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WO2025010462A1 - Recyclage pyrométallurgique de batteries en fin de vie - Google Patents

Recyclage pyrométallurgique de batteries en fin de vie Download PDF

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Publication number
WO2025010462A1
WO2025010462A1 PCT/AU2023/051308 AU2023051308W WO2025010462A1 WO 2025010462 A1 WO2025010462 A1 WO 2025010462A1 AU 2023051308 W AU2023051308 W AU 2023051308W WO 2025010462 A1 WO2025010462 A1 WO 2025010462A1
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WO
WIPO (PCT)
Prior art keywords
matte
life battery
furnace
base metal
valuable
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/AU2023/051308
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English (en)
Inventor
Stuart Nicol
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.)
Glencore Technology Pty Ltd
Original Assignee
Glencore Technology Pty Ltd
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
Priority claimed from AU2023902216A external-priority patent/AU2023902216A0/en
Application filed by Glencore Technology Pty Ltd filed Critical Glencore Technology Pty Ltd
Publication of WO2025010462A1 publication Critical patent/WO2025010462A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/025—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper, or baths
    • 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
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/003—Bath smelting or converting
    • C22B15/0032—Bath smelting or converting in shaft furnaces, e.g. blast furnaces
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/025—Obtaining nickel or cobalt by dry processes with formation of a matte or by matte refining or converting into nickel or cobalt, e.g. by the Oxford process
    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/08—Dry methods smelting of sulfides or formation of mattes by sulfides; Roasting reaction 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
    • 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
    • C22B7/001—Dry processes
    • C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • 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
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • 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
    • 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
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for treating end-of-life batteries, obtaining a high recovery of one or more valuable base metals (e.g., Ni, Co, Cu, Zn, Pb, Mn etc.) and associated base metals (e.g., Au, Ag, Pt, etc.) into a molten matte phase.
  • the matte phase can then be processed in a base metal refinery.
  • the residual slag can be sold or safely disposed of.
  • the present invention relates to a method of extracting valuable battery materials and/or valuable metals, such as cobalt, copper, nickel, lithium, etc., from end-of-life batteries, preferably lithium-ion batteries.
  • the invention describes a method for smelting end-of- life lithium-ion batteries, wherein the process comprises feeding a mixture of these materials plus a sulfidising agent, fluxes, and fuel into a furnace, injecting air and/or oxygen into the molten charge to achieve an oxygen partial pressure between 10' 6 atm and 10' 11 atm such that a base metal matte is formed to which the majority of the valuable metals report. Also formed is a slag containing less than 5 wt.% of the base metals. The molten slag is subsequently sold (as aggregate), processed to recover non-base metals e.g., lithium) or discarded. The molten base metal matte may be further processed in a base metal refinery or smelted via known techniques.
  • Valuable metals are mined from their constituent ores at an exponentially- increasing rate. With the overall supply being strictly finite, some metals are already under supply and sustainability pressure. Without increased adoption of recycling practices, the global supply of certain metals will inevitably extinguish long before consumer demand subsides. Examples of such metals include nickel, copper, manganese, cobalt and lithium.
  • Cobalt’s value resides principally in its utility across industries such as alloys, batteries, catalysis, pigments, radioisotopes, electroplating and porcelain enamels.
  • Nickel is used across many industrial and consumer products including stainless steel, alnico magnets, coinage, rechargeable batteries (e.g., nickel-iron), electric guitar strings, microphone capsules, plating on plumbing fixtures and special alloys such as permalloy, elinvar, and invar. It is widely used in many other alloys, including nickel brasses and bronzes and alloys with copper, chromium, aluminium, lead, cobalt, silver, and gold.
  • Manganese is applied industrially across steelmaking, alloying, batteries, resistors, minting and ceramic colourings.
  • lithium is assuming ever-increasing popularity given its many uses: ceramics, glasses, batteries, electronics, lubricating greases, metallurgy, pyrotechnics, air purification, optics, polymer chemistry, military applications and medicine - to name but a few.
  • One of the principal uses of lithium is in batteries - and demand will only continue to grow as (amongst other emerging technologies) all-electric vehicles take to the roads over the next few years.
  • Lithium is especially amenable to use in batteries owing to its high electrode potential (the highest of all metals) and its low atomic mass, which leads to high charge-to-weight and power-to-weight ratios.
  • Lithium batteries are preferred over other batteries due to their relatively high charge density (long life), but presently suffer from a relatively high cost per unit.
  • lithium cells can produce voltages from 1.5 V (comparable to a zinc-carbon or alkaline battery) to about 3.7 V.
  • End-of-life battery waste is the industry term used to describe a type of e- waste comprising crushed and shredded end-of-life battery cells.
  • waste batteries are collected, sorted, discharged and disassembled. This is followed by mechanical crushing, drying, sorting sieving and pyrolysis to 700 °C to remove any remaining electrolyte and potentially hazardous to health fluorine-containing components.
  • the resulting material is what is referred to in the battery recycling industry as “treated end-of-life battery waste”.
  • Hydrometallurgy refers to the extraction of metal by preparing an aqueous solution of a salt of the metal and recovering the metal from the solution.
  • leaching or dissolution of the metal or metal compound in water, commonly with additional agents; separation of the waste and purification of the leach solution; and the precipitation of the metal or one of its pure compounds from the leach solution by chemical or electrolytic means.
  • Common leaching agents include sulfuric acid, hydrochloric acid and hydrogen peroxide, etc. Multiple steps are required, and significant wastewater is produced.
  • Pyrometallurgy refers to the extraction and purification of metals by processes involving the application of heat. The most important operations are roasting, smelting, and refining. Such processes are extremely energy-intensive, consume many environmentally harmful chemicals and result in the generation of hazardous gases.
  • US 11,661,638, to Umicore describes a process and a slag suitable for the recovery of Ni and Co from Li-ion batteries or their waste.
  • the slag composition is defined according to: 10% ⁇ MnO ⁇ 40%; (CaO+1.5*Li2O)/A12O3>0.3; CaO+0.8* MnO+0.8*Li 2 O ⁇ 60%; (CaO+2*Li 2 O+0.4*MnO)/SiO2>2.0; Li 2 >l%; and A12O3+SiO2+CaO+Li2O+MnO+FeO+MgO>85%.
  • This composition is particularly adapted to limit or avoid the corrosion of furnaces lined with magnesia-bearing refractory bricks.
  • US 2020/0263276, to Sumitomo Metal Mining Co., Ltd. describes method for treating lithium ion battery waste using a converter furnace in a copper smelting process, wherein, prior to a treatment for charging a copper matte produced in a flash smelter in a copper smelting process into a converter furnace and blowing oxygen into the converter furnace to produce crude copper, the lithium ion battery waste is introduced into the converter furnace or a ladle that is used for the charging of the copper matte into the converter furnace and then the lithium ion battery waste is burned with residual heat in the converter furnace or the ladle.
  • WO 2022/045973 to Green Li-Ion Pte. Ltd., describes a method of treating a leaching solution derived from a black mass (essentially synonymous with end-of-life battery waste) from spent lithium-ion batteries comprising setting pH of the leaching solution to about pH 1.2 to 2.5, adding iron powder to induce copper cementation, adding lime after copper cementation, and after adding lime, transiting pH of the leaching solution to about pH 6 to extract calcium fluoride, titanium hydroxide, aluminium hydroxide, iron hydroxide, and iron phosphate. Also disclosed is a black mass recycling system comprising an impurity removal reactor configured to receive a sodium hydroxide feed, an iron powder feed, and a lime feed.
  • US 9,484,606, to Hulico LLC describes a method of recycling and refurbishing battery electrode materials.
  • one disclosed embodiment provides a method comprising obtaining a quantity of spent electrode material, reacting the spent electrode material with an aqueous lithium solution in an autoclave while heating the spent electrode material and the aqueous lithium solution to form a hydrothermally reacted spent electrode material, removing the hydrothermally reacted spent electrode material from the aqueous lithium solution, and sintering the hydrothermally reacted spent material to form a recycled electrode material.
  • the valuable metals are selected from the group consisting of cobalt, nickel, manganese and lithium.
  • End-of-life battery materials refers to, essentially, whole or crushed end-of- life battery waste.
  • the end-of-life battery waste subject of the present invention is “raw” end-of-life battery waste. It was not pre-treated (for example, by pyrolysis, to remove the battery electrolytes, or sodium hydroxide leaching and sonication to remove aluminium). The economic potential of a recycling method that is efficacious despite avoiding expensive pre-treatment step/s is clear.
  • Valuable base metals refers to any metal that may be present in the end-of- life battery waste, including, not limited to, one or more of Li, Au, Ag, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V. “Valuable base metals” may also extend to oxides of such metals, for example, SiCh, CaO, AI2O3, Li2O, MnO, MgO, etc.
  • the phrase “consisting of’ excludes any element, step, or ingredient not specified in the claim.
  • the phrase “consists of’ (or variations thereof) appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
  • the phrase “consisting essentially of’ limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basis and novel characteristic(s) of the claimed subject matter.
  • FIG. 7 is a flowchart of a preferred embodiment of the present invention, which defines a method for the extraction of one or more valuable base metal/s from end- of-life battery materials, the method comprising the steps of: obtaining the mass end-of- life battery materials (“feed preparation”) having a content of the one or more valuable base metal/s; subjecting the black mass to a pyrometallurgical furnace (e.g., an ISASMELTTM furnace) defined by a molten turbulent bath comprising one or more sulfidising agent/s; one or more flux/es; one or more fuel/s; thereby to provide for an oxygen partial pressure of between about 10' 13 and about 10' 4 atm; subjecting the off-gas to a gas scrubber to provide for a clean off-gas and an effluent; forming a base metal matte (z.e., molten metal sulfide phase) and a slag (z.e., molten metal oxide phase), the slag comprising
  • the present invention relates generally to a method for the pyrometallurgical processing of end-of-life battery materials, preferably lithium-ion batteries, mixed with a low temperature ( ⁇ 900 °C) sulfidising agent, which may at least partially overcome some of the known disadvantages of past methods for high temperature spent battery treatment.
  • a processing method is presented in Figure 1.
  • the present invention utilises a “sulfur deficient matte”.
  • the advantage of the sulfur deficient matte is that an operator can adjust the liquidus temperature of the matte phase depending on the amount of sulfur in the melt. This means that if the slag has a high liquidus temperature, the operator can run with a sulfur deficient matte to prevent a superheated matte from forming.
  • a normal matte is a molten sulfide (NiS-C S-CoS-FeS, etc.), while a sulfur deficient matte is between a metal and a normal matte (Ni-NiS-Cu- CmS-Fc-FcS-Co-CoS, etc.).
  • a method for the extraction of one or more valuable base metal/s from end-of-life battery materials comprising the steps of:
  • one or more low temperature ( ⁇ 950 °C) sulfidising agent/s one or more low temperature ( ⁇ 950 °C) sulfidising agent/s
  • the inventive extraction method is complete in about ⁇ 1 minutes. At these high temperatures, the reaction kinetics are very fast. Those of skill in the art will appreciate that furnaces are typically sized based on the feed and product handling constraints rather than residence time in the vessel.
  • the method comprises the further step of:
  • the slag contains >0.1 wt.% sulfur.
  • the slag formed in the method of US 11,661,638 (discussed above) contains no sulfur.
  • the one or more low temperature sulfidising agent/s comprise sulfur, gypsum, metal sulfides and/or metal sulfates such as sodium, calcium, magnesium, copper, iron(II), iron (III), hydrogen and lead.
  • the one or more sulfidising agent/s comprise gypsum.
  • the gypsum comprises CaSO4.2H2O.
  • the one or more sulfidising agent/s is/are added such that the amount of sulfur in the base metal matte is between about 1 and about 28 wt.%.
  • the one or more sulfidising agent/s is/are added such that the amount of sulfur in the base metal matte is about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28 wt.%.
  • the one or more sulfidising agent/s is/are added such that the amount of sulfur in the base metal matte is between about 1 to 22, 2 to 21, 3 to 20, 4 to 19, 5 to 18, 6 to 17, 7 to 16, 7.5 to 15, 8 to 14, 8.5 to 13, 9 to 12, 9.5 to 11, or about 10 wt.%. In a preferred embodiment, the amount of sulfur in the base metal matte is about 10 wt.%.
  • the one or more sulfidising agent/s is/are added such that the amount of sulfur in the base metal matte is between about 5 and about 15 wt.%.
  • the one or more sulfidising agent/s is/are added such that the amount of sulfur in the base metal matte is about 10 wt.%.
  • a molar excess of sulfur is provided between about 0.1:1 and 25:1, preferably about 0.5:1, with the excess sulfur being relative to the stoichiometric Me® + S(i) MeS(i) reaction, where Me is the metal/s reporting to the matte phase.
  • the molar excess of elemental sulfur is about 0.11:1, 1.1:1, 2: 1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21: 1, 22:1, 23:1, 24:1, or 25:1.
  • the oxygen partial pressure within the pyrometallurgical furnace is between about 10' 11 5 and about 10' 6 atm.
  • the oxygen partial pressure within the pyrometallurgical furnace is between about 10' 105 and about 10' 7 atm.
  • the oxygen partial pressure within the pyrometallurgical furnace is about 10’ 13 , IO' 125 , IO’ 12 , 10' 11 5 , W 11 , IO' 105 , IO’ 10 , IO' 9 5 , IO’ 9 , 10' 8 5 , 10’ 8 , W 7 - 5 , IO’ 7 , IO’ 65 , IO’ 6 , IO’ 5 5 , 10’ 5 , IO’ 45 , or IO’ 4 atm.
  • the oxygen partial pressure within the pyrometallurgical furnace is between about 10' 12 to 10' 5 , 10 -11 to 10' 6 , 10' 105 to 10' 7 , 10' 10 to 10' 7 5 , 1 O' 9 5 to IO' 8 , or 10' 9 to 10' 8 5 atm.
  • the oxygen partial pressure within the pyrometallurgical furnace is about 10' 9 atm.
  • the further refining comprises converting the metal sulfides/s present in the base metal matte to their respective elemental metal or chemical products (e.g., nickel sulfate, nickel hydroxide) via conventional techniques.
  • metal sulfides/s present in the base metal matte to their respective elemental metal or chemical products (e.g., nickel sulfate, nickel hydroxide) via conventional techniques.
  • the pyrometallurgical furnace is further defined by a temperature greater than about 1000 °C.
  • the pyrometallurgical furnace is further defined by a temperature between about 1000 and about 1800 °C.
  • the pyrometallurgical furnace is further defined by a temperature greater than about 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650,1700, 1750 or 1800 °C.
  • the pyrometallurgical furnace is further defined by a temperature between about 1000 to 1800, 1100 to 1750, 1200 to 1700, 1250 to 1650, 1300 to 1600, 1350 to 1550, 1400 to 1500 or about 1450 °C.
  • step b), step c) and step d) are conducted in a single vessel.
  • step b) and step c) are conducted in a separate vessel to step d), optionally operatively connected to enable substantially continuous operation.
  • step d) is conducted in a settling furnace from which the slag can be separated from the base metal matte.
  • the method comprises employing a plurality of vessels arranged in series or parallel, preferably in series.
  • the method is adaptable and/or scalable to a continuous flow or batch-type scenario.
  • the inventive method is adaptable and/or scalable to a continuous flow or batch-type scenario.
  • the method is performed on a continuous or semi- continuous basis.
  • Semi-continuous operation may involve a batch-type process whereby each batch is run in a semi-continuous process. This could be achieved in a plurality of reactors each operating independently of the other or in fluid communication with each other.
  • the one or more valuable base metals comprises Li, Au, Ag, Al, Ca, Cr, Co, Cu, Fe, Ga, K, Mg, Mn, Na, Ni, and V.
  • the one or more valuable base metals comprises Li, Mn, Cu, Co, Au, Ag and Ni.
  • the one or more valuable base metals comprises Ni.
  • the one or more valuable base metals comprises Mn.
  • the one or more valuable base metals comprises Cu.
  • the one or more valuable base metals comprises Co.
  • the one or more valuable base metals comprises Au.
  • the one or more valuable base metals comprises Ag.
  • any one or more of the impurities reporting to the slag is present at a concentration between about 0.5% and about 40% of the valuable metals concentration on a molar basis.
  • the inventive method gives rise to a yield (on an extracted valuable metals basis) of between about 1% and about 99.99999%.
  • the inventive method gives rise to a yield (on an extracted valuable metals to end-of-life battery materials basis) of between about 1% and about 100%.
  • the yield is between about 10% and about 99.99%. More preferably, the yield is between about 25% and about 99%. More preferably, the yield is between about 50% and about 99%. More preferably, the yield is about 99%.
  • the pyrometallurgical furnace is further defined by an end- of-life battery materials feed concentration between about 0.1 and about 99% w/w.
  • the end-of-life battery material feed concentration equates to the weight/weight percentage of solids within the feed to pyrometallurgical furnace.
  • the end-of-life battery materials feed concentration is between about 0.1% w/w and about 99% w/w. As such, the claimed range includes 0.1, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20,
  • the end-of-life battery materials feed concentration is between about 0.1 and about 99.99% w/w. In another preferred embodiment, the end-of-life battery materials feed concentration is between about 40 and about 98% w/w. In another preferred embodiment, the predetermined end of life battery materials feed concentration is between about 50 and about 95% w/w. In another preferred embodiment, the predetermined solids concentration is between about 55 and about 94% w/w. In another preferred embodiment, the end-of-life battery materials feed concentration is between about 75 and about 90% w/w. In another preferred embodiment, the end-of-life battery materials feed concentration is about 80% w/w.
  • the end-of-life battery materials concentration is between about 0.1 and about 99.99% w/w. In another preferred embodiment, the end-of- life battery materials concentration is between about 10 and about 99% w/w. In another preferred embodiment, the end-of-life battery materials concentration is between about 50 and about 98% w/w. In another preferred embodiment, the end-of-life battery materials concentration is between about 60 and about 97% w/w. In another preferred embodiment, the end-of-life battery materials concentration is between about 65 and about 96% w/w.
  • the end-of-life battery materials concentration is between about 0.1 and about 99.9999% w/w. In another preferred embodiment, the end- of-life battery materials concentration is between about 1 and about 98% w/w. In another preferred embodiment, the end-of-life battery materials feed concentration is between about 5 and about 95% w/w. In another preferred embodiment, the end-of-life battery materials feed concentration is between about 60 and about 90% w/w. In another preferred embodiment, the end-of-life battery materials feed concentration is between about 70 and about 85% w/w.
  • the end-of-life battery materials is obtained by breaking or crushing the end-of-life battery waste to a predetermined average particle size.
  • the end-of-life battery materials have an average particle size between about 0.1 pm and about 1000
  • the end-of-life battery materials have an average particle size between about 25 nm and about 1000 mm (10 9 nm). In other embodiments, the end- of-life battery materials have an average particle size between about 25, 50, 75, 100, 10 3 , 10 4 , 10 5 , 10 6 , 10 7 , 10 8 or 10 9 nm.
  • the larger average particle sizes allow for, in some embodiments, whole (z.e., not crushed/shredded) batteries to be used in the method of the invention.
  • the end-of-life battery materials have an average particle size between about 500 nm and about 500 pm.
  • the end-of-life battery materials have an average particle size between about 2500 pm and about 100 pm.
  • the end-of-life battery materials have an average particle size of about 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500 or 10,000 nm (i.e., 10 pm).
  • the end-of-life battery materials have an average particle size of about 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 or about 500 pm.
  • the end-of-life battery materials have an average particle size between about 500 nm and about 500 pm. In a preferred embodiment, the end-of- life battery materials have an average particle size between about 2000 nm and about 450 pm. In a preferred embodiment, the end-of-life battery materials have an average particle size between about 4000 nm and about 400 pm. In a preferred embodiment, the end-of- life battery materials have an average particle size between about 6000 nm and about 350 pm. In a preferred embodiment, the end-of-life battery materials have an average particle size between about 8000 nm and about 300 pm. In a preferred embodiment, the end-of- life battery materials have an average particle size between about 10,000 nm and about 250 pm.
  • the end-of-life battery materials have an average particle size between about 12,000 nm and about 200 pm. In a preferred embodiment, the end-of-life battery materials have an average particle size between about 14,000 nm and about 150 pm. In a preferred embodiment, the end-of-life battery materials have an average particle size between about 16,000 nm and about 100 pm. In a preferred embodiment, the end-of-life battery materials have an average particle size between about 20,000 nm and about 90
  • the end-of-life battery materials have an average particle size between about 30 pm and about 70 pm. In a preferred embodiment, the end-of-life battery materials have an average particle size between about 35 pm and about 60 pm. [00115] The average particle size of the end-of-life battery materials is between about 500 nm and about 500 pm, more preferably, between about 40 pm and about 60 pm, and most preferably about 44 pm. This defined range is intended to encompass the stated endpoints and all average particle sizes therebetween.
  • the claimed range includes 0.5 pm (i.e., 500 nm), 1, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480 and 500 pm, including intermediary values such as 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 and 99 pm, etc.
  • intermediary values such as 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79,
  • the end-of-life battery materials is untreated (chemical, mechanical, physical such as heating or pyrolysis) prior to use.
  • the end-of-life battery materials is treated (chemical, mechanical and/or physical such as heating or pyrolysis) prior to use.
  • electrolytes from a battery are still present in the end-of- life battery materials.
  • electrolytes from a battery are not still present in the end-of-life battery materials.
  • the end-of-life battery materials may comprise one or more of a binder or electrolyte.
  • the electrolyte is lithium hexafluorophosphate (LiPFe).
  • the binder is selected from one or more of fluoroethylene carbonate (FEC), 1,3-propane sultone (PS), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), polyvinylidene fluoride (PVDF) or propylene carbonate (PC).
  • FEC fluoroethylene carbonate
  • PS 1,3-propane sultone
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • EC ethylene carbonate
  • PVDF polyvinylidene fluoride
  • PC propylene carbonate
  • the pyrometallurgical furnace comprises any suitable pyrometallurgical vessel or furnace.
  • the pyrolytic vessel or furnace is a bath or blast furnace.
  • the pyrolytic vessel or furnace is an ISASMELTTM furnace.
  • An ISASMELTTM furnace is an upright-cylindrical shaped steel vessel that is lined with refractory bricks. There is a molten bath of slag, matte or metal (depending on the application) at the bottom of the furnace.
  • a steel lance is lowered into the bath through a hole in the roof of the furnace, and air or oxygen-enriched air that is injected through the lance into the bath causes vigorous agitation of the bath.
  • Mineral concentrates or materials for recycling are dropped into the bath through another hole in the furnace roof or, in some cases, injected down the lance. These feed materials react with the oxygen in the injected gas, resulting in an intensive reaction in a small volume (relative to other smelting technologies).
  • ISASMELTTM lances contain one or more devices called “swirlers” that cause the injected gas to spin within the lance, forcing it against the lance wall, cooling it.
  • the swirler consists of curved vanes around a central pipe forming an annular flow. They are designed to minimise pressure losses by changing the angle from axial to tangential thus creating a strong vortex. The vortex helps mix liquids and solids with oxygen in the bath.
  • the cooling effect results in a layer of slag “freezing” on the outside of the lance. This layer of solid slag protects the lance from the high temperatures inside the furnace.
  • the tip of the lance that is submerged in the bath eventually wears out, and the worn lance is easily replaced with a new one when necessary. The worn tips are subsequently cut off and a new tip welded onto the lance body before it is returned to the furnace.
  • ISASMELTTM furnaces typically operate in the range of 1000-1500 °C, depending on the application.
  • the refractory bricks that form the internal lining of the furnace protect the steel shell from the heat inside the furnace.
  • the products are removed from the furnace through one or more “tap holes” in a process called “tapping”. This can be either continuous removal or in batches, with the tap holes being blocked with clay at the end of a tap, and then reopened by drilling or with a thermic lance when it is time for the next tap.
  • a slag notch or underflow weir can be used to continuously remove molten materials from the furnace.
  • the products are allowed to separate in a settling vessel, such as a rotary holding furnace or an electric furnace.
  • ISASMELTTM furnaces can use a variety of fuels, including coal, coke, petroleum coke, oil and natural gas.
  • the solid fuel can be added through the top of the furnace with the other feed materials, or it can be injected down the lance. Liquid and gaseous fuels are injected down the lance.
  • the one or more valuable metals is selected from the group consisting of: Li, Mn, Cu, Co, Au, Ag and Ni.
  • an apparatus for the extraction of one or more valuable base metal/s from end-of-life battery waste comprising:
  • a) means for subjecting the end-of-life battery waste to a pyrometallurgical furnace defined by a turbulent bath comprising:
  • one or more low temperature ( ⁇ 900 °C) sulfidising agent/s one or more low temperature ( ⁇ 900 °C) sulfidising agent/s
  • [00135] b) means for forming a base metal matte and a slag, the slag comprising less than about 5 wt.% base metal/s with the balance reporting to the matte;
  • the one or more valuable metals comprise Li, Mn, Cu, Co, Au, Ag and Ni.
  • the apparatus comprises a plurality of reactors arranged in fluid communication in series.
  • the apparatus comprises a plurality of reactors arranged in fluid communication in parallel.
  • the apparatus further comprises means for effecting an initial milling step, whereby the end-of-life battery materials is milled to a predetermined average particle size (as defined above) prior to being provided to step a).
  • the inventive apparatus further comprises filtration means, for filtering off any precipitated respective metal sulfate following extraction from the end-of-life battery waste.
  • the apparatus is used for performing a method as defined according to the first aspect of the present invention.
  • a metal sulfide when extracted within a matte by a method as defined according to the first aspect of the present invention is provided.
  • the metal sulfide comprises LiySx within the matte.
  • the metal sulfide comprises Mn y Sx within the matte.
  • the metal sulfide comprises Cu-S within the matte.
  • the metal sulfide comprises Co y Sx within the matte.
  • the metal sulfide comprises Au y Sx within the matte.
  • the metal sulfide comprises AgySx within the matte.
  • the metal sulfide comprises NiySx within the matte.
  • the metal sulfide comprises Fe y Sx within the matte.
  • the process parameters are as defined above in respect of the first and third aspects of the present invention.
  • step c the resultant metal sulfide/s are solidified from solution, or optionally upgraded or separated prior to such solidification.
  • the metal sulfide may be converted back to their respective elemental valuable metals via conventional techniques.
  • the slag is either discarded or subjected to a secondary recycling process, for instance, to recover valuable metals that are not recoverable via the inventive method.
  • the present invention relates to a method for the pyrometallurgical processing of lithium-ion batteries, mixed with a sulfidising agent, which may at least partially overcome the known disadvantages of past methods for high temperature lithium-ion battery treatment.
  • a processing method is presented in Figure 1.
  • the sulfidising agent that is currently used in industry is elemental sulfur, injected as a liquid into a molten alloy phase or a pre-reduced calcine. This is performed in nickel laterite smelting flowsheets. However, if element sulfur is added to a bath smelting furnace processing lithium-ion batteries, like an ISASMELTTM furnace, some of the sulfur may combust before it can react in the bath.
  • An alternative sulfidising agent is a molten matte from a primary base metal smelter. This is performed at some primary copper and primary nickel smelters, where black mass and other materials are added into the converting vessels. However, this requires a smelter to have a large quantity of base metal sulfide concentrates. This prevents the recovery of base metals from lithium-ion batteries in locations where these base metal sulfide concentrates are unable to be obtained.
  • An alternative sulfidising agent is pyrite (or a pyrite containing concentrate), which can be fed into the bath smelting furnace and react with the base metal alloy to form a matte.
  • pyrite or a pyrite containing concentrate
  • the slag chemistry will be modified, and the smelting process will become more challenging.
  • gypsum is not currently known to those processing lithium-ion batteries.
  • This sulfidising agent contains both sulfur (as a sulfate) and lime, both of which are required in the process to decrease the required smelting temperature.
  • the lime in the gypsum is used to flux the slag and the sulfur reacts to form a matte phase.
  • the sulfur in the gypsum will not burn as it enters the furnace and will be reduced once it has been digested in the bath.
  • pyrite or iron sulfide containing concentrates
  • the gypsum does not contain iron and will not impact the slag chemistry.
  • the recovery of sulfur to the matte will be much higher due to kinetic limitations and the avoidance of S2(g) generation (as an intermediate step).
  • the ISASMELTTM furnace injects oxygen-enriched air, and sometimes fuel, into a molten slag that smelts the incoming feed materials in a turbulent bath.
  • a person skilled in the art can select the correct ratio of oxygen-enriched air and fuel so that the oxygen potential of the furnace is maintained in the range of 10' 7 to 10" 11 atm.
  • the ratio of feed materials, sulfidising agents and fluxes added to the ISASMELTTM furnace must be carefully chosen to obtain a fluid slag and matte.
  • the matte phase can be sulfur deficient such that it contains between 1 and 22 wt.% sulfur, when it leaves that ISASMELTTM furnace.
  • the oxygen-enriched air injected through the ISASMELT lance, and feed materials charged to the furnace should be added in a ratio that will obtain partial combustion, such that many of the gaseous compounds are substantially oxidised but leaving some uncombusted FeS, ZnS, NiS, Cu 2 S, CoS, MnS, Fe, Ni, Cu, Zn, Co and Mn to form a molten matte in the bottom of the furnace.
  • a suitable atmosphere for partial combustion of the charge would be an oxygen partial pressure between 10' 13 and 10' 4 atm, more suitably it will be an oxygen partial pressure between 10" 11 and 10' 6 atm and more suitably still, it will be an oxygen partial pressure between 10' 105 and 10' 8 5 atm.
  • the resulting matte will then be suitable for addition to a base metal refinery for downstream processing.
  • the matte/alloy obtained had a mass of 243 kg and a nickel content of 47.8 wt.%, a copper content of 22.0 wt.%, a cobalt content of 10.6 wt.% and a sulfur content of 10.0 wt.%.
  • the 189 kg of S-containing slag contained only 0.2 wt.% Ni, 0.6 wt.% Cu and 0.5 wt.% Co.
  • the 218 kg of S-containing slag contained only 0.3 wt.% Ni, 0.4 wt.% Cu and 0.6 wt.% Co.
  • the matte/alloy obtained had a mass of 256 kg and a nickel content of 51.0 wt.%, a copper content of 23.3 wt.%, a cobalt content of 13.1 wt.% and a sulfur content of 9.9 wt.%.
  • the 228 kg of S-containing slag contained only 0.3 wt.% Ni, 0.7 wt.% Cu and 0.7 wt.% Co.
  • the matte/alloy obtained had a mass of 253 kg and a nickel content of 51.5 wt.%, a copper content of
  • the 235 kg of S-containing slag contained only 0.6 wt.% Ni, 0.5 wt.% Cu and 1.5 wt.% Co.
  • Table 3c Exemplary inputs used in, and outputs obtained from the inventive method [00170] As demonstrated above in respect of Table 3c, to an initial mass of 500 kg spent nickel-containing batteries was added 120 kg of gypsum and 20 kg silica.
  • the matte/alloy obtained had a mass of 257 kg and a nickel content of 50.9 wt.%, a copper content of 22.9 wt.%, a cobalt content of 13.3 wt.% and a sulfur content of 8.5 wt.%.
  • the 224 kg of S-containing slag contained only 0.3 wt.% Ni, 1.2 wt.% Cu and 0.4 wt.% Co.
  • the matte/alloy obtained had a mass of 257 kg and a nickel content of 51.1 wt.%, a copper content of 23.2 wt.%, a cobalt content of 13.4 wt.% and a sulfur content of 7.2 wt.%.
  • the 210 kg of S-containing slag contained only 0.2 wt.% Ni, 0.9 wt.% Cu and 0.2 wt.% Co. Table 5.
  • the matte/alloy obtained had a mass of 254 kg and a nickel content of 44.7 wt.%, a copper content of 23.7 wt.%, a cobalt content of 20.1 wt.% and a sulfur content of 8.3 wt.%.
  • the 216 kg of S-containing slag contained only 0.2 wt.% Ni, 0.6 wt.% Cu and 0.7 wt.% Co.
  • the matte/alloy obtained had a mass of 256 kg and a nickel content of 55.8 wt.%, a copper content of 23.6 wt.%, a cobalt content of 8.9 wt.% and a sulfur content of 8.5 wt.%.
  • the 214 kg of S-containing slag contained only 0.2 wt.% Ni, 0.5 wt.% Cu and 0.3 wt.% Co.
  • the matte/alloy obtained had a mass of 253 kg and a nickel content of 39.6 wt.%, a copper content of 35.8 wt.%, a cobalt content of 13.3 wt.% and a sulfur content of 8.3 wt.%.
  • the 217 kg of S-containing slag contained only 0.2 wt.% Ni, 0.8 wt.% Cu and 0.6 wt.% Co.
  • the matte/alloy obtained had a mass of 256 kg and a nickel content of 59.1 wt.%, a copper content of 15.7 wt.%, a cobalt content of 13.3 wt.% and a sulfur content of 8.4 wt.%.
  • the 214 kg of S-containing slag contained only 0.2 wt.% Ni, 0.4 wt.% Cu and 0.4 wt.% Co.
  • the matte/alloy obtained had a mass of 249 kg and a nickel content of 49.1 wt.%, a copper content of 24.2 wt.%, a cobalt content of 13.6 wt.% and a sulfur content of 8.5 wt.%.
  • the 223 kg of S-containing slag contained only 0.2 wt.% Ni, 0.6 wt.% Cu and 0.5 wt.% Co.
  • the methodology further demonstrates the efficacy of modified pyrometallurgical conditions employing a furnace for other valuable metal recycling from end-of-life battery materials.
  • metals preferably include Mn, Ni, Co and/or Li.
  • the present invention provides for an environmentally friendly approach to what has traditionally been a somewhat damaging and wasteful pursuit.

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Abstract

La présente invention concerne un procédé d'extraction d'un ou plusieurs métaux de base de valeur à partir de déchets de batteries en fin de vie, le procédé comprenant les étapes consistant à : obtenir les déchets de batteries en fin de vie ayant une teneur en ledit ou lesdits métaux de valeur ; soumettre la masse noire à un four pyrométallurgique défini par un bain turbulent comprenant : un ou plusieurs agents de sulfuration ; un ou plusieurs flux ; un ou plusieurs combustibles ; ce qui permet d'obtenir une pression partielle d'oxygène comprise entre environ 10-13 et environ 10-4 atm ; former une matte métallique de base et un laitier, le laitier comprenant moins d'environ 5 % en poids de métal/métaux de base ; séparer la matte et le laitier ; et raffiner encore la matte métallique de base, ce qui permet d'obtenir le ou les métaux de base de valeur.
PCT/AU2023/051308 2023-07-11 2023-12-15 Recyclage pyrométallurgique de batteries en fin de vie Pending WO2025010462A1 (fr)

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AU2023902216 2023-07-11
AU2023902216A AU2023902216A0 (en) 2023-07-11 A method for the pyrometallurgical recycling of end-of-life batteries
AU2023903803A AU2023903803A0 (en) 2023-11-27 Pyrometallurgical recycling of end-of-life batteries
AU2023903803 2023-11-27

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169206B2 (en) * 2004-04-19 2007-01-30 Umicore Battery recycling
EP2677048A1 (fr) * 2011-02-18 2013-12-25 Sumitomo Metal Mining Co., Ltd. Procédé de récupération de métal de valeur
WO2023004476A1 (fr) * 2021-07-29 2023-02-02 Glencore Technology Pty Limited Traitement de résidus de lixiviation de zinc

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169206B2 (en) * 2004-04-19 2007-01-30 Umicore Battery recycling
EP2677048A1 (fr) * 2011-02-18 2013-12-25 Sumitomo Metal Mining Co., Ltd. Procédé de récupération de métal de valeur
WO2023004476A1 (fr) * 2021-07-29 2023-02-02 Glencore Technology Pty Limited Traitement de résidus de lixiviation de zinc

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