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WO2025233268A1 - Récupération de cuivre à partir de matériaux de batterie au lithium-ion - Google Patents

Récupération de cuivre à partir de matériaux de batterie au lithium-ion

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Publication number
WO2025233268A1
WO2025233268A1 PCT/EP2025/062185 EP2025062185W WO2025233268A1 WO 2025233268 A1 WO2025233268 A1 WO 2025233268A1 EP 2025062185 W EP2025062185 W EP 2025062185W WO 2025233268 A1 WO2025233268 A1 WO 2025233268A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
thiosulfate
solution
aqueous solution
acidic aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/062185
Other languages
English (en)
Inventor
Maximilian RANG
Fabian Seeler
Wolfgang Rohde
Kerstin Schierle-Arndt
Vincent Smith
Jia Jin FOO
Jian Gao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2025233268A1 publication Critical patent/WO2025233268A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present disclosure relates to a method for removing and recovering copper via sulfide precipitation from an acidic solution produced from black mass material and other materials liberated from lithium-ion batteries.
  • Background Lithium-ion rechargeable batteries are increasingly powering automotive, consumer electronic, and industrial energy storage applications.
  • a portion of the lithium-ion batteries can be described as ternary batteries, which can include lithium batteries that use lithium-nickel-manganese-cobalt-oxide (NMC) as the cathode and graphite as the anode.
  • NMC lithium-nickel-manganese-cobalt-oxide
  • LFP batteries can include lithium iron phosphate (LFP) batteries and these batteries may have a different composition than other types of lithium-ion batteries.
  • LFP batteries utilize LiFePO4 as a cathode material, usually in combination with a graphitic carbon-based anode.
  • LFP batteries typically include relatively lower amounts of metals, such as nickel and cobalt, than other types of lithium-ion batteries. As nickel and cobalt can be relatively valuable, the relatively low amounts of these metals in LFP batteries may make LFP batteries less desirable to recycle than other forms of batteries that would yield relatively larger amounts of these valuable metals.
  • Several of the materials in a lithium-ion battery or battery pack can be recycled and may form separate outputs from an overall battery recycling process.
  • WO 2018/218358 A1 discloses a process to recover materials from rechargeable lithium-ion batteries, thus recycling them.
  • the process involves processing the batteries into a size-reduced feed stream; and then, via a series of separation, isolation, and/or leaching steps, allows for recovery of a copper product, cobalt, nickel, and/or manganese product, and a lithium product; and, optional recovery of a ferrous product, aluminum product, graphite product, etc.
  • WO 1996/025361 A1 discloses a method for separating copper and other metals in solution comprising the steps of precipitating the copper in a reactor at a free acid range of about 0.05 to 180 grams per liter, at a temperature from about 25°C to about 90°C in an aqueous solution with elemental sulfur, or chalcopyrite, and material selected from the group consisting of soluble sulfites and soluble bisulfites, and separating the precipitated copper, in the form of copper sulfides, by thickening the solution, recycling part to the precipitation step, and filtering copper sulfides from the other part.
  • CN 1115338 A discloses a process for removing Cu from acidic solution of Ni or Co which includes adding and suspending sulfur flour pretreated with wetting agent into the acidic solution, and blowing-in SO2 gas under a certain temperature, pressure and solution pH value to crystallize copper sulfide.
  • CN 1318619 C discloses a method for removing copper from a cobalt electrolyte during electrolytic production of cobalt.
  • US 2693404 A relates to a method of treating a sulfide material containing sulfides of at least one of the metals nickel and cobalt and copper sulfide.
  • the method comprises the steps of leaching the material with strong aqueous ammonia under super atmospheric pressure and at elevated temperature, agitating the mixture, feeding an oxidizing gas into the agitated mixture during the leaching operation, continuing the leaching operation for a period of time sufficient to produce in the ammoniacal solution, in addition to dissolved metal values, free ammonia, and at least one sulfur compound of the group consisting of thiosulfate and polythionates, said polythionates having more than two sulfur atoms in their molecular structure, heating the ammoniacal solution for a period of time sufficient to reduce the free ammonia content and convert dissolved copper values to and precipitate them as copper sulfides, separating precipitated copper sulfides from the ammoniacal solution, and recovering values of at: least one of the metals nickel and cobalt from the resultant solution.
  • WO 2022/183285 A1 provides a method of precipitating copper sulfide from an incoming feed stream comprising copper liberated from within battery materials.
  • the method includes the steps of: a) receiving an incoming feed stream comprising copper entrained in a carrier liquid in a precipitation apparatus; b) introducing a sulfide reductant to the feed stream to precipitate copper sulfide solids out of the feed stream during a precipitation residence time that is less than 24 hours to produce a copper sulfide slurry; and processing the copper sulfide slurry to separate the precipitated copper sulfide solids and provide a copper-depleted stream.
  • CN 111945002 B discloses a method for recycling waste lithium batteries and removing copper by a wet process.
  • the method comprises the following steps of sequentially discharging, crushing, screening and magnetically separating the waste lithium batteries to obtain battery powder and a copper-aluminum foil; adding a solvent into the battery powder, adding an acid and a reducing agent, stirring, and reacting to obtain a leaching solution; pickling the copper-aluminum foil, adding the leaching solution for reaction, and filtering to obtain sponge copper and copper removal liquid; and adding alkali metal carbonate into the copper removal liquid for reaction, adjusting the pH value to be acidic, filtering to obtain filter residues and a purified solution, extracting the purified solution, preparing a metal salt solution, and adding alkali liquor for co-precipitation in order to obtain a ternary precursor.
  • the reducing agent added to the battery powder can be hydrogen peroxide, sodium thiosulfate or sodium sulfite. It is added to reduce Ni, Co and/or Mn present in higher oxidation states.
  • CN 108545706 A provides a method for treating tellurium-containing waste liquor.
  • the method comprises the following steps: S1, the tellurium-containing waste liquor is concentrated and crystallized for obtaining copper sulfate and crystallization mother liquor respectively, and the tellurium-containing waste liquor contains elements of tellurium and copper and sulfuric acid; S2, the crystallization mother liquor is reduced with a reducing agent, and tellurium- copper slag and reduced liquor are obtained respectively; S3, an acid solution and an oxidant are adopted for acid oxidation leaching on the tellurium-copper slag, an acid leaching solution is obtained, and the acid solution is a hydrochloric acid solution or a sulfuric acid solution; S4, the acid leaching solution is subjected to solid-liquid separation, a liquid phase is taken, pH is adjusted with sodium hydroxide to 12-14, heating is performed to a boiling state for reaction, and an alkaline conversion solution is obtained; S5,the alkaline conversion solution is subjected to acidic hydrolysis, and a tellurium dioxide product is obtained.
  • the present disclosure provides a method of precipitating copper sulfide from an acidic aqueous solution comprising copper liberated from within battery materials including the steps of: a) receiving an acidic aqueous solution comprising copper in a precipitation apparatus; b) introducing a thiosulfate salt into the acidic aqueous solution to precipitate copper sulfide and produce a copper sulfide slurry; and c) processing the copper sulfide slurry to separate the precipitated copper sulfide and provide a copper-depleted solution.
  • a thiosulfate salt is introduced into the acidic aqueous solution to precipitate copper sulfide and produce a copper sulfide slurry.
  • thiosulfate salts show higher selectivity towards Cu. Sulfide supersaturation is reached instantly when adding sulfides, while CuS 2 O 3 is intermittently formed on addition of thiosulfate salts, improving selectivity of the precipitation process significantly. Larger copper sulfide particles having a narrower particle size distribution are obtained when using thiosulfate salts.
  • the thiosulfate salt is selected from the group consisting of ammonium thiosulfate, alkali metal thiosulfates, and alkaline earth thiosulfates. In a further embodiment of the process, the thiosulfate salt is selected from the group consisting of ammonium thiosulfate, lithium thiosulfate, sodium thiosulfate, magnesium thiosulfate, and calcium thiosulfate. In a further embodiment of the process, the thiosulfate salt is sodium thiosulfate. In another further embodiment of the process, the thiosulfate salt is ammonium thiosulfate.
  • the thiosulfate salt is lithium thiosulfate. In another further embodiment of the process, the thiosulfate salt is magnesium thiosulfate. In another further embodiment of the process, the thiosulfate salt is calcium thiosulfate. In an embodiment of the process, the thiosulfate salt is added to the acidic aqueous solution comprising copper as a solid. In another embodiment of the process, the thiosulfate salt is added to the acidic aqueous solution comprising copper in dissolved form as an aqueous solution.
  • the thiosulfate salt is freshly prepared in a separate reactor by reaction of a sulfite salt with sulfur and then added to the acidic aqueous solution comprising copper.
  • the thiosulfate salt is prepared in situ by reaction of a sulfite salt with sulfur.
  • the thiosulfate salt is introduced into the acidic aqueous solution so that it has a molar concentration within the acidic aqueous solution of from 0.95 to 1.3 times the molar concentration of copper in the acidic aqueous solution, e.g., from 1.05 to 1.20 times the molar concentration of copper in the acidic aqueous solution.
  • the precipitation of the copper sulfide in step b) is conducted at an operating temperature of from 60°C to 90°C, for instance, from 75°C to 85°C. A minimum temperature of 60°C is needed for the precipitation to take place. The best performance is observed at temperatures above 75°C.
  • the residence time is from 60 min to 300 min, e.g., from 90 min to 240 min.
  • the precipitation of the copper sulfide in step b) is conducted at a solution pH that is in the range of from -1 to +2, for instance, from 0.5 to 1.5.
  • the solution pH in step b) is adjusted to the desired value by addition of a basic agent.
  • the basic agent is a metal hydroxide or a metal carbonate.
  • the basic agent is magnesium carbonate.
  • the basic agent is manganese carbonate.
  • the basic agent is a mixed hydroxide precipitate (MHP).
  • the solution pH in step b) is adjusted to a value of (1.0 ⁇ 0.1) before addition of the thiosulfate salt.
  • Processing the copper-depleted solution to separate the precipitated copper sulfide includes using a solid/liquid separator.
  • the solid/liquid separator may include a separation apparatus having a filter, and wherein the copper sulfide slurry may form a filter cake on the filter and the output stream comprises filtrate passing through the filter.
  • the solid/liquid separator comprises a filter press.
  • the solid/liquid separator comprises a thickener.
  • the solid/liquid separator comprises a settler.
  • the solid/liquid separator comprises a centrifuge.
  • a copper concentration in the acidic aqueous solution is from 3 to 20 g/L or from 4 to 16 g/L, and a copper concentration in the copper-depleted solution is lower than 2 g/L, e.g., lower than 1.5 g/L, for instance, lower than 1 g/L, or even lower than 0.1 g/L.
  • at least 60 wt.%, e.g., at least 70 wt.%, for instance, at least 90 wt.%, or even at least 99 wt.% of the copper present in the acidic aqueous solution is precipitated in step b).
  • the acidic aqueous solution comprising copper has been obtained from lithium-ion battery materials from NCM batteries. In another embodiment of the process, the acidic aqueous solution comprising copper has been obtained from lithium-ion battery materials from LFP batteries. In an embodiment of the process, the battery materials comprise black mass. Examples of suitable lithium ion battery materials for preparing the acidic aqueous solution comprising copper include black mass, cathode active materials, and mixed hydroxide precipitates (MHP).
  • MHP mixed hydroxide precipitates
  • Black mass refers to a combination of some of the components of rechargeable lithium-ion batteries that can be liberated from within the batteries during a processing step (such as a mechanical processing, disassembly, comminuting, and/or pyrolysis step) and includes at least a combination of cathode and/or anode electrode powders that may include lithium, nickel, cobalt, copper, iron, phosphorus, and manganese.
  • Materials present in rechargeable lithium-ion batteries include the anode and cathode materials, as well as a suitable electrolyte (residual organic electrolyte such as C 1 -C 6 alkyl carbonates, such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), and mixtures thereof) and possibly a solid separator which may be sulfide, oxide, ceramic or glass for SSBs.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • PC propylene carbonate
  • solid separator which may be sulfide, oxide, ceramic or glass for SSBs.
  • the metals included in the black mass may be expected to include lithium, nickel, cobalt, copper, iron, phosphorus, manganese and other such materials.
  • the black mass is a particulate material having an average particle diameter (D50) in the range of from 1 ⁇ m to 500 ⁇ m, obtained by mechanical comminution of at least one battery material chosen from a lithium ion battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material, and combinations thereof, drying the comminuted battery material at a temperature below 200°C, and sifting the comminuted and dried battery material to obtain a fine fraction having an average particle diameter (D50) in the range of from 1 ⁇ m to 500 ⁇ m (oxidic black mass), or obtained by mechanical comminution of at least one battery material chosen from a lithium ion battery, lithium ion battery waste, lithium
  • Black mass generally comprises from 0.1 to 10 wt.% Li, from 10 to 50 wt.% Ni , from 0.1 to 20 wt.% Co, from 0.1 to 15 wt.% Mn, from 0 to 10 wt.% Cu, from 0 to 40 wt.% C, e.g., graphite, from 0 to 8 wt.% Al, and from 0 to 5 wt.% F.
  • MHP mixed hydroxide precipitate
  • MHP mixed hydroxide precipitate
  • the MHP is obtained by precipitating metal hydroxides from a metal salt solution.
  • MHP typically comprises from 0 to 2 wt.% Li, from 10 to 50 wt.% Ni, from 0.1 to 20 wt.% Co, from 0.01 to 15 wt.% Mn.
  • Moisture content generally is in the range of from 20 to 60 wt.%, relative to the total weight of MHP.
  • a typical range for D(50) is from 1 to 150 ⁇ m.
  • the MHP is an intermediate nickel product produced from laterite nickel ore, which contains both nickel and a small percentage of cobalt.
  • MHP is typically produced using a high-pressure acid leaching (HPAL) process.
  • HPAL high-pressure acid leaching
  • the mixed hydroxide precipitate mostly consists of nickel hydroxide, but also contains valuable cobalt hydroxides and various other impurities, the main one being manganese.
  • Ni content typically is 34-55 wt.%
  • Co content typically 1- 4.5 wt.%.
  • the process of the present disclosure includes, prior to step a), the steps of: i) receiving a black mass feed material comprising at least lithium, copper, and graphite liberated from within battery materials, ii) acid leaching the black mass material at a pH that is less than 2, thereby producing a pregnant leach solution (PLS) comprising copper from the black mass feed material, wherein the acidic aqueous solution comprises the PLS.
  • PLS pregnant leach solution
  • the systems and processes for obtaining the black mass from batteries can generally include one or more suitable, size reduction operations in which incoming batteries in the form of whole batteries, cells and/or portions thereof, along with any associated leads, housings, wires and the like (collectively referred to as battery materials) are at least physically processed to liberate the black mass materials within the battery cell for further processing.
  • This can include physically shredding the incoming battery materials, such as using a suitable comminuting apparatus, in an operation that can break open the battery cells and can convert the incoming battery materials into a plurality of relatively small, size-reduced battery materials that can be further processed, for instance, by thermal treatment.
  • the acidic aqueous solution that is processed using the described techniques is a pregnant leach solution that contains at least some of the desired target metals that have been obtained/liberated from battery materials or that have been obtained from other sources.
  • the acidic aqueous solution can be received in any suitable processes apparatus, such as a precipitation apparatus, that can include one or more suitable vessels or tanks, solid/liquid separators, pumps, controllers, flow control devices, settling tanks, suitable containment and ventilation systems, and gas scrubbers; and under suitable residence times and operating conditions.
  • the precipitation apparatus can include any suitable combination of physical tanks, vessels and the like.
  • the material within the precipitation apparatus can be described as a copper sulfide slurry.
  • the copper sulfide slurry is processed to separate at least some, and preferably substantially the entire precipitated copper sulfide from the copper sulfide slurry. Processing may include treating the copper sulfide slurry using a suitable solid/liquid separator, such as a filter, to collect the metal sulfide as a filter cake material while allowing a now copper-depleted filtrate to pass through the filter and to form a copper-depleted solution.
  • a suitable solid/liquid separator such as a filter
  • the copper-depleted filtrate will include at least most, if not substantially all of the lithium, nickel, and cobalt that was present in the incoming black mass feed stream so that it can be recovered in later processing steps.
  • the separated solids can be further processed by drying and/or packaging the metal sulfide for sale or other commercial uses, e.g., in a smelter.
  • the copper-depleted, but generally lithium- rich filtrate can be further processed to recover metal present in the copper- depleted filtrate.
  • Pre-processing can include the use of a size-reduction apparatus or comminuting apparatus that can help to cause a size reduction of the incoming battery materials to form reduced-size battery materials and to liberate electrolyte materials and a black mass material comprising anode and cathode powders from within the battery materials.
  • Pre-processing may include at least partially leaching the black mass material so that a pregnant leach solution (PLS) is provided.
  • PLS pregnant leach solution
  • the black mass material may be leached using suitable reagents (such as sulfuric acid or other acids, sulfur dioxide, hydrogen peroxide, oxygen or a combination thereof and other reagents) to generate the PLS.
  • the leaching process comprises leaching black mass with sulfuric acid under inert atmosphere in a first leaching step, subsequently leaching the mixture obtained in the first leaching step with sulfuric acid while injecting air into the mixture, and optionally, leaching the mixture obtained in the second leaching step with sulfuric acid while adding a sulfur-containing reducing agent, e.g., sulfur dioxide, to the mixture.
  • a sulfur-containing reducing agent e.g., sulfur dioxide
  • the resulting stream can be filtered to separate the unwanted residues and solids, which may include at least a portion of any carbon that was in the black mass material, and produce a pregnant leach solution.
  • a precipitation apparatus receives the acidic aqueous solution and can also receive a supply of the desired thiosulfate salt.
  • the precipitation apparatus includes a primary precipitation vessel that can receive the acidic aqueous solution and the thiosulfate salt.
  • This vessel can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).
  • a solid/liquid separator is provided downstream from the precipitation vessel and can receive the copper sulfide slurry. The separator can be a filter press, and the separated metal sulfide can be extracted via a solids stream, while the now copper-depleted solution can be sent for further processing.
  • the copper-depleted solution can exit the precipitation apparatus as the copper-depleted filtrate.
  • the copper-depleted filtrate is sent for further processing via a downstream hydrometallurgical processing system which can include any suitable processes and systems, including extraction, precipitation, filters and other operations that can help separate and extract the various target products.
  • the downstream hydrometallurgical processing may include the steps of adjusting the oxidation reduction potential (ORP) of the copper-depleted filtrate to help make it more suitable for a downstream process.
  • ORP oxidation reduction potential
  • the ORP of the copper-depleted filtrate may be adjusted to be equal to or above 400 mV, and preferably to be about 500 mV which converts Fe2+ in the solution to Fe3+, which can help facilitate the downstream separation of iron from other target metals (such as cobalt and nickel).
  • Other suitable separation systems can be used to further process the process slurries and material streams and can be configured to recover at least the target lithium metal as a lithium output stream. Examples Unless otherwise specified, all percentages in the examples refer to weight percent (w/w).
  • H 2 SO 4 was added under stirring with a ratio of 150%, relative to the weight of the black mass. After stirring for a first time period, the mixture was aerated and stirred for a second time period. Then, the mixture was filtered yielding feed I and a solid residue. 800 g of feed I stemming from leaching of pyrolyzed NCM battery waste and having a pH of ⁇ 0.5 was heated to 75°C. Then, 1.15 mol of Na2S2O3 per mol of Cu were added into the reaction mixture and stirring was continued for 240 min. The suspension was filtered and the residue was washed and then dried at 75°C and 100 mbar. 804 g filtrate and 5.2 g dry solid were obtained.
  • the D(50) of the solid was determined to be 17 ⁇ m.
  • leaching NCM black mass was suspended in water in a solid-to-liquid-ratio of 1:4, the vessel was inertized and the mixture was subsequently heated to 90°C. Then, H 2 SO 4 was added under stirring with a ratio of 150%, relative to the weight of the black mass. After stirring for a first time period, the mixture was aerated and stirred for a second time period. Then, the mixture was filtered yielding feed I and a solid residue.
  • 900 g of feed I stemming from leaching of pyrolyzed NCM battery waste and having a pH of ⁇ 0.5 was heated to 75°C and the pH was adjusted to 1.5 using NaOH.
  • leaching NCM black mass was suspended in water in a solid-to-liquid-ratio of 1:4, the vessel was inertized and the mixture was subsequently heated to 90°C. Then, H 2 SO 4 was added under stirring with a ratio of 150%, relative to the weight of the black mass. After stirring for a first time period, the mixture was aerated and stirred for a second time period. Then, the mixture was filtered yielding feed I and a solid residue. 800 g of feed I stemming from leaching of pyrolyzed NCM battery waste and having a pH of ⁇ 0.5 was heated to 75°C and the pH was adjusted to 1.5 using NaOH.
  • Example 7 MHP leaching A mixed hydroxide precipitate (MHP) containing Co, Mn, and Ni was suspended in water to a final solid-to-liquid-ratio of 1:5. The suspension was heated to 60°C, its pH was adjusted to 1.5 using H2SO4 and stirring was continued until all added solid was dissolved yielding feed IIa. 401 g of feed IIa stemming from leaching of MHP precipitated from an aqueous battery waste stream and having a pH of 0.7 was spiked with CuSO4 to prepare feed II, then heated to 75°C. Subsequently, 1.05 mol of Na2S2O3 per mol of Cu was added into the reaction mixture and stirring was continued for 120 min.
  • MHP mixed hydroxide precipitate
  • Example 8 MHP leaching A mixed hydroxide precipitate (MHP) containing Co, Mn, and Ni was suspended in water to a final solid-to-liquid-ratio of 1:5. The suspension was heated to 60°C, its pH was adjusted to 1.5 using H 2 SO 4 and stirring was continued until all added solid was dissolved yielding feed IIa.
  • MHP mixed hydroxide precipitate
  • Example 9 MHP leaching A mixed hydroxide precipitate (MHP) containing Co, Mn, and Ni was suspended in water to a final solid-to-liquid-ratio of 1:5. The suspension was heated to 60°C, its pH was adjusted to 1.5 using H 2 SO 4 and stirring was continued until all added solid was dissolved yielding feed IIa. 401 g of feed IIa stemming from leaching of MHP precipitated from an aqueous battery waste stream and having a pH of 0.7 was spiked with CuSO4 to prepare feed II, then heated to 85°C. Subsequently, 1.05 mol of Na 2 S 2 O 3 per mol of Cu were added into the reaction mixture and stirring was continued for 120 min. The suspension was filtered and the residue was washed and then dried at 75°C and 100 mbar. 400 g filtrate and 2.6 g dry solid were obtained. The D(50) of the solid was determined to be 6.0 ⁇ m.
  • Example 10 LFP leaching LFP black mass was suspended in water in a solid-to-liquid-ratio of 1:5, then H 2 SO 4 was added at a ratio of 50%, relative to the weight of the black mass. The reaction mixture was heated to 90°C and was stirred for 180 min. Then the mixture was filtered off yielding feed III and a solid residue. 443 g of feed III stemming from leaching of LFP battery waste and having a pH of 1.3 was heated to 85°C. Then, 1.05 mol of Na2S2O3 per mol of Cu were added into the reaction mixture and stirring was continued for 120 min, whereafter a pH of 0.9 was reached. The suspension was filtered and the residue was washed and then dried at 75°C and 100 mbar.
  • Example 11 NCM leaching NCM black mass was suspended in water in a solid-to-liquid-ratio of 1:4, the vessel was inertized and the mixture was subsequently heated to 90°C. Then H2SO4 was added under stirring at a ratio of 120%, relative to the weight of the black mass. After stirring for a first time period, the mixture was aerated and stirred for a second time period. Then, the mixture was filtered yielding feed IV and a solid residue. A solution containing Mn and impurities was heated to 60°C and treated with Na 2 CO 3 solution until a pH value of 8.0 was reached.
  • the reaction mixture was stirred for some time before it was filtered yielding a Mn-depleted filtrate and a solid residue mainly consisting of MnCO 3 .
  • 427 g of feed IV stemming from leaching of NCM battery waste and having a pH of 0.1 was heated to 85°C and the pH was adjusted to 1.5 using MnCO 3 obtained from the precipitation stage of a Mn-containing solution from a battery recycling stream.
  • 1.05 mol of Na2S2O3 per mol of Cu were added into the reaction mixture and stirring was continued for 120 min, whereafter a pH of 0.4 was reached.
  • the suspension was filtered and the residue was washed and then dried at 75°C and 100 mbar. 446.2 filtrate and 10.0 g dry solid were obtained.
  • the D(50) of the solid was determined to be 11.6 ⁇ m.
  • Example 12 NCM leaching NCM black mass was suspended in water in a solid-to-liquid-ratio of 1:4, the vessel was inertized and the mixture was subsequently heated to 90°C. Then H 2 SO 4 was added under stirring at a ratio of 150%, relative to the weight of the black mass. After stirring for a first time period, the mixture was aerated and stirred for a second time period. Then the mixture was filtered yielding feed I and a solid residue. 800 g of feed I stemming from leaching of pyrolyzed NCM battery waste having a pH of ⁇ 0.5 was heated to 85°C and the pH was adjusted to 1.5 using NaOH.
  • Example 13 NCM leaching NCM black mass was suspended in water in a solid-to-liquid-ratio of 1:4, the vessel was inertized and the mixture was subsequently heated to 90°C. Then H 2 SO 4 was added under stirring at a ratio of 150%, relative to the weight of the black mass.
  • Table 1 Weight percentages of selected elements in the filtrates obtained Example Cu Ni Co Fe P 1 0.11% 2.70% 1.10% 0.08% 0.10% 2 0.02% 2.40% 0.82% 0.07% 0.10% 4 0.07% 2.20% 0.84% 0.06% 0.10% 5 0.12% 2.00% 0.69% 0.05% 0.10% 6 0.21% 2.30% 0.92% 0.06% 0.10% 7 0.10% 2.80% 2.50% / / 8 0.003% 2.70% 2.30% / / 9 0.06% 2.90% 2.50% / / 10 0.00% 0.08% 0.00% 1.50% 0.86% 11 0.07% 2.5% 1.2% 0.04% / 12 0.12% 2.6% 1.1% 0.07% / 13 0.07% 2.8% 1.7% 0.08% /
  • Table 2 Weight percentages of selected elements in the dry solids obtained Example Cu Ni Co Fe P 1 56% 0.26% 0.10% 0.10% / 2 59% 0.30% 0.10% 0.02% / 4 44% 1.00% 0.39% 0.10% / 5 65% 0.11% 0.39% 0.07% / 6 54% 0.38% 0.15% 0.33% / 7 65% 0.40% 0.30% / / 8 64% 0.30% 0.20% / / 9 64% 0.26% 0.24% / / 10 14% 0.00% 0.00% 12% 8.50% 11 59% 0.6% 0.3% / / 12 58% 0.3% 0.12% 0.14% / 13 56% 0.25% 0.22% 0.15% / Table 3: Yields of selected elements in the dry solids obtained Example Cu Ni Co Fe 1 75.6% 0.08% 0.09% 1.10% 2 96.3% 0.08% 0.08% 0.19% 4 82.3% 0.24% 0.27% 0.90% 5 66.6% 0.02% 0.19% 0.4
  • metal yields were determined using the elemental content determined in the dry solids.
  • Cu-yields in solid were determined from the Cu-content measured in the obtained liquid phases.
  • ⁇ ( ⁇ ) ⁇ ⁇ ⁇ ( ⁇ ) (2) wherein L denotes the liquid phase, Cu ICP ⁇ L is the determined percentage-based content in the liquid phase, m(L) is the mass of the liquid phase, m(Cu L ) is the weight content of Cu in the liquid phase, m(Cu Max ) is the total amount of Cu introduced with the feed, and MY Cu is the yield of Cu.

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Abstract

La présente invention concerne un procédé d'élimination et de récupération de cuivre par précipitation de sulfure à partir d'une solution acide produite à partir d'un matériau de masse noire et d'autres matériaux de batterie au lithium-ion.
PCT/EP2025/062185 2024-05-06 2025-05-05 Récupération de cuivre à partir de matériaux de batterie au lithium-ion Pending WO2025233268A1 (fr)

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* Cited by examiner, † Cited by third party
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US2693404A (en) 1951-01-18 1954-11-02 Sherritt Gordon Mines Ltd Method of separating metal values from ammoniacal solutions
CN1115338A (zh) 1994-07-18 1996-01-24 西安建筑科技大学 一种从镍或钴的酸性溶液中除铜的方法
WO1996025361A1 (fr) 1995-02-17 1996-08-22 Baker Hughes Incorporated Procede de precipitation du cuivre
CN1318619A (zh) 2000-04-19 2001-10-24 气体产品与化学公司 回收c2+烃的氮制冷方法
JP2013095988A (ja) * 2011-11-04 2013-05-20 Sumitomo Metal Mining Co Ltd 金属の硫化物沈殿方法
CN108545706A (zh) 2018-05-31 2018-09-18 阳谷祥光铜业有限公司 一种含碲废液的处理方法
WO2018218358A1 (fr) 2017-05-30 2018-12-06 Li-Cycle Corp. Procédé, appareil et système de récupération de matériaux à partir de batteries
CN111945002B (zh) 2020-07-06 2022-06-14 广东邦普循环科技有限公司 一种废旧锂电池回收湿法除铜的方法
WO2022183285A1 (fr) 2021-03-02 2022-09-09 Li-Cycle Corp. Procédé d'élimination de métaux cibles par précipitation de sulfure
AU2021230421A1 (en) * 2020-03-02 2022-10-13 Li-Cycle Corp. A method for processing lithium iron phosphate batteries
US20230313337A1 (en) * 2020-09-03 2023-10-05 Mitsubishi Materials Corporation Method for separating cobalt and nickel
CN117721309A (zh) * 2023-12-12 2024-03-19 中伟新材料股份有限公司 废水中有价金属的资源化回收方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2693404A (en) 1951-01-18 1954-11-02 Sherritt Gordon Mines Ltd Method of separating metal values from ammoniacal solutions
CN1115338A (zh) 1994-07-18 1996-01-24 西安建筑科技大学 一种从镍或钴的酸性溶液中除铜的方法
WO1996025361A1 (fr) 1995-02-17 1996-08-22 Baker Hughes Incorporated Procede de precipitation du cuivre
CN1318619A (zh) 2000-04-19 2001-10-24 气体产品与化学公司 回收c2+烃的氮制冷方法
JP2013095988A (ja) * 2011-11-04 2013-05-20 Sumitomo Metal Mining Co Ltd 金属の硫化物沈殿方法
WO2018218358A1 (fr) 2017-05-30 2018-12-06 Li-Cycle Corp. Procédé, appareil et système de récupération de matériaux à partir de batteries
CN108545706A (zh) 2018-05-31 2018-09-18 阳谷祥光铜业有限公司 一种含碲废液的处理方法
AU2021230421A1 (en) * 2020-03-02 2022-10-13 Li-Cycle Corp. A method for processing lithium iron phosphate batteries
CN111945002B (zh) 2020-07-06 2022-06-14 广东邦普循环科技有限公司 一种废旧锂电池回收湿法除铜的方法
US20230313337A1 (en) * 2020-09-03 2023-10-05 Mitsubishi Materials Corporation Method for separating cobalt and nickel
WO2022183285A1 (fr) 2021-03-02 2022-09-09 Li-Cycle Corp. Procédé d'élimination de métaux cibles par précipitation de sulfure
CN117721309A (zh) * 2023-12-12 2024-03-19 中伟新材料股份有限公司 废水中有价金属的资源化回收方法

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