter 154 (e.g., the fourth filtrate) may be collected for further drying and packaging. (31) may be sent to wastewater treatment and / or recycled to reactor 110 to facilitate dilution of the acid and enhance the lithium concentration in subsequent processes performed in system 100.

[0227] In various embodiments, the contents from reactor 132 of FIG. 1 may be provided to another suitable module instead of evaporator 144 before being collected in reactor 142. For example, 10 m 3 In some cases where larger volumetric applications are being processed, the evaporator may provide limited capacity. As such, in some embodiments, the contents may be passed through a thermal shock module coupled with electrode ionization to facilitate thermal shock by lowering the temperature. In some variations, the temperature after the thermal shock process may be about 30°C or less, optionally about 25°C or less, and in some embodiments, about 0°C or more to about 30°C or less, optionally about 0°C or more to about 25°C or less. In such instances, the thermal shock process may be less costly, energy intensive, and time-consuming than the evaporation process.

[0228] In one variation, the thermal shock module is advantageous when the intermediate liquid stream contains lithium sulfate (LiSO) and sodium sulfate (NaSO). Prior to introduction into the lithium precipitation reactor, the intermediate liquid stream is subjected to a thermal shock process and then ionized in an electrode ionization unit to promote the precipitation of sodium sulfate (NaSO) from the intermediate liquid stream. Because sodium sulfate is less soluble than lithium sulfate, it is desirable to remove sodium sulfate from solution. Sodium carbonate (NaCO) may then be added to the lithium precipitation reactor to produce a lithium carbonate (LiCO) precipitate.

[0229] For example, FIG. 3 illustrates a process occurring in a system 300 that is substantially similar to the process performed in the system 100 of FIG. 1, except that the contents that have passed through the filter 140 (e.g., the third filtrate) (22) The contents pass through a thermal shock module 302 and an electrode ionization module 304. The process performed in system 300 includes steps 102, 104, 106, and 108 of FIG. 1, where the contents are collected and processed in reactors 110, 122, 132, and 142 (also individually identified as E-82, E-83, E-84, and E-78 in FIG. 3). , pumped through pumps 118, 128, 138, 146, 152 (E-74, E-69, E-72, E-77, E-70, E-81, respectively, in FIG. 3). In various embodiments, the processes completed in modules 302 and / or 304 may be considered part of co-precipitation stage 106 and / or precipitation stage 108. In other embodiments, such processes may be considered separate stages.

[0230] In the example of FIG. 3, the contents from the filter 140 (22) is passed to a thermal shock module (e.g., freeze crystallization module) 302, which converts the lithium sulfate / sodium sulfate stream into sodium sulfate. (23)In module 302, lithium sulfate may be extracted from a solution containing sodium cations and sulfate anions. For example, monovalent cation precipitation can be difficult in heating and distillation / evaporation processes due to its high solubility product and solubility in water. However, in module 302, the lithium sulfate / sodium sulfate solution is thermally shocked to lower the temperature of both precipitates. Because sodium sulfate has a lower solubility product than lithium sulfate, more sodium sulfate can be removed as a precipitate after the thermal shock.

[0231] Next, the remaining solution (24) is pumped through the electrode ionization module 304 (Also identified as E-79 in Figure 3) The solution is pumped to the (25) Remove lithium sulfate (26) The sediment and its sludge are collected as the main product, while the permeate (25) is collected and recycled to the reactor 110 to facilitate dilution of the acid, which may increase the lithium concentration in the remaining sludge. (26) The primary product (e.g., precipitate and its sludge) containing sodium carbonate is then pumped via pump 146 to reactor 142, where it is (27) is added to precipitate the lithium sulfate as lithium carbonate as explained above.

[0232] The method also contemplates separation by a chromatographic separation process rather than or in addition to a coprecipitation process. The method may include passing the purified filtrate stream in a first direction through a chromatography column or packed-bed column / reactor containing a chelating resin to perform the chromatographic separation process. In some variations, the pH in the column may be about 4.5 or less. After passing through the chromatography column or packed-bed column / reactor, a raffinate stream containing at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exits the chromatography column, while at least one nickel (Ni)-containing species, more specifically nickel (Ni) ions, and at least one cobalt (Co)-containing species, more specifically cobalt (Co) ions, are retained on the chelating resin in the chromatography column or packed-bed column / reactor. The method may also include regenerating the chromatography column or packed-bed column / reactor by passing a regenerating solution through the chromatography column. The regenerating solution may be passed through the chromatography column or packed-bed column / reactor in a countercurrent or concurrent direction. For example, in some embodiments, the regeneration may be a countercurrent regeneration, in which a regeneration solution is passed through a chromatography column or a packed-bed column / reactor to form an extract stream containing at least one nickel (Ni)-containing species (e.g., nickel (Ni) ions) and at least one cobalt (Co)-containing species (e.g., cobalt (Co) ions). The regeneration solution may have a pH of about 1.5 or less. The collected extract stream may then be subjected to a precipitation reaction to precipitate nickel hydroxide (Ni(OH)2) and cobalt hydroxide (Co(OH)2) from the extract.

[0233] The method may further include adjusting the pH of the purified filtrate stream to between about 4 and about 5 as it enters the chromatography column or packed bed column / reactor. Thus, the method may further include precipitating manganese hydroxide (Mn(OH)2) from the raffinate stream, which may be accomplished by adjusting the pH to between about 8 and about 10 by adding a strong alkaline base such as sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), etc. to form an intermediate liquid stream. The manganese hydroxide (Mn(OH)2) may then be removed or separated from the stream prior to entering the lithium precipitation reactor.

[0234] In one variation, the method includes forming a precursor of the LiNiCoAlO electroactive material by combining nickel hydroxide (Ni(OH)) and cobalt hydroxide (Co(OH)) with at least one compound including aluminum hydroxide (Al(OH)) and lithium (Li).

[0235] In various embodiments, the contents from reactor 122 in FIG. 1 may undergo another alternative separation process, such as passing through a chromatography column or packed-bed column / reactor with a chelating resin before being collected in reactor 132 and / or reactor 142. In some cases, the chelating resin may be capable of selectively capturing metal ions, such as Ni and Co, from an acidic pH solution (e.g., the solution from reactor 122). For example, the low-pH leachate (e.g., the second filtrate) that passed through filter 130 may be passed through one or more selective columns (e.g., fixed-bed columns), and the contents from the columns may then be collected in reactor 132 and / or reactor 142. Both the raffinate and the resin regeneration stream pass through V-003, dripping off any precious metals they contain. In such an example, the chelating resin process may replace or be part of co-precipitation step 106 in FIGS. 1 and 3.

[0236] The column contains a stationary phase of a chelating resin, which can be any resin known in the art that has selectivity for nickel ions (Ni) and / or cobalt ions (Co). In one variation, the stationary phase is a matrix of macroporous styrene divinylbenzene and functionalized iminodiacetic acid. The purified liquid can flow through the resin from the top of the column to the bottom of the column. In some embodiments, the resin can have a bed height of about 0.6 m or more and about 1 m or less. In various embodiments, the flow rate of the solution through the column can be monitored and maintained within a desired range, and the removal efficiency of Ni and Co can be monitored by measuring the concentrations before and after the resin column.

[0237] In some embodiments, the resin in the column may need to be regenerated when it is exhausted or its exchange capacity is full. In such instances, an appropriate acid (e.g., sulfuric acid, hydrochloric acid, etc.) or ammonium solution may be used to regenerate the resin. Regeneration can be performed from top to bottom (cocurrent) or bottom to top (countercurrent). During regeneration, the resin elutes Ni and Co with the eluate, and the regenerated resin is used for further cycles of Ni and Co removal.

[0238] For example, Figure 4 shows a first chromatographic separation process using a chelating resin as the stationary phase in system 400 that may be implemented with systems 100, 300 (or portions thereof), in which a leachate from an impurity removal step (e.g., the second filtrate from impurity removal step 104 in Figures 1 and 3) is passed through a selective column (e.g., a fixed bed column) 402 containing a resin as described above. Process 400 may be included in step 106 in Figures 1 and 3, or may be a separate step that replaces step 106 in Figures 1 and 3.

[0239] In the example of Figure 4, after the pH of the leachate is adjusted to a desired level (e.g., 4.5), the leachate is passed through column 402. The resin in column 402 co-separates and adsorbs Ni and Co ions in the leachate (extract), while other ions such as Mn and Li in the remaining leachate (raffinate) pass through.

[0240] Figure 6 is an illustrative diagram of this metal ion separation phase of the process carried out in system 400. As shown, sodium hydroxide (NaOH) is added to the leachate to adjust the pH to 4.5. The leachate is then fed to the top of column 402 (designated by the letter A in Figure 6). The resin within the column adsorbs Ni and Co ions from the leachate, and the remaining solution exits column 402 (designated by the letter B in Figure 6).

[0241] Continuing with reference to FIG. 4, after the resin co-separates and adsorbs the Ni and Co ions, the ions can be recovered through a regeneration process in column 402. The recovery process begins by introducing a regeneration solution from a source or vessel 408 into the bottom of column 402 to elute the Ni and Co ions from the resin. The pH of the regeneration solution can be 1.5. The solution containing Ni and Co ions can then be collected in vessel 410, where the Ni and Co can be separated from the solution by a precipitation process that raises the pH of the solution to a precipitation pH. The Co and Ni in the solution may be precipitated in the form of hydroxides (cobalt hydroxide and nickel hydroxide) after concentration adjustment. In some embodiments, the hydroxides and lithium precipitate (from the remaining leachate produced in the metal ion separation phase) can then be combined to produce LiNiCoAlO.

[0242] 7 is an illustrative diagram of this metal ion recovery phase of the process carried out in system 400. As shown, regenerant solution from tank #1 (e.g., vessel 408 in FIG. 4) is introduced into the bottom of column 402, and the solution containing Ni and Co ions passes to tank #2 (e.g., vessel 410 in FIG. 4).

[0243] In some embodiments, the remaining leachate from the metal ion separation phase and the contents from the metal ion recovery phase may be collected in a reactor (e.g., reactor 132 or reactor 142 in FIGS. 1 and 3). For example, as shown in FIG. 4, the remaining leachate may be pumped to a reactor via pump 404. In this reactor, the solution (containing Mn and Li) can be used to produce LiMnO active material. For example, the solution can be processed to first precipitate Mn (e.g., as manganese hydroxide, Mn(OH)), and then sodium carbonate (NaCO) can be added to precipitate lithium (e.g., as lithium carbonate, LiCO). From these chemicals (Mn(OH) and LiCO), LiMnO can be produced.

[0244] In other embodiments, the chromatographic separation process using a chelating resin as a stationary phase can be carried out using multiple columns. Thus, a method provided in certain aspects of the present disclosure can include, for example, a separation performed by passing a purified filtrate stream through a first chromatographic column or packed-bed column / reactor containing a first chelating resin in a first direction and carrying out the chromatographic separation process at a pH of about 1.5 or less, thereby producing a first raffinate stream containing at least one manganese (Mn)-containing species (e.g., manganese (Mn) ions), at least one cobalt (Co)-containing species (e.g., cobalt (Co) ions), and at least one lithium (Li)-containing species, which exits the first chromatographic column or packed-bed column / reactor. At least one nickel (Ni)-containing species (e.g., nickel (Ni) ions) is retained on the first chelating resin in the first chromatographic column or packed-bed column / reactor. The method may also include passing the first raffinate stream in a first direction through a second chromatography column or packed-bed column / reactor containing a second chelating resin, for example, performing a chromatographic separation process at a pH of about 2.5 or less to produce a second raffinate stream containing at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species that exits the second chromatography column or packed-bed column / reactor. At least one cobalt (Co)-containing species (e.g., cobalt (Co) ions) is retained on the second chelating resin in the second chromatography column or packed-bed column / reactor. The method may also include regenerating the first chromatography column or packed-bed column / reactor by, for example, passing a first regenerant solution having a pH of about 1.5 or less through the first chromatography column or packed-bed column / reactor to form a first extract stream containing at least one nickel (Ni)-containing species (e.g., nickel (Ni) ions). In some embodiments, the first regenerant solution may be passed through the column in a second direction opposite to the first direction.The method includes precipitating nickel hydroxide (Ni(OH)2) from the first extract stream. The method also includes regenerating the second chromatography column or packed bed column / reactor, e.g., by passing a second regenerant having a pH of about 2.5 or less through the second chromatography column or packed bed column / reactor to form a second extract stream comprising at least one cobalt (Co)-containing species (e.g., cobalt (Co) ions). The method can include precipitating cobalt hydroxide (Co(OH)2) from the second extract stream. In some embodiments, the second regenerant can be passed through the column in a second direction opposite the first direction.

[0245] In one variation, the method may include forming a precursor of the LiNiCoAlO electroactive material by combining nickel hydroxide (Ni(OH)) and cobalt hydroxide (Co(OH)) with at least one compound including aluminum hydroxide (Al(OH)) and lithium (Li).

[0246] In other embodiments, the method may further include precipitating manganese hydroxide (Mn(OH)2) from the second raffinate stream, which may be accomplished by adjusting the pH to between about 8 and about 10 by adding a strong alkaline base, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), or lithium hydroxide (LiOH), to form an intermediate liquor stream. The manganese hydroxide (Mn(OH)2) may then be removed or separated from the stream prior to entering the lithium precipitation reactor. In some embodiments, the manganese hydroxide (Mn(OH)2) thus formed may be removed or separated from the stream prior to entering the lithium precipitation reactor. water Manganese oxide (Mn(OH)2) can then be combined with at least one compound containing lithium (Li), such as lithium carbonate (Li2CO3), to form a LiMnO4 electroactive material.

[0247] The method may also further include adding sodium hydroxide (NaOH) to the purified filtrate stream to adjust the pH of the purified filtrate stream to have a pH of about 2.5, and adding sodium hydroxide (NaOH) to the first raffinate stream to adjust the pH of the first raffinate stream to have a pH of about 3.5.

[0248] In one variation, the stationary phase in the first chromatographic column or packed bed column / reactor and the stationary phase in the second chromatographic column or packed bed column / reactor are any resins having selectivity for manganese (Mn), nickel (Ni), and / or cobalt (Co) ions, and in particular, nickel (Ni) and / or cobalt (Co) ions known in the art. In one variation, the stationary phase of the first chromatographic column or packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid, and the stationary phase of the second chromatographic column or packed bed column / reactor comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

[0249] For example, Figure 5 shows yet another chromatographic separation process performed in system 500, which may be implemented in conjunction with systems 100, 300 of Figures 1 and 3, in which leachate from an impurity removal stage (e.g., impurity removal stage 104 of Figures 1 and 3) is passed through two selective columns (e.g., fixed bed columns) 502A, 502B containing resin, as described above. System 500 may be included in stage 106 of Figures 1 and 3, or may be a separate stage that replaces stage 106 of Figures 1 and 3.

[0250] In the example of FIG. 5, after the pH of the leachate is adjusted to a desired level (e.g., 2.5), the leachate is passed through column 502A. For example, the leachate is introduced from the top of column 502A. The resin in column 502A separates and adsorbs Ni ions, while other ions such as Mn, Co, and Li pass through column 502A. The solution collected at the bottom of column 502A is passed through column 502B after the pH of the solution is adjusted to a desired level (e.g., 3.5). In column 502B, Co ions are separated and adsorbed.

[0251] FIG. 8 is an illustration of this metal ion separation phase of the process implemented in system 500. As shown, sodium hydroxide (NaOH) is added to the leachate to adjust the pH to 2.5. The leachate is then fed to the top of column 502A (designated by the letter A in FIG. 8), where the resin in column 502A absorbs Ni ions while other ions, such as Mn, Co, and Li, pass through. The remaining solution then exits the bottom of column 502A (designated by the letter B in FIG. 8) and passes to column 502B. Before entering the top of column 502B, sodium hydroxide (NaOH) is added to the solution to adjust the pH to 3.5. The resin in column 502B absorbs Co ions while other ions, such as Mn and Li, pass through. Any Mn ions not separated in column 502B can be removed in a subsequent precipitation process, if desired.

[0252] Continuing with FIG. 5, Ni and Co ions in the leachate can be measured before and after the leachate passes through resin columns 502A and 502B (e.g., at the top and bottom of the resin columns). Monitoring the effluent of columns 502A and 502B during use can be a continuous process. Metal ion breakthrough or leakage from the bottom of columns 502A and 502B can provide an indication of when action needs to be taken and the unit regenerated. When the concentration of either Ni or Co ions exceeds a defined or predetermined amount, the separation phase stops and the system proceeds to the regeneration (e.g., metal ion recovery) phase.

[0253] After the resin in the stationary phase of columns 502A and 502B co-separates and adsorbs Ni and Co ions, the ions can be recovered by a regeneration process in columns 502A and 502B. The recovery process begins by introducing a first regeneration solution (e.g., shown as regeneration solution #1 in FIG. 5) from a source or container 508A at the bottom of column 502A. The first regeneration solution can have an adjusted pH of about 1.5. The first regeneration solution elutes Ni ions from the resin in column 502A and then collects in container 510A. Ni can be separated from the solution in a precipitation process after adjusting the pH to a precipitation pH. Similarly, for Co, a second regeneration solution (e.g., shown as regeneration solution #2 in FIG. 5) is introduced from a source or container 508B at the bottom of column 502B. The second regeneration solution can have an adjusted pH of about 2.5. The second regeneration solution elutes Co ions from the resin in column 502B and then collects in vessel 510B. The Co can be separated from the solution in a precipitation process after adjusting the pH to a precipitation pH. The amount of solution passing through columns 502A and 502B during each run, the amount of regeneration solution required for a complete recovery cycle of each metal ion, and the pH of the regeneration solution used can be monitored, if necessary.

[0254] 9 is an illustrative diagram of this metal ion recovery phase of process 500. As shown, regenerant solution from tank #1 (e.g., vessel 508A in FIG. 5) is introduced into the bottom of column 502A, and the solution containing Ni ions is passed to tank #3 (e.g., vessel 510A in FIG. 5). Additionally, regenerant solution from tank #2 (e.g., vessel 508B in FIG. 5) is introduced into the bottom of column 502B, and the solution containing Co ions is passed to tank #5 (e.g., vessel 510B in FIG. 5).

[0255] In some embodiments, the remaining leachate from the metal ion separation phase and the contents from the metal ion recovery phase may be collected in a reactor (e.g., reactor 132 or reactor 142 in FIGS. 1 and 3). For example, as shown in FIG. 5, the remaining leachate may be pumped to a reactor via pump 504. In this reactor, the solution (containing Mn and Li) can be used to produce LiMnO. For example, the solution can be processed to first precipitate Mn (e.g., as manganese hydroxide, Mn(OH)), and then sodium carbonate (NaCO) can be added to precipitate lithium (e.g., as lithium carbonate, LiCO). From these chemicals (Mn(OH) and LiCO), LiMnO can be produced. Additionally, the leached Co and Ni ions can be precipitated as cobalt hydroxide and nickel hydroxide and combined with Al to produce LiNiCoAlO.

[0256] Figures 10-14 illustrate an exemplary system 1000 that may be used to implement the process shown in system 100 of Figure 1. As shown in Figures 10-14, system 1000 may be employed in a two-level configuration with various components located on one or both levels.

[0257] For example, system 1000 of Figures 10-14 includes four reactors 1110, 1122, 1132, 1142, five pumps 1118, 1128, 1138, 1146, 1152, four filters 1120, 1130, 1140, 1154, an evaporator 1144, and a scrubber 1114. Reactors 1110, 1122, 1132, 1142 may each be a jacketed stirred tank internally coated with a corrosion-resistant lining that can withstand high temperature acidity (see also Appendix A). In such an example, reactors 1110, 1122, 1132, 1142 include agitators 1112, 1124, 1134, 1148 (individually) for agitating the contents (see also Appendix A), and reactors 1110, 1122, 1132 further include thermal jackets 1116, 1126, 1136 (respectively) that surround a portion of their respective reactor and circulate a heating / cooling medium to maintain a desired temperature, as described herein. The reactors 1110, 1122, 1132, 1142, pumps 1118, 1128, 1138, 1146, 1152, filters 1120, 1130, 1140, 1154, evaporator 1144, scrubber 1114, agitators 1112, 1124, 1134, 1148, and jackets 1116, 1126, 1136 function similarly to the reactors 110, 122, 132, 142, pumps 118, 128, 138, 146, 152, filters 120, 130, 140, 154, evaporator 144, scrubber 114, agitators 112, 124, 134, 148, and jackets 116, 126, 136 shown in FIG. 1 and described above.

[0258] 10-14, reactors 1110, 1122, 1132, 1142, pumps 1118, 1128, 1138, 1146, 1152, filters 1120, 1130, 1140, 1154, and evaporator 1144 are in fluid communication. For example, pump 1118 and filter 1120 may be in fluid communication with reactors 1110 and 1122, pump 1128 and filter 1130 may be in fluid communication with reactors 1122 and 1132, pump 1138 and filter 1140 may be in fluid communication with reactors 1132 and 1142, evaporator 1144 may be in fluid communication with filter 1140 and reactor 1142, and pump 1152 and filter 1154 may be in fluid communication with reactor 1142. In some examples, the reactors 1110, 1122, 1132, 1142, the pumps 1118, 1128, 1138, 1146, 1152, the filters 1120, 1130, 1140, 1154, and the evaporator 1144 are arranged in a serial flow path. For example, the flow path may include, in order: reactor 1110, pump 1118, filter 1120, reactor 1122, pump 1128, filter 1130, reactor 1132, pump 1138, filter 1140, evaporator 1144, pump 1146, reactor 1142, pump 1152, and filter 1154.

[0259] For example, as described herein in connection with FIG. 1 , a reactor (e.g., leaching reactor) 1110 receives an inorganic acid (e.g., sulfuric acid (H2SO4)), an oxidizing agent (e.g., hydrogen peroxide (H2O2)), and black mass (e.g., from sources thereof in fluid communication with the reactor 1110, such as sources disposed in communication with the reactor 1110 via an inlet toward the top of the reactor 1110, as shown in FIG. 1). The inorganic acid, oxidizing agent, and black mass may be introduced into the reactor 1110 in different phases. For example, as described above in connection with FIG. 1 , the black mass and inorganic acid may be added before the oxidizing agent. An agitator 1112 extending into the reactor 1110 may mix the contents, and a jacket 1116 extending around the exterior of the reactor 1110 may be used to maintain and / or adjust the temperature of the contents via a heating / cooling medium, as described herein.

[0260] After the desired amount of agitation, as described above, pump 1118 may pump the contents from reactor 1110 through filter 1120 (e.g., a filter by which the contents may exit reactor 1110 via an outlet (e.g., an outlet disposed toward the bottom of reactor 1110)). Filter 1120 may remove carbon (graphite) particles from the contents of reactor 1110. The remaining contents that pass through filter 1120 (e.g., a first filtrate) are then provided to reactor 1122. The carbon (graphite) particles collected by filter 1120 may then be processed as desired.

[0261] Reactor 1122 receives the first filtrate that passed through filter 1120, an oxidant (e.g., hydrogen peroxide (H2O2)), sodium hydroxide (NaOH), iron (Fe) powder, and a lime component (e.g., calcium oxide (CaO)) (e.g., from a source thereof in fluid communication with reactor 1122, such as depicted in FIG. 1 (e.g., a source positioned in communication with reactor 1122 via an inlet toward the top of reactor 1122)). The first filtrate, oxidant, sodium hydroxide, iron powder, and lime may be introduced to reactor 1122 in different phases. For example, the first filtrate, sodium hydroxide, and iron powder may be added before the oxidant and lime, as described above with respect to FIG. 1. An agitator 1124 extending into the reactor 1122 may mix the contents, and a jacket 1126 extending around the exterior of the reactor 1122 may be used to maintain and / or adjust the temperature of the contents through heating / cooling media as described herein.

[0262] After the desired amount of agitation as described above, pump 1128 may pump the contents from reactor 1122 through filter 1130 (e.g., a filter by which the contents may exit reactor 1122 via an outlet (e.g., an outlet disposed toward the bottom of reactor 1122)). Filter 1130 may remove impurities from the contents, such as copper, fluoride, iron, phosphate, titanium, aluminum, etc. The remaining contents that pass through filter 1130 (e.g., a second filtrate) are then provided to reactor 1132. The impurities collected by filter 1130 may again be processed as desired.

[0263] Reactor 1132 receives the second filtrate that passed through filter 1130 and sodium hydroxide (NaOH). In some examples, reactor 1132 may receive defined amounts (e.g., dosages) of NiSO4, MnSO4, and CoSO4 (e.g., from sources thereof in fluid communication with reactor 11321 (e.g., a reactor disposed in communication with reactor 1132 via an inlet toward the top of reactor 1132), etc.), as described above in connection with system 100 of FIG. 1. An agitator 1134 extending into reactor 1132 may mix the contents, and a jacket 1136 extending around the exterior of reactor 1132 may be used to maintain and / or adjust the temperature of the contents via a heating / cooling medium, as described herein.

[0264] After the desired amount of agitation as described above, pump 1138 may pump the contents from reactor 1132 through filter 1140 (e.g., a filter by which the contents may exit reactor 1132 through an outlet (e.g., an outlet disposed toward the bottom of reactor 1132)). Filter 1140 may remove NMC product from the contents. The remaining contents that pass through filter 1140 (e.g., a third filtrate) are then provided to evaporator 1144.

[0265] In evaporator 1144, the third filtrate is heated and water is removed from the filtrate by an evaporation process. For example, in some embodiments, about 50% of the water in the third filtrate may be evaporated. The remaining contents of the third filtrate (e.g., a concentrate stream) are then pumped to reactor 1142 via pump 1146.

[0266] Reactor 1132 receives the concentrate stream, sodium carbonate (NaCO), and sodium hydroxide (NaOH). The concentrate stream, sodium carbonate, and sodium hydroxide may be introduced to reactor 1132 in different phases. For example, as described above with respect to FIG. 1, the concentrate stream and sodium carbonate may be added before the sodium hydroxide. An agitator 1148 extending into reactor 1132 may mix the contents as described herein.

[0267] After the desired amount of agitation, as described above, pump 1152 may pump the contents from reactor 1142 through filter 1154. Filter 1154 may remove lithium carbonate from the contents. The remaining contents that pass through filter 1154 may be sent to wastewater treatment and / or recycled to reactor 1110.

[0268] In various embodiments, components within reactors 1110, 1122, 1132, 1142 may generate undesirable gases. For example, in some embodiments, fluorine within reactors 1110, 1122, 1132 may be converted to hydrogen fluoride (HF). In such instances, a portion of the undesirable gas (e.g., HF) may be released and vented through scrubber 1114 of FIGS. 10-14.

[0269] In various embodiments, a controller may be implemented to determine the precise dosage of components to be added to the reactors 1110, 1122, 1132, 1142 of Figures 10-14. Such dosages may be determined based on sensed characteristics of the contents within the reactors 1110, 1122, 1132, 1142, the contents entering the reactors 1110, 1122, 1132, 1142, the contents exiting the reactors 1110, 1122, 1132, 1142, etc. For example, the precise dosage of NaOH, NiSO4, MnSO4, and CoSO4 may be automatically determined based on sensed characteristics of the contents within the reactor 1132 (e.g., pH level, concentrations of different metals, etc.) and then dosed accordingly using a controller (e.g., PLC, etc.), as described above in connection with Figures 1 and 2.

[0270] For example, FIG. 15 illustrates an exemplary system 1500 that can be used to implement the process implemented in system 100 of FIGS. 1 and 2. System 1500 of FIG. 15 may be substantially similar to system 1000 of FIGS. 10-14, but includes a controller 1502 (e.g., a computing device, computer, computing module, etc. consistent with the description provided above; etc.) (see also Appendix A), one or more sensors (collectively referred to as sensors 1504), and one or more pumps (collectively referred to as pumps 1506). System 1500 includes reactors 1110, 1122, 1132, 1142 of FIGS. 10-14. In the example of FIG. 15, sensor 1504 is in communication with the contents in and / or entering reactor 1132, and pump 1506 is in communication with reactor 1132.

[0271] In various embodiments, controller 1502 may include a PLC and / or other suitable control device for determining the exact dosage of components that may be added to reactor 1132. Additionally, sensors 1504 may include, for example, one or more analyzers for measuring the concentrations of nickel, manganese, and cobalt in the solution entering (and / or within) reactor 1132, one or more sensors for measuring the pH level of the contents in (and / or entering) reactor 1132, etc.

[0272] In system 1500, controller 1502 may receive feedback signals 1508 from sensors 1504 that represent characteristics of the contents entering and / or within reactor 1132. For example, feedback signals 1508 may include signals that represent the concentrations of nickel, manganese, and cobalt in the solution entering reactor 1132, signals that represent the pH level of the contents within reactor 1132, etc. Based on feedback signals 1508, controller 1502 may determine the exact amounts of components that need to be added to reactor 1132. For example, controller 1502 may determine the desired amounts of nickel sulfate (NiSO), manganese sulfate (MnSO), cobalt sulfate (CoSO), and sodium hydroxide (NaOH) to add to reactor 1132, as described above with respect to FIGS. 1 and 2. Once the desired amounts of nickel sulfate (NiSO4), manganese sulfate (MnSO4), cobalt sulfate (CoSO4), and sodium hydroxide (NaOH) are determined, the controller 1502 can generate a control signal 1510 to control a pump 1506 to add the components to the reactor 1132.

[0273] It will be appreciated that while system 1500 of Figure 15 is described in connection with controlling the components added to reactor 1132, controller 1502 and / or additional controllers may be implemented, if desired, to control the precise amounts of components added to other reactors 1110, 1122, 1142. It will further be appreciated that controller 1502 and / or additional controllers of Figure 15 may be implemented in other systems disclosed herein to control the precise amounts of components added to reactors of such systems.

[0274] In various embodiments, a thermal shock process may be implemented in system 1500 and / or any other system disclosed herein. In such examples, the system may include a module for implementing the thermal shock process, for example, in place of an evaporator (e.g., evaporator 1144 of FIG. 15 ). For example, FIG. 16 shows an exemplary system 1600 that may be used to implement the process implemented in system 300 of FIG. 3 . System 1600 of FIG. 16 may be substantially similar to system 1000 of FIGS. 10-14 , but also includes a thermal shock module and an electrode ionization module in place of an evaporator. Specifically, system 1600 includes reactors 1110, 1122, 1132, and 1142, thermal shock module 1602, and electrode ionization module 1604 of FIGS. 10-14 .

[0275] In system 1600, thermal shock module 1602 and electrode ionization module 1604 are disposed in fluid communication between reactors 1132, 1142. For example, thermal shock module 1602 may receive contents from a filter (e.g., 1130 in FIGS. 10-14) on the output side of reactor 1132 and provide the contents to electrode ionization module 1604 (e.g., via a pump). In turn, electrode ionization module 1604 may provide the contents to reactor 1142 (e.g., via a pump).

[0276] The thermal shock module 1602 may be controlled to apply a thermal shock to the contents within the module 1602. For example, the temperature within the module 1602 may be reduced to a prescribed level to remove components (e.g., sodium sulfate, etc.) from the contents. After the components are removed, a pump may provide the remaining contents from the thermal shock module 1602 to the electrode ionization module 1604.

[0277] The electrode ionization module 1604 may remove water from its contents. For example, the electrode ionization module 1604 may utilize electricity, an ion exchange membrane, and a resin to deionize the water and separate dissolved ions from the water. Such ions may form a precipitate / sludge containing, for example, lithium sulfate, as described above with respect to FIG. 3. In such an example, the precipitate and its sludge may be provided to the reactor 1142, and the removed water may be recycled back to the reactor 1110 and provided to a wastewater treatment facility, as described above.

[0278] In various embodiments, the chelating resin process can be implemented in any one of the systems disclosed herein. In such instances, one or more columns containing the resin can be implemented to separate and absorb specific components in a solution passing therethrough.

[0279] For example, Figure 17 shows an exemplary system 1700 that can be used to perform any one of the processes performed in systems 100, 300, and 400 of Figures 1-4 and 6-7 described herein. System 1700 of Figure 17 may be substantially similar to system 1000 of Figures 10-14, but includes a column 1702 having a matrix of macroporous styrene divinylbenzene and a resin such as functionalized iminodiacetic acid. Specifically, system 1700 includes reactors 1110, 1122, 1132, and 1142, column 1702, and vessels 1708 and 1710 of Figures 10-14.

[0280] 17, column 1702 may be disposed in fluid communication between reactors 1122, 1132. In such an example, contents from reactor 1122 may be fed to column 1702, and contents from column 1702 may be fed to reactor 1132. In other examples, column 1702 may be disposed in fluid communication between reactors 1122, 1142, and reactor 1132 may be omitted. In such an example, contents from column 1702 may be fed to reactor 1142.

[0281] For example, column 1702 receives a leachate (e.g., a second filtrate as described above) from reactor 1122. In some embodiments, the leachate may be passed to column 1702 after its pH has been adjusted to a desired level (e.g., 4.5). The resin in column 1702 co-separates and adsorbs certain metal ions (e.g., Ni and Co ions) in the leachate, while other ions, such as Mn and Li (raffinate), in the remaining leachate pass through.

[0282] Column 1702 may then undergo a regeneration process to recover the separated and adsorbed metal ions. For example, column 1702 may receive a regeneration solution from vessel 1708 to elute the ions from the resin. The solution containing the eluted ions may then be collected in vessel 1710, where the ions may be separated from the solution in a precipitation process that raises the pH of the solution to a precipitation pH. The remaining leachate and / or recovered metal ions that pass through column 1702 may then be passed to a subsequent reactor (e.g., reactor 1132 or reactor 1142), as described herein in connection with FIGS. 4 and 6-7.

[0283] In other examples, the chelating resin process can be carried out using two columns. For example, Figure 18 shows an exemplary system 1800 that can be used to carry out any one of the processes carried out in systems 100, 300, and 500 of Figures 1-3, 5, and 8-9 described herein. System 1800 of Figure 18 can be substantially similar to system 1700 of Figure 17, but includes two columns 1802A and 1802B having a matrix of macroporous styrene divinylbenzene and a resin such as functionalized iminodiacetic acid. Specifically, system 1800 includes reactors 1110, 1122, 1132, and 1142 of Figures 10-14, columns 1802A and 1802B, and vessels 1808A, 1808B, 1810A, and 1810B.

[0284] 18 , columns 1802A, 1802B may be disposed in fluid communication between reactors 1122, 1132. In such an example, contents from reactor 1122 may be fed to column 1802A, contents from column 1802A may be fed to column 1802B, and contents from column 1802B may be fed to reactor 1132. In other examples, columns 1802A, 1802B may be disposed in fluid communication between reactors 1122, 1142, and reactor 1132 may be omitted. In such an example, contents from column 1802B may be fed to reactor 1142.

[0285] For example, column 1802A receives a leachate (e.g., the second filtrate as described above) from reactor 1122. In some embodiments, the leachate may be passed to column 1802A after its pH has been adjusted to a desired level (e.g., 2.5). The resin in column 1802A co-separates and adsorbs certain metal ions (e.g., Ni ions) in the leachate, while other ions, such as Mn, Co, and Li, in the remaining leachate pass through.

[0286] Column 1802B receives the remaining leachate from column 1802A. In some embodiments, this leachate may be passed to column 1802B after its pH has been adjusted to a desired level (e.g., 3.5). The resin in column 1802B co-separates and adsorbs other metal ions (e.g., Co ions) in the remaining leachate, while other ions such as Mn, Co, and Li in the remaining leachate pass through.

[0287] Columns 1802A, 1802B may then undergo a regeneration process to recover the separated and adsorbed metal ions. For example, column 1802A may receive a regeneration solution from vessel 1808A to elute Ni ions from the resin. The solution with the eluted ions may then be collected in vessel 1810A, where the Ni ions may be separated from the solution in a precipitation process that raises the pH of the solution to its precipitation pH. Additionally, column 1802B may receive a regeneration solution from vessel 1808B to elute Co ions from the resin. The solution with the eluted ions may then be collected in vessel 1810B, where the Co ions may be separated from the solution in a precipitation process that raises the pH of the solution to its precipitation pH. The leachate that has passed through both columns 1802A, 1802B and / or the recovered metal ions (Ni ions, Co ions) may then be passed to a subsequent reactor (e.g., reactor 1132 or reactor 1142) as described herein in connection with Figures 4 and 6-7.

[0288] In various embodiments, any one of the agitators disclosed herein may include a shaft extending into the reactor, one or more impellers attached to the shaft, and a motor for rotating the shaft and impellers. In some embodiments, the impellers may each include one or more blades (or fins) for stirring the contents within the reactor. For example, one agitator may include two impellers spaced a specified distance apart, each having three blades. Examples of reactors and impellers that may be used herein are illustrated in Appendix A. Of note, agitators may also include other forms of mixers or agitators (e.g., sonicators, bubblers, etc.).

[0289] In various embodiments, black mass can be fed into the system's reactor (e.g., reactor 1110 in Figures 10-14) through a hopper. For example, black mass in a conventional supersack container can be delivered to the site where the system is installed. In some examples, 1,000 kg (2,200 lbs) of black mass can be provided. The container of black mass can be unloaded onto a transfer system using a lift truck or similar device, and the black mass can then be transferred via a material handling system to a feed hopper located above the reactor. The feed hopper can be sized to hold two batches of black mass, each having, for example, 500 kg (1,100 lbs) of black mass. Alternatively, the feed hopper can be sized to hold one or more batches of black mass.

[0290] In various embodiments, any one of the filters disclosed herein can include any suitable type of filter. For example, the filter can be a pressure (or press) filter, a hydraulic filter, a gravity filter, etc. Furthermore, any one of the pumps disclosed herein can include any suitable type of pump. For example, the pump can be a centrifugal pump, a positive displacement pump, an axial pump, etc.

[0291] In various embodiments, any one of the scrubbers disclosed herein may include a tower, one or more blowers, one or more pumps, and an exhaust. For example, gas may be passed through the tower by a pump and exhausted from the tower by an exhaust and a blower.

[0292] In various embodiments, any one of the reactors disclosed herein may be a jacketed stirred tank internally coated with a corrosion-resistant lining to withstand high-temperature acidic conditions. For example, one reactor may include a suitable agitator extending to the interior portion of the reactor and a thermal jacket surrounding the exterior portion of the reactor for circulating a heating / cooling medium to maintain and / or adjust the temperature of the contents within the reactor at a desired level. In various embodiments, the thermal jacket may include, for example, a pipe (e.g., a metal pipe) coiled around the reactor. The thermal jacket may extend a specified distance (e.g., length) from the bottom of the reactor. The circumference of the pipe and / or the distance the jacket extends above the reactor may depend, for example, on the amount of energy required to change and / or maintain the temperature with the heating / cooling medium.

[0293] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the present disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, may be interchangeable and used in selected embodiments even if not specifically shown or described. The same may also be varied in various ways. Such variations are not to be considered departures from the present disclosure, and all such variations are intended to be included within the scope of the present disclosure.

Claims

1. 1. A process for recovering metals from a lithium ion battery waste stream, comprising: Sulfuric acid (H ２ SO ４ purifying a lithium ion battery effluent stream comprising fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti) in a first reactor to remove fluorine (F), phosphate (P), and one or more impurity metals selected from the group consisting of copper (Cu), aluminum (Al), iron (Fe), and titanium (Ti), wherein said purification comprises: (i) Removing copper (Cu) from waste streams; (ii) Adding a calcium oxide source and an oxidizing agent to precipitate calcium fluoride (CaF ２ ) ) ) ); and (iii) (i) removing copper (Cu), and (ii) adding a calcium oxide source and an oxidizing agent followed by aluminum hydroxide (Al(OH) ３ ), titanium hydroxide (Ti(OH) ４ ), iron phosphate (FePO ４ adding a first inorganic base to increase the pH of the waste stream to produce one or more metal precipitating compounds selected from the group consisting of: iron hydroxide; the steps of: The waste stream exiting the first reactor is passed through a filter to produce a purified filtrate stream and the one or more metal precipitate compounds, copper (Cu), and calcium fluoride (CaF ２ a second retentate comprising: Separating nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream to produce an intermediate liquid stream comprising lithium (Li) and one or more recovered products by passing the purified filtrate stream through one or more of the following, wherein the one or more recovered products comprise one or more of nickel (Ni), manganese (Mn), and cobalt (Co) removed from the intermediate liquid stream: (i) a second reactor for carrying out the co-precipitation process by increasing the pH; or (ii) one or more chromatography columns; and introducing the intermediate liquid stream into a lithium precipitation reactor to precipitate at least one compound comprising lithium (Li);

2. removing copper (Cu) from the waste stream; (i) adding a source of iron (Fe) and a second inorganic base to the waste stream to precipitate copper (Cu) by a cementation reaction; (ii) adding sodium sulfide (Na ２ adding a source of sulfur to precipitate copper (Cu) by a sulfidation reaction; or 10. The process of claim 1, comprising: (iii) subjecting the waste stream to a solvent extraction process by mixing it with an extractant and an organic phase to remove copper (Cu).

3. The step of removing copper (Cu) from the waste stream comprises (i) precipitating copper (Cu) by a cementation reaction, wherein the source of iron (Fe) comprises iron powder, the first inorganic base and the second inorganic base each comprise sodium hydroxide (NaOH), and the source of calcium oxide comprises lime (CaO), calcium hydroxide (Ca(OH)), or a mixture of calcium hydroxide (Ca(OH)). ２ ), and combinations thereof, and the oxidizing agent is selected from the group consisting of hydrogen peroxide (H ２ O ２ ), ozone (O ３ ), sodium hypochlorite (NaClO), and combinations thereof; Optionally, the second inorganic base is added until the pH reaches 5, the first inorganic base is added until the pH reaches 10.5, and the oxidizing agent is hydrogen peroxide (H ２ O ２ ), wherein the hydrogen peroxide is added at a concentration of 4% to 6% by volume of the total liquid content; Optionally, adding the source of iron (Fe) and the second inorganic base to the waste stream is carried out at a pH of 1 to 2, with mixing at a temperature of 55° C. to 65° C. for a period of 15 minutes or more; and / or 3. The process of claim 2, optionally adding 2.5 g of iron powder per liter (L) of the waste stream.

4. 3. The process of claim 2, wherein the step of removing copper (Cu) from the waste stream comprises (iii) subjecting the waste stream to a solvent extraction process, wherein the extractant comprises 2-hydroxy-5-nonylbenzaldehyde oxime and the organic phase comprises kerosene.

5. The purification step comprises the step of: ４ (ii) after adding the calcium oxide source and the oxidizing agent and (iii) before adding the first inorganic base to increase the pH of the waste stream, introducing a source of phosphate into the waste stream to produce a precipitate; Optionally, the source of phosphate is sodium phosphate (Na ３ P.O. ４ 2. The process of claim 1, comprising:

6. Calcium fluoride (CaF ２ 2. The process of claim 1, wherein adding the source of calcium oxide and the oxidizing agent to produce a slag is carried out at a temperature of at least 55°C and at most 65°C with mixing for at least 30 minutes at a pH of at least 1 and at most 2.

7. adding the first inorganic base to raise the pH of the waste stream to between 4 and 5; 2. The process of claim 1, wherein optionally, the addition of the first inorganic base to increase the pH is carried out with mixing at a temperature of at least 55°C and at most 65°C for a period of at least 60 minutes.

8. The purified filtrate stream is nickel sulfate (NiSO ４ ), manganese sulfate (MnSO ４ ) and cobalt sulfate (CoSO ４ 2. The process of claim 1, wherein separating nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream occurs by passing the purified filtrate stream through a second reactor to carry out the co-precipitation process comprising: Raising the pH of the purified filtrate stream to above 11 in an inert environment to form nickel hydroxide hydrate (Ni(OH) ２ ・6H ２ O), manganese hydroxide hydrate (Mn(OH) ２ ・H ２ O), and cobalt hydroxide hydrate (Co(OH) ２ ・7H ２ and co-precipitating from said purified filtrate stream to produce one or more recovered products.

9. Increasing the pH of the purified filtrate stream may include increasing the pH of nickel sulfate (NiSO ４ ), manganese sulfate (MnSO ４ ) and cobalt sulfate (CoSO ４ 10. The process of claim 8, further comprising initially adding ammonia to the purified liquid stream comprising:

10. The one or more recovered products include Ni ｘ Mn ｙ Co １－ｘ－ｙ (OH) ２ 9. The process of claim 8, wherein x is <1 and y is <1.

11. The process of claim 8 further comprising the steps of: determining a first ratio of Ni:Mn:Co in the purified filtrate stream prior to the co-precipitation process; comparing the first ratio to a target stoichiometric ratio of Ni:Mn:Co for the one or more recovered products; and and adjusting the pH of the one or more recovered products to have a second ratio corresponding to a target stoichiometric ratio by adding nickel sulfate (NiSO ) to the one or more recovered products. ４ ), manganese sulfate (MnSO ４ ) and cobalt sulfate (CoSO ４ ) to the purified filtrate stream to produce nickel sulfate (NiSO ４ ), manganese sulfate (MnSO ４ ), and cobalt sulfate (CoSO ４ ) adjusting the amount of

12. 10. The process of claim 1, wherein the separation occurs by: passing the purified filtrate stream in a first direction through a chromatography column comprising a chelating resin and performing a chromatographic separation process at a pH of 4.5 or less to produce a raffinate stream comprising at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exiting the chromatography column, while nickel (Ni) ions and cobalt (Co) ions are retained on the chelating resin in the chromatography column; and regenerating the chromatography column by passing a regenerant solution having a pH of 1.5 or less through the chromatography column to form an extract stream comprising nickel (Ni) ions and cobalt (Co) ions; and Nickel hydroxide (Ni(OH) ２ ) and cobalt hydroxide (Co(OH) ２ ) precipitating.

13. Nickel hydroxide (Ni(OH) ２ ) and cobalt hydroxide (Co(OH) ２ ) in a solution of at least one compound containing lithium (Li) and aluminum hydroxide (Al(OH) ３ ) to form a precursor of the electroactive material; Optionally, the pH of the purified filtrate stream is further adjusted to between 4 and 5 as it enters the chromatography column, and optionally, sodium hydroxide (NaOH) is added to the purified filtrate stream while adjusting the pH, and the process continues by adjusting the pH to between 8 and 10 to produce manganese hydroxide (Mn(OH) ２ precipitation of manganese hydroxide (Mn(OH)) from said intermediate liquid stream to form an intermediate liquid stream; and ２ or manganese dioxide (MnO) is produced by one or more of adding sodium permanganate or potassium permanganate to the raffinate stream and subjecting the raffinate stream to ozonation. ２ 13. The process of claim 12, wherein

14. 10. The process of claim 1, wherein the stationary phase of the one or more chromatography columns comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

15. The separation comprises: passing the purified filtrate liquid stream in a first direction through a first chromatography column comprising a first chelating resin and performing a chromatographic separation process at a pH of 1.5 or less to produce a first raffinate stream comprising at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exiting the first chromatography column, while nickel (Ni) ions and cobalt (Co) ions are retained on the chelating resin in the chromatography column; passing the first raffinate stream in a first direction through a second chromatography column comprising a second chelating resin and performing a chromatographic separation process at a pH of 2.5 or less to produce a second raffinate stream comprising at least one manganese (Mn)-containing species and at least one lithium (Li)-containing species exiting the second chromatography column, while nickel (Ni) ions and cobalt (Co) ions are retained on the chelating resin in the chromatography column; regenerating the first chromatography column by passing a first regenerant solution having a pH of 1.5 or less through the first chromatography column to form a first extract stream comprising nickel (Ni) ions; Nickel hydroxide (Ni(OH)) from the first extract stream ２ ) precipitating; regenerating the second chromatography column by passing a second regenerant solution having a pH of 2.5 or less through the second chromatography column to form a second extract stream comprising cobalt (Co) ions; and Cobalt hydroxide (Co(OH)) from the second extract stream ２ ) precipitating It occurs due to Optionally, nickel hydroxide (Ni(OH) ２ ) and cobalt hydroxide (Co(OH) ２ ) in the presence of at least one compound containing lithium (Li) and aluminum hydroxide (Al(OH) ３ ) to further form a precursor of an electroactive material; and / or Optionally, manganese hydroxide (Mn(OH)) is isolated from the second raffinate stream by adjusting the pH to between 8 and 10. ２ ) to form an intermediate liquid stream, and manganese hydroxide (Mn(OH) ２ 10. The process of claim 1, further comprising separating

16. Manganese hydroxide (Mn(OH) ２ ) in combination with at least one compound containing lithium (Li) to form a lithium manganate (LMO) electroactive material, and the at least one compound is lithium carbonate (Li ２ CO ３ 16. The process of claim 15, comprising:

17. and / or adding sodium hydroxide (NaOH) to the purified filtrate stream to adjust the pH of the purified filtrate stream to 2.5, and adding sodium hydroxide (NaOH) to the first raffinate stream to adjust the pH of the first raffinate stream to 3.

5.

16. The process of claim 15, wherein the stationary phase of the first chromatographic column comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid, and the stationary phase of the second chromatographic column comprises macroporous styrene divinylbenzene with functional groups comprising iminodiacetic acid.

18. The at least one compound containing lithium (Li) is manganese oxide (Mn(OH) ２ ) to form lithium manganese oxide (LMO) electroactive material. ２ CO ３ 2. The process of claim 1, comprising:

19. The lithium ion battery waste stream is black mass, and prior to the purification, further comprises the steps of: generating a lithium ion battery effluent stream by subjecting said black mass to a leaching process comprising: mixing an inorganic acid with said black mass to form an acidic mixture; mixing an oxidizing agent with the acidic mixture; and adding deionized water to the acidic mixture; and passing the leachate stream through a second filter to produce a filtrate stream comprising one or more metal sulfates and a first retentate comprising graphite; Optionally, both the combining of the inorganic acid and the combining of the oxidizing agent are carried out at a temperature of 100° C. or less; Optionally, the inorganic acid is sulfuric acid (H ２ SO ４ ), and the oxidizing agent is hydrogen peroxide (H ２ O ２ ), wherein the pH of the acidic mixture is 2.5 or less; and The mixing of the inorganic acid is carried out by adding sulfuric acid (H ２ SO ４ ), and mixing the oxidizer includes adding 30% by weight of hydrogen peroxide (H ) to the acid mixture so that the acid mixture has a solid / liquid ratio of 100 g / L. ２ O ２ ) is added, followed by mixing for 2 hours or more, and then the deionized water is added to the sulfuric acid (H ２ SO ４ ) to a molar concentration of 2M, followed by mixing for at least 30 minutes; Optionally, the one or more recovered products have a purity level of 95% or greater and contain a total cumulative amount of 5% by weight or less of impurities including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F); Optionally, the one or more recovered products have a purity level of 98% or greater and contain a total cumulative amount of impurities of 2% by weight or less, including aluminum (Al), copper (Cu), iron (Fe), phosphorus (P), titanium (Ti), and fluorine (F); and / or 2. The process of claim 1, wherein the separation optionally recovers greater than or equal to 80 wt. % each of nickel (Ni), manganese (Mn), and cobalt (Co) from the purified filtrate stream.

20. subjecting the intermediate liquid stream to a solvent extraction process by combining the waste liquid stream with an extractant and an organic phase to remove impurities including metals selected from the group consisting of copper (Cu), iron (Fe), aluminum (Al), and combinations thereof prior to introducing the intermediate liquid stream into the lithium precipitation reactor; 20. The process of claim 19, wherein optionally the extractant comprises bis-(2-ethylhexyl) phosphoric acid and the organic phase comprises kerosene.

21. introducing the intermediate liquid stream into the lithium precipitation reactor into a solution of sodium carbonate (Na ２ CO ３ ) and a second inorganic base to the lithium precipitation reactor, wherein lithium carbonate (Li ２ CO ３ ) the intermediate liquid stream has a temperature of 80°C or higher and 90°C or lower for 90 minutes or longer to produce a precipitate; Optionally, the intermediate liquid stream comprises lithium sulfate (Li ２ SO ４ ) and sodium sulfate (Na ２ SO ４ ), and prior to said introduction, said intermediate liquid stream is subjected to a thermal shock process to have a temperature of 0° C. or more and 30° C. or less, and then ionized in an electrode ionization unit to remove sodium sulfate (Na ) from said intermediate liquid stream. ２ SO ４ ) and then sodium carbonate (Na ２ CO ３ ) was added to the lithium precipitation reactor to form lithium carbonate (Li ２ CO ３ 20. The process of claim 19, wherein the precipitate is formed.

22. 20. The process of claim 19, wherein the separation efficiency of each of copper (Cu), aluminum (Al), titanium (Ti) and iron (Fe) is individually 95% or more, and the separation efficiency of fluorine is 80% or more.

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