Method for inorganic material recycling and compositions produced therefrom

Abstract

A method for recovery of metals and minerals from electronic waste includes introducing a black mass (BM) of crushed electronics into a thermal chamber to perform a carbothermal reduction or pyrolysis on the black mass to yield recoverable graphitics. Water is then introduced to a remaining portion of the treated black mass to form a black mass froth flotation and a first water leaching of the black mass froth flotation is performed to form a leached solution and a filtrate or cake is formed. A second leaching is performed with a strong acid on the cake and a second filtering to form a filtrate. The filtrate is subjected to a copper extraction or electrowinning, aluminum and iron precipitation, or vice versa, to recover a copper portion, and aluminum and / or iron.

Description

METHOD FOR INORGANIC MATERIAL RECYLCING AND COMPOSITIONS PRODUCED THEREFROMRELATED APPLCIATIONS

[0001] This application claims priority benefit of U.S. Provisional Application Serial Number 63 / 532,933 filed 16 August 2023 and U.S. Provisional Application Serial Number 63 / 619,425 filed 10 January 2024; the contents of which are hereby incorporated by reference.FIELD OF THE INVENTION

[0002] The present invention in general relates to inorganic material recycling and in particular, to ecologically friendly and sustainable material recovery processes for recycling of lithium-ion batteries.BACKGROUND OF THE INVENTION

[0003] With the growing recognition and acceptance of global climate change, there has been an acceleration in the movement towards electrification and away from a reliance on fossil fuels. Electric storage solutions have become a prime focus in the electrification effort. By 2030, lithium-ion demand is expected to surge by over 500% due to electrification, including the pending mass adoption of electric vehicles, with an expected global demand of 300 terawatts of battery capacity to be fully sustainable. However, the current supply chain is not equipped to handle this growth. Supply chain issues are highlighted by the fact that the number of miles that materials must move before they reach a battery cell factory is 50,000 miles. The supply chain is further complicated by geo-political considerations of where minerals required for battery manufacturing are located and their availability.

[0004] The movement towards electrification is further complicated by the adverse ecological aspects related to mining for required minerals and the pollutants generated by therefining processes to isolate the minerals. Expanding mines and increasing the size of landfills does more harm than good in the collective mission to protect the planet. Furthermore, current refining processes and recycling of recovered materials are pollutant-heavy and energy- demanding and employ methods like hydrometallurgy and pyrometallurgy.

[0005] Therefore, with the increasing demand for essential metals and minerals, especially for electric storage, there is a need for improved recycling processes that are environmentally friendly, energy efficient, economically viable, and yield a high percentage of useable reclaimed products including metals and minerals.SUMMARY OF THE INVENTION

[0006] The present invention provides methods for recovery of metals and minerals from batteries, electronic devices, or electronic waste. A first method includes introducing a black mass (BM) into a thermal chamber to perform a carbothermal reduction on the black mass, the black mass made up of at least one of crushed batteries, crushed electronic devices, or electronic waste, the carbothermal reduction yielding recoverable graphitics. The method continues by introducing water to a remaining portion of carbothermally treated black mass to form a black mass froth flotation and then a first water leaching of the black mass froth flotation to form a water leached solution followed by filtering the water leached solution to form a cake, or vice versa. The method continues by performing a second leaching with a strong acid on the cake and a second filtering to form a filtrate. Then the filtrate is subjected to a precipitation process to extract phosphate (POT ) and iron (Fe) by adjusting pH levels at temperatures.

[0007] A second method for recovery of metals and minerals from batteries, electronic devices, and electronic waste includes introducing a black mass (BM) into a thermal chamber to perform pyrolysis on the black mass, the black mass made up of at least one of crushed batteries, crushed electronic devices, or electronic waste, the pyrolysis yielding recoverablegraphitics. This method continues by introducing water to a remaining portion of the pyrolysis treated black mass to form a black mass froth flotation and then a first leaching with water and strong acid of the black mass froth flotation to form a leached solution or filtering the leached solution to form a filtrate, or vice versa. Next, the filtrate is subjected to a copper extraction or electrowinning , then aluminum and iron precipitation, or vice versa, to obtain a copper portion and aluminum and iron, if present.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The present invention is further detailed with respect to the following drawings. These figures are not intended to limit the scope of the present invention but rather illustrate certain attributes thereof.

[0009] FIG. 1 is a high-level flowchart of the recycling process in accordance with embodiments of the invention;

[0010] FIG. 2 is a flowchart of a recycling process according to embodiments of the invention;

[0011] FIG. 3 is a flowchart of a recycling process in accordance with an embodiment of the invention;

[0012] FIG. 4 is a flowchart of a copper extraction portion of a recycling process according to embodiments of the invention;

[0013] FIG. 5 is a flowchart of a recycling process in accordance with an embodiment of the invention;

[0014] FIG. 6 is a flowchart of a crystallization and evaporation portion of a recycling process according to embodiments of the invention; and

[0015] FIG. 7 is a flowchart of a black mass froth floatation portion of a recycling process according to embodiments of the invention.DESCRIPTION OF THE INVENTION

[0016] The present invention has utility as a method and system for improved recycling of inorganic materials that illustratively include batteries, electronic devices, and other assemblies or electronic waste (e-waste) that contain metals and minerals that is environmentally friendly, energy efficient, economically viable, and yields a high percentage of useable reclaimed products including metals and minerals. Unlike existing recycling technologies that employ pollutant-heavy, energy-demanding methods like hydrometallurgy and pyrometallurgy, embodiments of the present invention rely primarily on electricity and water during recycling so as to limit waste, require less space, and reduce environmental impact. Embodiments of the present invention are flexible and utilize eco-friendly electrowinning and water solution, designed for on-site installation, that recovers essential minerals from a plethora of sources such as e-waste, low-grade ores, mine tailings, and various forms of mineral scrap and waste. Embodiments of the invention may be used by battery manufacturers, electric vehicle original equipment manufacturers (OEMs), consumer electronics recyclers, energy storage systems providers, e-mobility service providers (including e-bikes and e-scooters), along with battery recyclers, scrap handlers, refining entities, and mining corporations. It is appreciated that while batteries with different chemistries are difficult for smelters to reprocess to recycle constituents therefrom, the present invention affords predictable and controlled feedstocks for subsequent reprocessing, such as that performed by melt recycling smelters. While the present invention is further detailed largely in the context of lithium battery recycling, it should be appreciated that the methods detailed herein are readily deployed to recycle the aforementioned electronic devices, and other assemblies or electronic waste that illustratively include computers, displays, routers, and servers.

[0017] Embodiments of the inventive recycling method require less electricity compared to conventional techniques, where the el ectrowinning and water leaching process curbs greenhouse gas emissions by 87% relative to traditional mining methods. In comparison to standard recycling techniques, the inventive recycling system reduces greenhouse gas emissions by 76%. Electrowinning, also referred to herein synonymously as electroextraction, is the electrodeposition of metals from their ores that have been put in solution via a process commonly referred to as leaching. In el ectrowinning, an electrical current is passed from an inert anode through a leach solution containing the dissolved metal ions so that the metal is recovered as it is deposited in an electroplating process onto the cathode (reduction, stainless steel, aluminum (Al), titanium (Ti)). In electrorefining, the anode consists of the impure metal (e.g., copper) to be refined. The impure metallic anode is oxidized and the metal dissolves into solution. The metal ions migrate through the acidic electrolyte towards the cathode where the pure metal is deposited. Insoluble solid impurities sedimenting below the anode often contain valuable rare elements such as gold, silver and selenium.

[0018] Embodiments of the inventive recycling process recover approximately 95% of essential elements from batteries, supplying battery manufacturers with indispensable raw materials. Embodiments of the invention are also capable of transforming raw lithium into lithium carbonate, a valuable compound in various industries, as well as returning battery- based lithium compounds to lithium carbonate. The inventive recycling method is operative with a variety of battery chemistries that illustratively include lithium cobalt oxide (LCO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium nickel manganese spinel (LNMO) and lithium titanium phosphate (LTP) - and encompasses a diverse range of battery types. It is further noted that intermediate compositions realized during embodiments of the recycling process are based on the composition of a given battery being reacted throughwater leaching and may have unique properties in terms of particulate size, chemistry, and combinations thereof.

[0019] Essential metals and minerals that may be obtained with the inventive recycling process of lithium-ion batteries illustratively include lithium (Li), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), aluminum (Al), titanium (Ti), carbon (C), and silicon (Si). Lithium is the lightest metal and the third-lightest element (after hydrogen and helium) on the periodic table. Lithium has a low density and is highly reactive, which makes it useful for a variety of applications, including in batteries, ceramics, and even medication for certain health conditions. Manganese is a common component in lithium-ion batteries. Manganese is often used in the cathode to enhance the battery's energy density. Manganese can be recycled from old batteries and used to produce new ones. Iron is not typically used in batteries, but it is a common component of steel, which is used to make battery cases and other components. Recycled iron can be used to make new steel for these purposes. Silver is sometimes used in the electrodes of batteries, but it is a relatively rare occurrence. However, silver is a highly recyclable metal that can be reused in the production of new batteries. Cobalt is used in lithium- ion batteries to increase their energy density. Cobalt is a valuable mineral, but its mining can have negative environmental impacts. Battery recycling can help reduce the need for new mining and conserve valuable resources. Nickel is a key component in the cathode of many types of batteries, including nickel-cadmium, nickel-metal hydride, and lithium-ion batteries. Nickel can be recycled from old batteries and used to produce new ones. Copper is used in many battery components, including wires, connectors, and terminals. Copper is also a highly recyclable metal that can be reused in the production of new batteries. Aluminum is not directly used in batteries, but it is often used to make battery casings and other components. Recycling aluminum can help conserve energy and reduce greenhouse gas emissions. Carbon is used in the anode of many types of batteries, including lithium-ion batteries. Carbon can be recycledfrom old batteries and used to produce new ones. Silicon is a versatile metalloid abundant in the Earth's crust. With electrical conductivity, heat resistance, and oxygen affinity, silicon is crucial in electronics, solar panels, fiber optics, concrete, and glass production.

[0020] The present invention will now be described with reference to the following embodiments. As is apparent by these descriptions, this invention can be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. For example, features illustrated with respect to one embodiment can be incorporated into other embodiments, and features illustrated with respect to a particular embodiment may be deleted from the embodiment. In addition, numerous variations and additions to the embodiments suggested herein will be apparent to those skilled in the art in light of the instant disclosure, which do not depart from the instant invention. Hence, the following specification is intended to illustrate some particular embodiments of the invention, and not to specify all permutations, combinations, and variations thereof exhaustively.

[0021] It is to be understood that in instances where a range of values are provided that the range is intended to encompass not only the end point values of the range but also intermediate values of the range as explicitly being included within the range and varying by the last significant figure of the range. By way of example, a recited range of from 1 to 4 is intended to include 1-2, 1-3, 2-4, 3-4, and 1-4.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments, only, and is not intended to be limiting of the invention.

[0023] Unless indicated otherwise, explicitly or by context, the following terms are used herein as set forth below.

[0024] As used in the description of the invention and the appended claims, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0025] Also as used herein, “and / or” refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (“or”).

[0026] Referring now to the figures, FIG. 1 illustrates a high-level flowchart of the inventive recycling process 10. Batteries, battery packs, production scrap, consumer electronics, and lithium ore are sourced from black mass producers, battery collectors, and auto recyclers (Blocks 12, 14, 16) for collection and receipt (Block 18) for storage and preparation (Block 20). Preparation may include sorting the recycling materials collected and storing the recycling material by category or type, which will provide an indication of the target minerals that will be recovered from a category or type. In addition, the materials may be crushed to turn the materials into a black mass (BM) that is introduced into the inventive extraction process (Block 22). Embodiments of the inventive recycling and extraction process will be described in greater detail in FIGS. 2 and 3. Minerals obtained from the recycling process may be further refined (Block 24) and provided to the lithium market, the Ni / Co / Al market, cell manufacturers, and graphite processors (Blocks 26, 28, 30, 32) to produce new recycled products such as anodes, cathodes, electronics, and for use in glass and ceramic industries, as well as fertilizers.

[0027] While the following figures detail process steps according to the present invention, it should be apparent to one of ordinary skill in the art that several steps may be performed in a varied sequence relative to those depicted. Some factors in the specific sequence include thechemical specifics of the black mass, the relative concentrations of constituents, the relative value placed on the yield of various constituents recycled, and combinations of these factors.

[0028] FIG. 2 is a flowchart of an embodiment of an inventive recycling process 40 that converts a black mass (BM) into precious metals and other reusable materials. The process 40 is to scalp lithium from lithium ion black mass by producing lithium carbonate (which is then washed out) at 700°C. The method is useful for black mass that is processed at smelters (as the vast majority is) since lithium cannot be recovered in this case. Since the method requires heating the material to about 700°C, there are other improvements to the quality of the black mass that can be gained during the heating cycle, especially if the black mass is produced by dry shredding. Other contents of the black mass that are not desired by smelters are carbon (CO2 penalty during smelting) and fluorine, both in the form of LiF and LiPF6electrolyte. The general concept is that one thermal treatment, steadily increasing in temperature, will enable the recovery of the four components of electrolyte, fluorine, graphite, and lithium. It is appreciated that the water, reagents, and chemicals used in the recycling process 40 are all recycled and are self-contained in the process. The recycling process 40 starts with the introduction to a heat chamber to subject the BM to a carbothermal reduction (Block 42). The carbothermal reduction of the BM may be conducted at a temperature of between 400-1000 °C for a duration of 15-720 minutes. According to embodiments, the carbothermal reduction (CTR) is conducted at a temperature between 400 to 600 °C. Carbonic materials operative as the reductants in the carbothermal reduction illustratively include graphite and carbon black, as well as other waste materials. The CTR converts lithium primarily to Li2CO3 and Li2O. This step removes organic impurities and enhances the leaching of valuable metals like Ni / Co and lithium. Lithium has significant value in the black mass and can only be recovered hydrometallurgically . Scalping lithium removes value from the black mass that smelters would have to pay for but not receive the value therefrom.

[0029] Electrolyte recovery (Block 44) is conducted. Standard electrolyte, LiPFg, is volatile at low temperatures (~125°C) but is highly reactive with water. This means that it must be heated in either an inert gas or a vacuum. Integration of this in a single thermal process may be difficult. This step focuses on recovering electrolytes (LiPF6) from the black mass. According to embodiments, this stage in a continuous operation and condenses the LiPF6 without damaging it. The black mass is dissolved in an appropriate solvent at a temperature range of 50-80°C for 30-120 minutes. The leachate is then filtered to remove solid residues. Next, Fluorine removal (Block 46) is the conducted to remove fluorine from the leachate through volatilization at higher temperatures (150-300°C). According to some embodiments, a graphite pre-processing treatment is then conducted to remove polymeric binders by heating between 100-500C for 2 hours in a muffle furnace and undergo analyses such (inductively coupled plasma-optical emission spectroscopy (ICP-OES), scanning elelctron microscopy - energy dispersive X-ray spectroscopy (SEM.EDS), C&O analysis, or combinations thereof. Fluorine is associated with the electrolyte but will also be in other forms like LiF and from partial hydrolysis if shredding is not airtight. Fluorine left after electrolyte removal will likely be very difficult to remove and will likely require hydrolysis at temperatures of about 300°C and above. The fluorine would leave the kiln as HF gas and would need to be scrubbed. This is preferred over having to deal with fluorine at a smelter.

[0030] Next, a black mass froth floatation (Block 48) is conducted. A mix of collectors and reagents is added to enhance recovery rates by increasing the hydrophobicity of graphite and aluminum particles. The graphite undergoes further treatment with pyrolysis under N2 between 450°C to 600°C and is separated with a wet magnet, resulting in the final recycled graphite. The graphite can be removed post-thermal treatment by flotation. Thermal treatment at about 500°C (in inert conditions) can greatly influence the ability for the graphite to be recovered from the black mass for a much cleaner graphite concentrate, which can be sold toreprocessing companies. The separation can be done in a separate operation, but the pre- treatment can be done in the thermal process. In addition to the graphite, there are plastics that can be pyrolyzed. The pyrolysis will provide a carbon source which can be used in the lithium recovery step.

[0031] Water leaching (Block 50) is then conducted. According to some embodiments, the water leaching is conducted at a temperature of between near 0 and 40 °C for a duration of 5-720 minutes. A solid / liquid (S / L) ratio of 1 / 10-1 / 200 is maintained. In specific embodiments, carbon dioxide is added during the process step. It is appreciated that the carbon dioxide is present at above ambient atmospheric pressure in some inventive embodiments; while in other inventive embodiments, the carbon dioxide is bubbled through the contents.

[0032] Following the water leaching, filtration (Block 52) occurs. Here, the solid products are blended, and under specific time and solid-liquid ratios at room temperature, only Li2CO3 / Li2O will leach in water, while the other metals remain in the solid residue, or cake. This process dramatically curtails both water consumption and energy usage. According to some embodiments, filtration techniques operative at Block 52 include microfiltration, ultrafiltration, reverse osmosis, forward osmosis, or nanofiltration. Nanofiltration uses membranes with pore sizes from 1-10 nanometers than are larger than those reverse osmosis and smaller than micro- or ultrafiltration or forward osmosis. The leached Li2CO3 / Li2O pass to an Li precipitation unit for evaporation (Block 54), while the cake is subjected to an additional leaching and filtration step (Block 56) with water and a mineral acid such as H2SO4being added to the cake for leaching and filtration.

[0033] Water is added to reach the pulpy density. First, water is added to the system to create the pulp density. Then, a collector and frother will be added and kept for a specific time, respectively. In specific embodiments the filtrated solution is placed in a Li precipitation unit (Block 54) to perform crystallization and evaporation on the solution at a temperature ofbetween 50-120 °C for a duration of 15-1440 minutes in the presence of carbon dioxide or a facile carbonate to obtain a Li carbonate product at a 60% or higher yields.

[0034] According to embodiments, the Li Precipitation unit (crystallization and evaporation) includes the process detailed in FIG. 6. Specifically, a leaching solution from filtration step 54 is provided to the Li Precipitation unit as subjected to evaporation (Block 54a) for 5 to 300 minutes. The concentrated solution is then subjected to a precipitation (Block 54b) at a temperature of 50-120 °C for a duration of a maximum of 120 minutes. Here, an additive of Na2CO3can be added in an amount that is more than the stoichiometry of Li. Then, the process includes washing (Block 54c) for 5 to 300 minutes and subsequent drying (Block 54d) for 5 to 300 minutes. The result is Li Carbonate or Hydroxide at greater than a 80% yield.A frother and a collector additive, if present in the flotation step are held for 5-60 minutes that creates a pulp density of 2-20% from which graphite may be recovered. A frother additive and a collector may be added and held for 5-60 minutes that creates a pulp density of 2-10%. A frother operative herein illustratively includes C4-18aliphatic alcohols such as methyl isobutyl carbinol, and a-terpineol; and polyglycols such as polyethylene glycols with number average molecular weights of 200-2,000. Typical loading of a frother is from 5 - 500 mg per kg of the leach residue. A collector operative herein illustratively includes carbamates, such as C2-8dialkylthionocarbamates, thionocarbamate sulfides, C2-8allylalkylthionocarbamates; sodium di-isobutyl dithiophosphinate; benzohydroxamic acid; octanohydroxamic acid; and xanthates such as potassium amyl xanthate, sodium ethyl xanthate, sodium propyl xanthate. Typical loading of a collector is from 50- 500 mg per kg of the leach residue. In order to produce bubbles, the airflow range is between 1 and 20 liters per minute. It is appreciated that pores may also be charged to further modify filtration efficiency for a given substance.

[0035] According to embodiments, the black mass froth flotation (Block 48) includes the process steps shown in FIG. 7. According to embodiments, after graphite and aluminum havebeen removed, to the process includes the steps of preheating (Block 48a), suspension in cyrene (Block 48b), pyrolysis (Block 48c), air classifier (Block 48d), a wet magnetic separation (Block 48e), a mild chemical leaching (Block 48f), and a particle size distribution (PSD) and BET surface area test (Block 48g). The result of this process is recycled graphite. According to embodiments, conditions for the process steps shown in FIG. 7 include a pretreatment of attrition or none, a temperature of 100-500C, a duration of 5-60 min, a frother additive (as described above), a pulp density of 2-10 %, a stirring speed of 500 -6000 rpm, an airflow of 1- 20 L / min, or a combination thereof. The preheating of Block 48a is an optional step that is used to remove polymeric binder, if needed. These samples are then subjected to the above described flotation of Block 48 under optimal conditions, above described. The final flotation concentration typically contains a graphite concentration of 90-95% C(T)). The suspension is cyrene step of Block 48b is used to reduce the amount of carbon agglomerates. According to embodiments, the cyrene (dihydrolevoglucosenone) is a waste-derived environmentally friendly solvent. It is appreciated that other solvents operative herein illustratively include ionic liquids, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and combinations thereof. The pyrolysis of Block 48c utilizes -N2 or Argon. The air classifier of Block 46d filters out particles of less than 4 pm, passing particles of 5-30 pm to the next step of wet magnetic separation. At Block 48e, the wet magnetic separation takes place and results in a by-product containing Ni, Co, Mn, Fe, Al, Cu, etc. Graphite is then passed to the mild chemical leaching step of Block 48f. The by-product of the mild chemical leaching of Block 48f contains Ni, Co, Mn, Fe, Al, Cu. The main product is the final recycles graphite, having a 99.995% C(T). The final recycled graphite is then subjected to particle size distribution (PSD) and BET surface area testing at Block 48g. Based on the purity and electrochemical properties of the recycled graphite, a determination is made as to whether the recycled graphite is suitable for batteries or not. Recycled graphite that is determined to be suitable for batteries, may be used as anodes forbatteries. Recycled graphite that is determined to be not suitable to batteries may then be used for graphene production, graphite and polymer composites, supercapacitor, electrochemical sensor, gas storage, and absorbent uses.

[0036] Following the fdtration (Block 52) a cake formed from the fdtered solution is introduced to a second leaching (Block 53) with water and a mineral acid. In some inventive embodiments, a drying stage is provided after flotation of Block 48 and before the second leaching of Block 53. Strong acids operative herein include sulfuric acid, nitric acid, hydrofluoric acid, chloroacetic acid, hydrochloric acid, and a combination of any of the aforementioned with a concentration of 0.5-12 M. The second leaching of Block 53 is conducted at a temperature of between 30-120 °C for a duration of 15-720 minutes. A solid / liquid (S / L) ratio of 5-800 g / L is obtained with a pH of between 0.5 and 5.5. Reductants from the second leaching may include none, or one or more of Cu, Fe, H2O2, or a weak organic acid such as tartaric, malic, ascorbic, or citric.

[0037] Following the second leaching, the solution undergoes a second fdtration (Block 56) and an optional washing (Block 58). The second fdtration of Block 56 being that detailed above with respect to Block 52. According to embodiments, such as that shown in FIG. 2, the fdtrate from the second fdtration (Block 56) is then subjected to phosphate and iron removal by precipitation (Block 60). To further purify the NMC leachate, a precipitation process is implemented to extract phosphate (POT ) and iron (Fe) by adjusting pH levels at temperatures ranging from 90 to 150 degrees Celsius. The recovered phosphate and iron by-products hold market value for cement and fertilizer manufacturers.

[0038] The resulting Nickel-Manganese-Cobalt (NMC) rich leachate is then passed to a recovery unit (Block 62) for processing. The recovery unit produces a pure, uncontaminated Ni / Co alloy, which is transformed into a low-CO2 product, eliminating impurities and fluorine. This intermediate product is utilized by smelters / pyro, hydro processes, and CAMmanufacturers. The recovered LiPF6 is dried at 60-80°C in a vacuum or inert atmosphere to remove residual solvent. If higher purity is required, recrystallization or sublimation can be employed. The recovered LiPF6 is stored in a dry, inert atmosphere using moisture-resistant containers to prevent degradation

[0039] According to some embodiments, as shown in FIG. 4, a copper extraction (Block 158) is conducted after the second fdtration step 52. The copper extraction is conducted at a temperature of between RT-90 °C for a duration of 5-720 minutes with a solution having a pH of 0.5-7. Copper solvent extractants used illustratively include SX, IL, or resins: (LX 54, Acorga M5640, A336 / Cy272, Aliquat 336, Cyanex 272, D2EPHA, LIX 984N, Cyanex 301, BmimBF4, or mixtures thereof). Additives illustratively include kerosene, toluene, heptane, n- heptane, isoparaffin, or mixtures thereof. A stripping acid used in the copper extraction illustratively includes nitric, sulfuric, hydrochloric, hydrofluoric, chloro-acetic acids, or combinations thereof. In some inventive embodiments, an inorganic and water-soluble hydroxide such as NaOH, KOH, ammounium hydroxide, or combinations thereof are added to adjust pH. In some inventive embodiments, the inorganic hydroxide is provided in a C1-6alcohol, alone in a solution with water to create a reaction pH of up to 40.

[0040] In specific embodiments, copper electrowinning (Block 160) to yield Cu is performed at a temperature of between 25-90 °C for a duration of 15-1440 minutes with a current density of 100-600A / m2. The anodes in the electro winning process are illustratively platinum, iridium, titanium, lead or stainless steel, and the cathodes are illustratively copper or stainless steel. According to some embodiments, following the copper extraction (Block 158) or el ectrowinning (Block 160), copper free leachate is fed to an aluminum and iron precipitation unit (Block 162). In some inventive embodiments, an inorganic and water soluble hydroxide such as NaOH, KOH, Ca(OH)2, NH4OH, or combinations thereof function as crystallization seeds and / or H3PO4are added and reacted for 15-1440 minutes in a temperaturerange of 20-90 °C in a solution of a pH between 1-7 to yield Al and Fe, and a rich nickel manganese cobalt oxides (NMC), if Ni / Co are present. In some inventive embodiments, the inorganic hydroxide is provided in a C1-6alcohol, alone in a solution with water to create a reaction pH of up to 40. The NMC rich solution is fed to a recovery unit (Block 164) where pure materials or semi-purified cakes of nickel sulfate, cobalt sulfate, and manganese carbonate are recovered with yields that can exceed 90%.. According to such embodiments, the filtrate from the second filtration (Block 52) is fed to an aluminum and iron precipitation unit (Block 162), as described above. Then the resulting leachate is subjected to a copper extraction (Block 158), as described above.

[0041] FIG. 3 is a flowchart of an embodiment of an inventive recycling process 70 that converts a black mass (BM) into precious metals and other reusable materials. It is appreciated that the water wash solution used in the recycling process 70 in some inventive embodiments is all recycled and is self-contained in the process. The recycling process 70 starts with the introduction to a heat chamber of the black mass of materials to subject the BM to pyrolysis (Block 72). The pyrolysis of the BM may be conducted at a temperature of between 400-700 °C for a duration of 15-720 minutes. Following the pyrolysis, the material is introduced at room temperature to form a black mass froth floatation (Block 74). In some inventive embodiments, a pretreatment attrition (Block 73) is provided with a speed of 10000 to 18000 rpm performed prior to froth floatation (Block 74) with conditions as detailed above with respect to Block 46. A frother additive and a collector may be added and held for 5-60 minutes that creates a pulp density of 2-10%. A frother operative herein illustratively includes C4-18aliphatic alcohols such as methyl isobutyl carbinol, and a-terpineol; and poly glycols such as polyethylene glycols with number average molecular weights of 200-2,000. Typical loading of a frother is from 5 - 500 mg per kg of the leach residue. A collector operative herein illustratively includes carbamates, such as C2-8dialkylthionocarbamates, thionocarbamate sulfides, C2-8allylalkylthionocarbamates; sodium di-isobutyl dithiophosphinate; benzohydroxamic acid; octanohydroxamic acid; and xanthates such as potassium amyl xanthate, sodium ethyl xanthate, sodium propyl xanthate. Typical loading of a collector is from 50- 500 mg per kg of the leach residue.

[0042] Leaching (Block 76) is subsequently conducted with the addition of water and a mineral acid. Strong acids operative herein include sulfuric acid, nitric acid, hydrofluoric acid, chloroacetic acid, hydrochloric acid, and a combination of any of the aforementioned with a concentration of 0.5-12 M to the product of black mass floatation (Block 74) to yield graphite, a graphitic composition, or a novel composition. The leaching is conducted at a temperature of between 30-120 °C for a duration of 15- 720 minutes. In some inventive embodiments, leaching occurs with an energy input of at least one of ultrasonic, microwave, magnetic, mechanical, or energy. A leached solution with a solid / liquid (S / L) ratio of 5-800 g / L and a pH of between 0.5-5.5 is obtained from Block 74. Reductants from the leaching may include none, or one or more of Cu, Fe, H2O2, or a weak organic acid such as tartaric, malic, ascorbic, or citric; and combinations thereof. Subsequently, the leached solution undergoes fdtration (Block 78). Filtration techniques operative at Block 78 include microfiltration, ultrafiltration, reverse osmosis, forward osmosis, or nanofiltration. Nanofiltration uses membranes with pore sizes from 1-10 nanometers than are larger than those reverse osmosis and smaller than micro- or ultrafiltration or forward osmosis. It is appreciated that pores may also be charged to further modify filtration efficiency for a given substance. Following the filtration of Block 78, an optional washing (Block 80) may be performed. Independent of the inclusion of a washing step, according to embodiments, such as shown in FIG. 3, the filtrate from the filtration (Block 78) is then subjected to a copper extraction (Block 82) to yield Cu. The copper extraction is conducted at a temperature of between 5 and 90 °C for a duration of 5-720 minutes in a solution having a pH of between 0.5-7. Copper solvent extractants used illustratively include SX, IL, orresins: (LX 54, Acorga M5640, A336 / Cy272, Aliquat 336, Cyanex 272, D2EPHA, LIX 984N, Cyanex 301, BmimBF4, or mixtures thereof). Additives illustratively include kerosene, toluene, heptane, n-heptane, isoparaffin, or mixtures thereof. A stripping acid used in the copper extraction illustratively includes sulfuric acid, nitric acid, hydrofluoric acid, chloroacetic acid, hydrochloric acid, and a combination of any of the aforementioned with a concentration of 0.5-12 M. In specific embodiments copper electro winning (Block 84) is performed at a temperature of between 50-90 °C for a duration of 15-1440 minutes with a current density of 100-600 A / m2The anodes in the el ectrowinning process may be platinum, iridium, titanium, lead, or stainless steel, and the cathodes may be copper or stainless steel. Minerals yielded may include Al, Cu, and Fe. Following the copper extraction (Block 82) or electrowinning (Block 84), copper free leachate is fed to an aluminum and iron precipitation unit (Block 86). In some inventive embodiments, an inorganic and water soluble hydroxide such as NaOH, KOH, or combinations thereof function as crystallization seeds and / or H3PO4are added and reacted for 15-720 minutes in a temperature range of 20-90 °C in a solution of a pH between 1-7 to yield Al and Fe. In some inventive embodiments, the inorganic hydroxide is provided in a C1-6 alcohol, alone in a solution with water to create a reaction pH of up to 40.

[0043] According to embodiments, shown in FIG. 5, the filtrate from the filtration (Block 78) is fed to an aluminum and iron precipitation unit (Block 86), as described above. Then, the Al and Fe leachate is subjected to a copper extraction (Block 82) to yield Cu, as described above.

[0044] The solution is then fed to a precipitation unit (Block 88) under a temperature of between 5-90 °C for a duration of 15-1440 minutes in a solution regardless of the pH. Additives may include phosphoric acid, oxalic acid, crystallization seeds, Li metal, or none in a stoichiometric amount or higher. In specific embodiments, Li selective is precipitated (Block90) under a temperature of between 5-120 °C for a duration of 15-720 minutes with an optionalcarbon dioxide to yield lithium carbonate. The precipitation unit (Block 88) yields rich nickel manganese cobalt oxides (NMC). The NMC rich solution is feed to a recovery unit (Block 92) where pure materials or semi-purified cakes of nickel sulfate, cobalt sulfate, and manganese carbonate is recovered.Other Embodiments

[0045] Embodiments of the invention may utilize electro-chemical leaching to extract lithium as a metal, or carbonate that is well suited for usage in a battery.

[0046] In still other embodiments, lithium iron phosphate (LFP) batteries are processed to extract phosphates and Fe cake for by-product sales to supply fertilizer manufacturers following filtration (Block 48 of process 40), In some inventive embodiments, optional LFP regeneration is provided to limit waste. LFP regeneration is readily accomplished by conventional techniques that include those detailed in Lui et al., Ind. Eng. Chem. Res. 2022, 61, 11, 3831-3839; or Liu et al. ACS Applied Energy Materials 2022, 5 (11), 14323-14334.

[0047] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the described embodiments in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the exemplary embodiment or exemplary embodiments. It should be understood that various changes may be made in the function and arrangement of elements without departing from the scope as set forth in the appended claims and the legal equivalents thereof.

[0048] The foregoing description is illustrative of particular embodiments of the invention, but is not meant to be a limitation upon the practice thereof. The following claims, including all equivalents thereof, are intended to define the scope of the invention.

Claims

CLAIMS1. A method for recovery of metals and minerals from batteries, electronic devices, or electronic waste, said method comprising: introducing a black mass (BM) into a thermal chamber to perform a carbothermal reduction on the black mass, the black mass made up of at least one of crushed batteries, crushed electronic devices, or electronic waste, the carbothermal reduction yielding recoverable graphitics; introducing water to a remaining portion of carbothermally treated black mass to form a black mass froth flotation; and a first water leaching of the black mass froth flotation to form a water leached solution followed by; filtering the water leached solution to form a cake, or vice versa; performing a second leaching with a strong acid on the cake and a second filtering to form a filtrate; and subjecting the filtrate to a precipitation process to extract phosphate (POT ) and iron (Fe) by adjusting pH levels at temperatures.

2. The method of claim 1 further comprising providing the water leached solution to a lithium precipitation unit to yield a lithium salt, such as lithium carbonate.

3. The method of claim 1 wherein lithium precipitation unit performs crystallization and evaporation on the water leached solution at a temperature of between 50- 120°C for a duration of 15-1440 minutes.

4. The method of claim 1 wherein the carbothermal reduction of the BM is conducted at a temperature of between 400-1000 °C for a duration of 15-480 minutes.

5. The method of claim 1 wherein the black mass froth flotation is formed over the course of 5-60 minutes and creates a pulp density of 2-20%.

6. The method of claim 1 wherein the first water leaching is conducted at a temperature of between 0-40 °C for a duration of 5-720 minutes.

7. The method of any one of claims 1 to 6 wherein water added during the first water leaching is measured so as to maintain a solid / liquid (S / L) ratio of 1 :20-100.

8. The method of claim 1 of any one of claims 1 to 6 wherein the filtering of the water leached solution is nanofiltration.

9. The method of any one of claims 1 to 6 wherein the second leaching is conducted at a temperature of between 30-120 °C for a duration of 15-720 minutes.

10. The method of any one of claims 1 to 6 wherein water added during the second leaching is measured so as to maintain a solid / liquid (S / L) ratio of 5-800 g / L with a pH of between 0.5 and 5.5.

11. The method of any one of claims 1 to 6 wherein reductants from the second leaching include none or one or more of Cu, Fe, H2O2, tartaric acid, malic acid, ascorbic acid, citric acid, or a combination thereof.

12. The method of any one of claims 1 to 6 wherein the phosphate (POT ) and iron (Fe) extraction is conducted at a temperature of 90 to 150 °C for a duration of 5-720 minutes with a solution having a pH of 0.5-7.

13. The method of any one of claims 1 to 6 wherein the phosphate (PO43-) and iron (Fe) extraction is conducted for a duration of 5-720 minutes with a solution having a pH of 0.5- 7..

14. The method of any one of claims 1 to 6 wherein water, reagents, and chemicals used in the method are all recycled and are self-contained in the process.

15. The method of any one of claims 1 to 6 wherein rich nickel manganese cobalt oxides (NMC) and present and collected with aluminum / iron and further comprising feeding the NMC to a recovery unit to obtain nickel sulfate, cobalt sulfate, and manganese carbonate.

16. The method of any one of claims 1 to 6 wherein the first water leaching occurs after the forming of the black mass froth flotation.

17. The method of any one of claims 1 to 6 wherein the precipitation process occurs after the first water leaching.

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