AU2023350690B2

AU2023350690B2 - Recycling of electronic waste to recover lithium

Info

Publication number: AU2023350690B2
Application number: AU2023350690A
Authority: AU
Inventors: Neil Michael Edwin Ireland; Gary Donald Johnson; Mark Daniel Urbani; Nicholas John VINES
Original assignee: Renewable Metals Pty Ltd
Current assignee: Renewable Metals Pty Ltd
Priority date: 2022-09-27
Filing date: 2023-08-16
Publication date: 2025-09-25
Anticipated expiration: 2043-08-16
Also published as: JP2025532429A; KR20250077556A; AU2023350690A1; EP4594542A1; WO2024064995A1; CA3268878A1; CN119968471A; TW202425395A

Abstract

Disclosed herein is a method for recovering metals from electronic waste or a leach residue thereof, the electronic waste or leach residue comprising elemental copper and one or more lithium compounds, the method comprising: leaching the electronic waste or leach residue with a leach solution comprising ammonium sulphate in the presence of an oxidant to provide a leachate comprising Cu ions and Li ions and a solid residue; and separating the leachate and the solid residue.

Description

RECYCLING OF ELECTRONIC WASTE TO RECOVER LITHIUM

Field

[0001] The invention generally relates to methods for recovering lithium and optionally other

transition metals from waste electronic material that comprises at least copper and one or more

lithium salts, and in particular, where the waste electronic material is waste lithium-ion batteries.

Background

[0002] The volume of waste electronics, and in particular, rechargeable Li-ion batteries used

worldwide has been growing rapidly in recent years and is set for further expansion with the

emerging markets of electric vehicles and mass electric power storage. As the demand for

electronic devices, and in particular those using Li-ion batteries increases, SO so does the demand

for the metal/metal oxide components that are used in these devices. The rapid increase in

demand for some of these metals, such as cobalt, has put pressure on the sustainable supply of

such resources. This has caused the cost of such metals to rapidly increase.

[0003] There has been little interest in developing processes for the recovery and recycling of

the various components in modern electronic devices and components thereof such as batteries.

In the case of batteries, this is mainly due to the relatively low volume of Li-ion batteries

available for recycling and the relatively high cost of the typical pyrometallurgical and

hydrometallurgical processes by which the recovery is achieved. As the demand for Li-ion

batteries continues to increase, SO so too does the volume of spent Li-ion batteries that are available

for recycling. There is a need for low-cost, efficient recycling processes, particularly in respect

of the more complex metal/metal oxide components. Whilst the discussion below is primarily in

respect of Li-ion batteries, it is applicable to a range of electronic devices since these likewise

incorporate a range of different metal compounds.

[0004] The composition of Li-ion batteries has evolved considerably over recent times. Whilst

some battery recycling processes have been developed, these have primarily been limited to the

recovery of certain specific metals from a certain specific type of battery or feed source. For

example, early batteries were predominantly lithium-cobalt and the focus of the recovery

methods was on recovering cobalt. As lithium demand increased, the recovery methods shifted

to the recovery of both cobalt and lithium. As battery technologies underwent further

2

developments,the thecathodes cathodesincorporated incorporatedother othermetals, metals,such suchasasmanganese, manganese, nickel, 05 Aug 2025 2023350690 05 Aug 2025

developments, nickel,

aluminium, ironand aluminium, iron andphosphorus. phosphorus.The The methods methods usedused to recover to recover lithium lithium andand cobalt cobalt areare notnot

suited for the suited for therecovery recoveryof of other other metals, metals, nor they nor are are they well suited well suited for different for different battery battery

chemistries. chemistries.

[0005] The

[0005] The uptake uptake in the in the usage usage of Li-ion of Li-ion batteries batteries will increase will increase theofvolume the volume of spent Li-ion spent Li-ion

batteries available for recycling. However, the supply of spent Li-ion batteries will include batteries available for recycling. However, the supply of spent Li-ion batteries will include 2023350690

many different types of batteries. The suitability of recovery methods to only a single battery many different types of batteries. The suitability of recovery methods to only a single battery

type presents a significant problem to the commercialisation of such processes. Specifically, type presents a significant problem to the commercialisation of such processes. Specifically,

such methods such methods require require onemore one or or sorting more sorting steps steps and and pre-processing pre-processing steps. steps. Given this, Given this, there is there is

aa need for the need for the development of aa process development of process for for the the recovery recovery of of aa range range of of metals metals from from a a range range of of

different Li-ionbattery different Li-ion batterytypes. types.

[0006] Mostdevelopments

[0006] Most developmentsin in batteryrecycling battery recyclingprocessing processinginvolve involve dissolutionofofthe dissolution themetal metal components components ininacidic acidicmedia. media.This Thisisis aa non-selective non-selective leaching leaching process process during during which whichmost most metals contained in a battery are dissolved. Batteries contain various non-valuable metals, metals contained in a battery are dissolved. Batteries contain various non-valuable metals,

such as iron, such as iron, manganese andaluminum, manganese and aluminum,at at anan appreciable appreciable amount. amount. Some Some batteries batteries may may also also

include include phosphorous. Acidconsumption phosphorous. Acid consumptionis is high high if ifthese thesenon-valuable non-valuablemetals metals and and phosphorous phosphorous

are are not not removed prior to removed prior to leaching. leaching. Consequently, pretreatmentprocesses Consequently, pretreatment processesare arerequired required to to separate separate iron, iron, aluminum fromvaluable aluminum from valuablemetal metalcomponents components suchsuch as cobalt, as cobalt, nickel, nickel, copper copper andand

lithium. Insosodoing, lithium. In doing,thethe recovery recovery of these of these valuable valuable metalsmetals diminishes diminishes as the separations as the separations

achieved in these achieved in these pretreatment processes are pretreatment processes are not not 100% efficient. 100% efficient.

[0007]

[0007] ItItis is desirable desirabletotoprovide provide a method a method forrecovery for the the recovery of metals, of metals, and in particular and in particular lithium, lithium,

from waste from waste electronic electronic devices devices such such as batteries as batteries of a range of a broad broadofrange of chemistries. chemistries.

[0008]

[0008] ItIt is is an anobject objectofofthe theinvention invention to address to address one one or or shortcoming more more shortcoming of art of the prior the prior art and/or provide and/or provide a useful a useful alternative. alternative.

Summary Summary ofofInvention Invention

[0008a] In one

[0008a] In aspect of one aspect of the the invention invention there there is isprovided providedaamethod method for for recovering recovering metals metals from from

electronic waste or a leach residue thereof, the electronic waste or leach residue comprising electronic waste or a leach residue thereof, the electronic waste or leach residue comprising

elemental copper elemental copperand andone oneorormore morelithium lithiumcompounds, compounds, the the method method comprising comprising leaching leaching the the

2a 2a

electronic waste waste or or leach leach residue residue with with aaleach leachsolution solutioncomprising comprising ammonium sulphate in in the 05 Aug 2025 2023350690 05 Aug 2025

electronic ammonium sulphate the

presence of an presence of an oxidant oxidant to to provide provide a a leachate leachate comprising Cuions comprising Cu ionsand andLiLiions ionsand andaasolid solid residue; separating the leachate and the solid residue; recovering Cu ions from the leachate; residue; separating the leachate and the solid residue; recovering Cu ions from the leachate;

and afterthe and after thestep stepofofrecovering recovering Cu ions Cu ions from from the leachate, the leachate, the further the method methodcomprises further comprises recovering Li ions from the leachate. recovering Li ions from the leachate.

[0009] Disclosedherein

[0009] Disclosed herein is is aa method for recovering method for recoveringmetals metalsfrom fromelectronic electronicwaste wasteororaa leach leach 2023350690

residue residue thereof, thereof, the theelectronic electronicwaste wasteororleach leachresidue comprising residue comprisingelemental elemental copper copper and and one or one or

morelithium more lithiumcompounds, compounds,thethe method method comprising: comprising:

leaching theelectronic leaching the electronic waste waste or leach or leach residue residue with awith leacha solution leach solution comprising comprising

ammonium sulphate ammonium sulphate in in thethe presence presence of of an an oxidant oxidant to to provide provide a leachatecomprising a leachate comprising Cu Cu ionsions

and and

Li ions and a solid residue; and

separating the leachate and the solid residue.

[0010] By elemental copper it is meant copper metal.

[0011] In an embodiment, the electronic waste comprises, consists of, or consists essentially of

one or more types of lithium ion batteries, preferably in the form of lithium ion battery shreds.

In alternative embodiments, the electronic waste comprises a mixture of one or more types of

lithium ion batteries and other electronic waste, such as printed circuit boards and the like.

[0012] In an embodiment, the one or more lithium compounds comprise lithium metal oxides

and/or lithium metal phosphates, such as in the form of LiMO2, LiMPO4,where LiMO, LiMPO4, whereMMis isaaone oneor or

more metals selected from the group consisting of Al, Co, Mn, and/or Ni. In a preferred form,

the the one one orormore morelithium metal lithium compounds metal comprises compounds LiNiwCoxAlyMnzO2 comprises whereinwherein LiNiwCoxAlyMnO w+x+y+z=1, w+x+y+z=1,

and/or LiNixMnyC01-x-yO2 where LiNiMnyCo-x-yO where 0 x+y <1, and/or and/or LiNiCoyAlO2 LiNixCoyAlO where where x+y+z=1, x+y+z=1, and/or and/or

LiFePO4.

[0013] In an embodiment, the Cu ions and the Li ions are in the form of CuSO4 and Li2SO4

respectively.

[0014] In an embodiment, the elemental copper is present in an amount sufficient to provide an

oxidation reduction potential of -100 mV or less as determined using an Ag/AgCl reference

electrode. Preferably, the oxidation reduction potential is - -150 -150 mVmV oror less. less. The The inventors inventors have have

found that an oxidation reduction potential of - -100mV or less is useful for ensuring

solubilisation of Li ions and reduction of transition metals in the electronic waste. In particular,

the inventors have found that an oxidation reduction potential of -100 mV or less is important

for forming soluble Mn ions. If the oxidation reduction potential is greater than - 100 -100mV, mV,Mn Mn

increasingly reports to the solid residue.

[0015] In an embodiment, the oxidant is present in an amount sufficient to provide an oxidation-

reduction potential of +50 mV or more as determined using an Ag/AgCl reference electrode.

Preferably, the oxidation reduction potential is +100 mV or more, and more preferably +150 mV

or more.

[0016] In an embodiment the elemental copper is present in an amount of at least 4 wt% with

respect to the total weight of the electronic waste. Preferably, elemental copper is present in an

amount of at least 5 wt%. More preferably, elemental copper is present in an amount of at least

6 wt%. Even more preferably, elemental copper is present in an amount of at least 7 wt%. Most

preferably, elemental copper is present in an amount of at least 8 wt%.

[0017] In an embodiment, the oxidant comprises, consists of, or consists essentially of a solid

oxidant. More preferably, the oxidant is in the form of a metal oxide present in the electronic

waste, and in particular an oxide of Co, Mn, or Ni. In some embodiments, the oxidant is a

component of the one or more lithium compounds, such as a Co, Mn, and/or Ni component of

the lithium metal oxides.

[0018] The inventors have found that the leaching step mediates oxidation reduction reactions

between the elemental copper and Co, Mn, and Ni salts which advantageously results in the

formation of soluble salts of Co, Cu, Mn and Ni ions.

[0019] In embodiments in which Ni is present, it is preferred that the Cu:Ni ratio is 0.5:1 or

greater, such as up to about 2:1.

[0020] In embodiments in which Co is present, it is preferred that the Cu:Co ratio is 0.5:1 or

greater, such as up to about 2:1.

[0021] In embodiments in which Mn is present, it is preferred that the Cu:Co ratio is 0.5:1 or

greater, such as up to about 2:1.

[0022] In embodiments in which both Ni and/or Co and/or Mn are present, it is preferred that

the Cu:(Ni+Co+Mn) ratio is 0.5:1 or greater, such as such as up to about 2:1.

[0023] In an embodiment, the temperature is from about 0 °C and up to a temperature at or less

than the boiling point of the leach solution at operating conditions of the leach, for example less

than 100 °C. Preferably, the temperature is from about 40 °C. Preferably the temperature is up to

about 60 °C.

[0024] In an embodiment, the leach is conducted at atmospheric pressure.

[0025] In an embodiment, the leach is conducted for up to 24 hours. Preferably, the leach is

conducted for up to 18 hours. More preferably, the leach is conducted for up to 12 hours. Most

preferably, the leach is conducted for up to 8 hours. Additionally or alternative, the leach is

conducted for at least 0.5 hours. Preferably the leach is conducted for at least 1 hour. More

preferably, the leach is conducted for at least 1.5 hours. Most preferably, the leach is conducted

for at least 2 hours.

[0026] In an embodiment, the method further comprises recovering Cu ions from the leachate.

Preferably, the Cu ions are recovered using a solvent extraction process, the solvent extraction

process comprising contacting the leachate with an extractant to adsorb Cu ions into the

extractant to form a Cu-loaded extractant, and separating the Cu-loaded extractant from the

leachate. More preferably, the method further comprises stripping the Cu ions from the Cu-

loaded extractant using a stripping agent, such as sulfuric acid.

[0027] In one form of the above embodiment, after the step of recovering Cu ions from the

leachate, the method further comprises:

crystallising ammonium lithium sulfate from the leachate, and

thermally decomposing the crystallised ammonium lithium sulfate to form a gas

comprising ammonia and sulfur oxides, and solid lithium sulfate.

[0028] Preferably, prior to the step of crystallising ammonium lithium sulfate, the leachate is

treated such that the leachate is an ammonia-, Cu-, Ni-, Co-, Mn-lean leachate and/or the

leachate comprises substantially no ammonia, Al, Cu, Fe, Ni, Co, or Mn.

[0029] Preferably, prior to the step of crystallising ammonium lithium sulfate, the leachate

comprises ammonia-, Cu-, Ni-, Co-, Mn each at a concentration of 100 mg/L or less. Preferably,

each at a concentration of 80 mg/L or less. Most preferably, each at a concentration of 60 mg/L

or less.

[0030] In an embodiment, the electronic waste further comprises one or more transition metal

salts, and more preferably transition metal oxides. In such cases, it is further preferred that the

oxidant is the one or more transition metal salts or oxides, and the leachate comprises ions of the

one or more transition metals.

[0031] In one form of the above embodiment, the one or more transition metal salts are a

component of the lithium metal oxides and/or lithium metal phosphates.

[0032] In one form of the above embodiment, the one or more transition metals are selected

from the group consisting of: Co, Mn, and/or Ni.

[0033] In the case where the electronic waste further comprises one or more transition metal

salts, it is further preferred that the leach is an alkaline leach, and the leach solution comprises

ammonia in sufficient amount to provide a pH of from about 8.5 to about 10.5. More preferably,

the leach solution further comprises ammonium chloride. Preferably, the ammonium chloride is

present at a concentration of at least 1 g/L.

[0034] In an embodiment, the leach is an alkaline leach.

[0035] In one form of the above embodiment, the leach solution further comprises ammonia

and/or ammonium chloride. Preferably, the ammonia is present in an amount sufficient that the

pH of the leach solution is from about 8.5 up to about 10.5. Preferably, the ammonium chloride

is present at a concentration of at least 1 g/L.

[0036] In an embodiment, the electronic waste further comprises one or more Ni salts,

preferably in the form of oxides of Ni, and the leach solution further comprises ammonia in an

amount that the pH of the leach solution is from about 8.5 to about 10.5, and wherein the

leachate comprises at least Cu, Li, and Ni ions. Preferably, the pH is from about 9. More

preferably, the pH is up to about 10.

[0037] In one form of the above embodiment, the leach solution comprises ammonia and

ammonium sulfate in a ratio of from about 1:2 to about 1:20.

[0038] In one form of the above embodiment, a ratio of Cu:Ni is from about 2:1 to about 0.5:1.

[0039] In one form of the above embodiment, the method further comprises contemporaneously

recovering Cu and Ni from the leachate via a solvent extraction process. Preferably, the solvent

extraction process comprising contacting the leachate with an extractant to adsorb Cu and Ni

ions into the extractant to form a Cu,Ni-loaded extractant, and separating the Cu,Ni-loaded

extractant from the leachate. More preferably, the method further comprises stripping the Cu and Ni ions from the Cu,Ni-loaded extractant using a stripping agent, such as sulfuric acid, wherein Ni ions are selectively recovered at a first stripping agent concentration and Cu ions are subsequently recovered at a second stripping agent concentration, the first stripping agent concentration being less than the second stripping agent concentration.

[0040] In an embodiment, the electronic waste further comprises Co, and the leach solution

further comprises ammonia in an amount that the pH of the leach solution is from about 8.5 to

about 10.5, and wherein the leachate comprises at least Cu, Li, and Co ions.

[0041] In one form of the above embodiment, a ratio of Cu:Co is from about 2:1 to about 0.5:1.

[0042] In one form of the above embodiment, the method further comprises recovering Cu ions

from the leachate, and after removal of Cu ions, precipitating Co from the leachate.

[0043] Preferably, the step of precipitating Co from the leachate comprises precipitating cobalt

sulfide from the leachate. In embodiments in which Ni and/or Mn is present in the electronic

waste, the step of precipitating Co from the leachate occurs subsequent to recovery of Mn and/or

Ni. That is, it is preferred that prior to the step of precipitating Co, the leachate is substantially

free of Cu, Mn, and Ni. By way of example, the leachate comprises Cu and/or Mn and/or Ni

each at a concentration of 100 mg/L or less. More preferably, each at a concentration of 80 mg/L

or less. Most preferably, each at a concentration of 60 mg/L or less. This is to minimize the co-

precipitation of sulfides of Cu, Mn, and Ni and thus provide cobalt product of higher purity.

[0044] In an embodiment, the electronic waste further comprises Mn, and the leach solution

further comprises leachate comprises Mn, and the method further comprises:

treating the leachate with an oxidant to form a precipitate of Mn and provide an Mn-lean

leachate comprising Cu ions and Li ions; and

separating the precipitate of Mn from the Mn-lean leachate.

[0045] In one form of the above embodiment, the oxidant is air.

[0046] In one form of the above embodiment, a ratio of Cu:Mn is from about 2:1 to about 0.5:1.

[0047] In an embodiment, the electronic waste further comprises Fe and Al, the solid residue

comprises Fe and Al, and the leachate is an Fe-, Al-lean leachate and/or the leachate comprises

substantially no Fe or Al.

[0048] In an embodiment, the leachate comprises Fe and Al each at a concentration of 100 mg/L

or less. More preferably, each at a concentration of 80 mg/L or less. Most preferably, each at a

concentration of 60 mg/L or less.

[0049] In an embodiment, the electronic waste comprises elemental copper, and one or more

compounds of Co, Li, and Ni, and wherein the leach solution further comprises ammonia, and

the leachate comprises Co ions, Cu ions, Li ions, and Ni ions; and after the step of separating the

leachate from the solid residue, the method further comprises:

subjecting the leachate to a solvent extraction step to remove Cu ions and Ni ions from

the leachate and form a Cu-,Ni-lean leachate;

subjecting the Cu-,Ni-lean leachate to a precipitation step to remove Co ions from the

Cu-,Ni-lean leachate and form a Co-,Cu-,Ni-lean leachate; and

recovering Li from the Co-,Cu-,Ni-lean leachate,

wherein prior to the step of recovering Li, the leachate is subjected to an ammonia

recovery step such that during the recovery of Li, the Co-,Cu-,Ni-lean leachate is substantially

free of ammonia.

[0050] In one form of the above embodiment, the Co ions comprise Co2+ ions, and Co² ions, and prior prior to to the the

step of subjecting the leachate to the solvent extraction step, the method further comprises

Co² ions treating the leachate with an oxidant to oxidise the Co2+ ions to to Co³ ions. Co3+ ions.

[0051] In an embodiment, the electronic waste comprises elemental copper, and one or more

compounds of Co, Li, Mn, and Ni, and wherein the leach solution further comprises ammonia,

and the leachate comprises Co ions, Cu ions, Li ions, Mn ions, and Ni ions; and after the step of

separating the leachate from the solid residue, the method further comprises:

treating the leachate with an oxidant to form a precipitate of Mn and to provide an Mn-

lean lean leachate leachatecomprising Co ions comprising in the Co ions inform the of Co3+ofions, form Co³ Cu ions,CuLiions, ions, ions, Li and ions, Ni ions; andand Ni ions; and

separating the precipitate of Mn from the Mn-lean leachate;

subjecting the Mn-lean leachate to a solvent extraction step to remove Cu ions and Ni

ions from the Mn-lean leachate and form a Cu-,Mn-,Ni-lean leachate; subjecting the Cu-,Mn-,Ni-lean leachate to a precipitation step to remove Co ions from the Cu-,Mn-,Ni-lean leachate and form a Co-,Cu-,Mn-,Ni-lean leachate; and recovering Li from the Co-,Cu-,Mn-,Ni-lean leachate; Co-,Cu,Mn-,Ni-lean leachate; wherein prior to the step of recovering Li, the leachate is subjected to an ammonia recovery step such that during the recovery of Li, the Co-,Cu-,Ni-lean leachate is substantially free of ammonia.

[0052] In an embodiment, the leach solution further comprises ammonia, the leachate is a first

leachate, and the solid residue is a first solid residue, and after the step of separating the first

leachate from the first solid residue the method further comprises:

leaching the solid residue with a second leach solution comprising ammonium sulfate to

provide a second leachate and a second solid residue; and

separating the second leachate and the second solid residue;

leaching the second solid residue with an acid to provide a third leachate and a third

solid residue;

separating the third leachate and the third solid residue; and

combining the first leachate, the second leachate, and the third leachate to form a

combined leachate.

[0053] In one form of the above embodiment, the electronic waste comprises elemental copper,

and one or more compounds of Co, Li, Mn, and Ni, and the method comprises recovering one or

more of Co, Cu, Li, Mn, and Ni from the combined leachate.

[0054] In an embodiment, the leach solution is substantially free of acid, and/or comprises no

added acid species. In some instances, the natural pH of the leach solution during the leach is

less than 7. In such instances, this is due to acid species that are evolved during the leach

process. Thus, in preferred forms of the invention, any acids present in the leach solution are

generated during the leach from the electronic waste.

[0055] In an embodiment, the leach solution is substantially free of organic compounds. By way

of example, the leach solution comprises no monomers, oligomers, polymers, surfactants,

organic lixiviants, organic acids, organometallic compounds and the like.

[0056] In an embodiment, the leach solution is substantially free of biological material. By way

of example, the leach solution comprises no vegetable, fruit, or animal biomatter.

[0057] In an embodiment, the method comprises: subjecting electronic waste to a first leach

with a first leach solution to provide a first leachate and the solid residue, and leaching the leach

residue with the leach solution comprising ammonium sulphate in the presence of the oxidant to

provide the leachate comprising Cu ions and Li ions and the solid residue.

[0058] The skilled person will appreciate that there may be additional leaching steps between

the first leach and the step of leaching the leach residue. For example, there may be a second

leach with a second leach solution which results in a second leachate and a second leach residue,

and the step of leaching the leach residue is one of leaching the second leach residue.

[0059] The first leach (and, in various embodiments the second leach) may be, for example, an

acid leach, an alkaline leach and the like. However, it is preferred that the first and/or second

leach solution comprises one or more of ammonia, ammonium sulfate, and ammonium chloride.

In embodiments thereof, the first and/or second leach solution comprises, consists of, or consists

essentially of a solution of (i) ammonia and ammonium chloride, (ii) ammonia and ammonium

sulfate, (iii) ammonium sulfate and ammonium chloride, and (iv) ammonia, ammonium

chloride, and ammonium sulfate. In embodiments, the leachate is combined with the first

leachate (and second leachate in embodiments which include a second leaching step) to form a

combined leachate from which Cu and Li can be recovered, along with Co, Mn, and Ni if

present according to the methods generally described above.

[0060] Reference to any prior art in the specification is not an acknowledgment or suggestion

that this prior art forms part of the common general knowledge in any jurisdiction or that this

prior art could reasonably be expected to be understood, regarded as relevant, and/or combined

with other pieces of prior art by a skilled person in the art.

[0061] As used herein, except where the context requires otherwise, the term "comprise" and

variations of the term, such as "comprising", "comprises" and "comprised", are not intended to

exclude further additives, components, integers or steps.

Brief Description of Drawings

[0062] Further aspects of the present invention and further embodiments of the aspects

described in the preceding paragraphs will become apparent from the following description,

given by way of example and with reference to the accompanying drawings.

[0063] Figure 1 is a process flow diagram illustrating the method of the invention in accordance

with one embodiment thereof.

[0064] Figure 2 is a process flow diagram illustrating the method of the invention in accordance

with another embodiment thereof.

Description of Embodiments

[0065] The invention broadly relates to a method for recovering valuable metals, and in

particular lithium, from electronic waste that comprises elemental copper and one or more

lithium containing salts.

[0066] The method comprises leaching the electronic waste with ammonium sulfate during

which the elemental copper is oxidized to copper ions thus providing a source of electrons to act

as a reductant and thereby produce soluble lithium ions from the lithium containing salts. If

transition metals such as cobalt, manganese, and nickel are present in the electronic waste, e.g.,

as a component of the lithium containing salts, or as a metal oxide and the like, these are

likewise reduced to soluble ions. The various soluble metals ions, and in particular, lithium can

be selectively recovered as products. The ammonium sulfate can likewise be recovered and

reused for further leaching.

[0067] The method is particularly applicable to the recovery of lithium from waste lithium-ion

batteries, and in particular battery shreds (whether of a single type of battery or a blend of

battery shreds from different lithium-ion batteries). The method can advantageously be applied

to raw battery shreds, that is, battery shreds (as opposed to black mass) that have not undergone

prior treatment process such as copper stripping and/or calcination. By way of non-limiting

example, the method may be applied to extract ions of Co, Cu, Li, Mn, and Ni depending on the

chemistry of the battery or blend of batteries in the battery shreds.

[0068] In preferred forms of the invention, the electronic waste comprises lithium-ion batteries

that include lithium metal oxides or lithium metal phosphates, a non-limiting disclosure of

which includes nickel manganese cobalt (NMC), lithium cobalt oxide (LCO), and lithium-ion

manganese oxide (LMO), lithium iron phosphate (LFP) and lithium nickel cobalt aluminium

oxide (NCA) batteries, and mixtures thereof. Generally, in these batteries, the lithium is present

in the form of one or more lithium salts of the form LiMO2, LiMPO4, where LiMO, LiMPO4, where MM is is aa transition transition metal, metal, and/or and/orLiNi.CoyAlO2 LiNixCoyAlOwhere x+y+z=1. where The electronic x+y+z=1. waste may The electronic further waste comprise comprise may further other electronic waste such as printed circuit boards and the like.

[0069] Without wishing to be bound by theory, the inventors are of the view that the ammonium

sulfate leach mediates a copper oxidation-reduction which ultimately provides a source of

electrons and soluble copper salts and, in doing so, reduces lithium metal salts (such as those

described above) to liberate Li ions into solution and optionally ions of Cu, Co, Mn, and Ni

depending on the chemistry of the Li-ion batteries in the battery shreds. The leach is selective in

that low value metals such as iron and aluminium that may be present in the electronic waste are

substantially retained in the solid residue, along with low value phosphate compounds.

[0070] In more detail, during the ammonium sulphate leach, copper metal is oxidized to Cu(I).

The Cu(I) in turn is oxidised to Cu(II) via an oxidation-reduction reaction with lithium metal

salts or other transition metal salts resulting in the formation of soluble ions of Li and/or of Co,

Mn, and Ni (if these are present). In the absence of a source of copper metal to act as a reductant

or a balance of lithium metal salts and/or other transition metal salts to act as an oxidant to

convert Cu(I) to Cu(II), the oxidation-reduction reaction would cease. Generally, the method

provides sufficient oxidant (in the form of lithium metal salts and/or other transition metal salts)

and sufficient copper to enable the reaction to carry through to completion. If insufficient

oxidant in the form of lithium metal salts and/or other transition metal salts is present, additional

oxidant may be added, for example air, hydrogen peroxide, hypochlorite and the like.

[0071] The inventors have also found that introducing ammonium chloride during the leach or

including it as a component of the leach solution is useful since this improves the stability of the

Cu(I) ions in solution which in turn results in a more effective and efficient leach.

[0072] The resultant leachate generally comprises at least Cu and Li ions, and may additionally

comprise Co, Mn, and Ni ions depending on the composition of the electronic waste. When

present, the Co, Mn, and Ni ions may be selectively recovered according to methods described

herein.

[0073] In the case where the leachate comprises Cu and Li ions, the Cu ions may be recovered

via a solvent extraction process. That is, the leachate is contacted with an extractant to recover

Cu ions from the leachate and form a Cu-loaded extractant. The extractant can then be stripped

with a stripping agent, such as sulfuric acid, to recover Cu such as in the form of CuSO4 (aq).

[0074] The leachate, being substantially free of Cu can then be treated to recover ammonium

sulphate and Li. The inventors have found that ammonium lithium sulfate can be crystallised

from the leachate, e.g., by concentrating the leachate, such as by evaporating water from the

leachate, to crystallise ammonium lithium sulfate. The ammonium lithium sulfate can then be

recovered by a solid-liquid separation process (e.g., filtration, centrifugation, and the like) and

then thermally decomposed to lithium sulfate crystals, ammonia gas, and sulfur trioxide gas.

The sulfur trioxide gas can be reacted with the ammonia gas and water to regenerate ammonium

sulfate.

[0075] If other transition metal ions, such as ions of Co, Mn, and Ni are present in the leachate,

then these can be selectively recovered prior to the recovery of lithium. In embodiments in

which Co, Mn, and Ni are present, it is preferred that Mn is recovered from the leachate prior to

recovery of Cu and Ni and then recovery of Co.

[0076] In embodiments in which Mn is present, Mn ions can be recovered via oxidation of Mn

to manganese oxides such as Mn2O3, Mn3O4 MnO, Mn3O4 and/or and/or MnO2 MnO (but (but notnot MnO) MnO) a suitable a suitable oxidant oxidant is is

air. If Co(II) ions are present during the oxidation process, then these will be oxidised to Co(III)

ions. To prevent precipitation of CoO, in addition to the oxidation of Co(II) ions to Co(III) ions,

the Mn recovery step is preferably carried out in the presence of ammonia since, as discussed

above, ammonia forms stable soluble sulphate complexes with Co ions, and thus mitigates

against the precipitation of CoO during the oxidation treatment step. Co ions can subsequently

be recovered via precipitation with a variety of different salts, for example, carbonate and/or

sulfides.

[0077] In embodiments which include Ni and/or Co, the inventors have also found that

introducing ammonia during the leach or including it as a component of the leach solution is

useful since complexes with Ni and/or Co to form stable soluble Ni and/or Co ammonia

sulphates, particularly at pH values in the range of 9-10. This aids in the selective extraction and

recovery of Ni and/or Co.

[0078] In embodiments in which the leachate includes both Ni ions and Co ions, it is preferred

that Cu and Ni ions are contemporaneously extracted from the leachate, followed by the

recovery of Co ions, and then the recovery of Li ions. However, the skilled person will

appreciate that these metal ions may be extracted or otherwise recovered from the leachate in different order and/or that other metal ions may be recovered from the leachate at intervening stages prior to the recovery of lithium or potentially after the recovery of lithium.

[0079] Ni ions can be contemporaneously extracted with Cu ions via solvent extraction. To

facilitate this, the method may include an upstream oxidation step to oxidise Co ions to Co(III).

This prevents cobalt from being recovered during solvent extraction, and thus poisoning of the

extractant with Co(II) ions. The Ni ions can then be selectively stripped from the extractant with

a stripping agent prior to stripping of Cu ions. It is preferred that the extractant is sulfuric acid,

in which case Ni ions can be stripped at relatively lower sulfuric acid concentration than Cu ions

thus permitting the selective recovery of Ni and Cu ions. Co can be subsequently recovered

from the leachate via precipitation, e.g., with sulfide.

[0080] If ammonia is present, then this can be recovered prior to the recovery of lithium.

Ammonia can be steam stripped from the leachate.

[0081] If ammonium chloride is present, this is retained in the leachate and can be recycled after

the recovery of lithium from the leachate (in the form of lithium ammonium sulfate as discussed

above).

[0082] The invention will be described below in relation to embodiments thereof which are

intended to be illustrative in nature and should not be construed in a limiting manner.

Embodiment 1

[0083] This embodiment describes a method for the recovery of metals from a feed containing

electronic waste comprising one or more lithium-ion battery types. In this embodiment, the feed

comprises copper metal and metal oxides of at least cobalt, lithium, and nickel.

[0084] The method includes an initial leaching step in which lithium-ion battery waste (which

may be blended with other sources of electronic waste) is subjected to an alkaline leach with a

first leach solution comprising ammonium sulphate. In this embodiment, the first leach solution

additionally comprises ammonia and ammonium chloride which are both found to enhance the

leach process. Ammonia assists in the formation of stable soluble complexes of Ni and Co, and

ammonium chloride promotes the stability of Cu(I) thus enhancing the effectiveness of the

leach. The leach is carried out at atmospheric pressure and at ambient temperatures. However, the leach may be carried out at elevated temperatures, for example, at temperatures of less than the boiling point of the leach solution.

[0085] The alkaline leach oxidises elemental copper contained in the lithium-ion batteries into

soluble copper ions, and this in turn provides a source of electrons to reduce or otherwise

liberate cobalt, lithium, and nickel ions contained in the batteries. Thus, the leach results in the

formation of a leachate comprising soluble ions of copper, cobalt, lithium, and nickel, and a

solid residue. The inventors have found that a significant proportion of the contained cobalt,

nickel, copper and lithium is leached into solution, for example, greater than about 90% nickel,

copper and cobalt, and greater than about 70% lithium. Likewise, a significant proportion of the

aluminium, iron, contained in the battery is retained in the solid residue, for example, greater

than about 99% of aluminium and iron,.

[0086] The leachate can be subjected to a solvent extraction step for the extraction of copper

and/or nickel. The solvent, loaded with copper and/or nickel can then be separated from the

combined leachate, with copper and/or nickel subsequently being recovered from the solvent.

Copper and nickel may be recovered from the solvent via stripping with a stripping agent, such

as sulfuric acid. Generally, nickel can be selectively stripped with a lower residual acid

concentration than for copper, e.g., in the pH range of about 1-4 with copper being subsequently

stripped by increasing the acid concentration e.g., to greater than about 50 g/L H2SO4. This two-

stage stripping allows the copper and nickel to be selectively recovered in separate streams.

[0087] The leachate can then be subjected to further treatment to recover cobalt. In this

embodiment, cobalt is recovered via a cobalt precipitation process whereby the leachate is

treated with a sulfide, such as hydrogen sulfide or ammonium sulfide, to precipitate cobalt

sulfide. The cobalt sulfide can then be recovered from the combined leachate using any solid-

liquid separation process generally known to those skilled in the art, such as filtration.

[0088] The leachate, now substantially depleted of cobalt, copper, and nickel can be further

treated to recover ammonia, ammonium salts, and lithium.

[0089] Ammonia is steam stripped from the leachate and the recovered ammonia is recycled and

reused as a component of the first leach solution. The lithium in the leachate is generally in the

form of lithium sulfate. This lithium sulfate can be crystallised with ammonium sulfate (e.g., via

an evaporation process) in the form of lithium ammonium sulfate and separated from the leachate. The lithium ammonium sulfate can then be subjected to thermal treatment to decompose the lithium ammonium sulfate to a lithium sulfate solid, ammonia gas, and sulfur trioxide gas. The ammonia and sulfur trioxide gases can be captured and reacted together with water, such as in a wet scrubber, to form ammonium sulfate which can then be recycled to the first and/or second leaching steps.

Embodiment 2

[0090] This embodiment describes a method for the recovery of metals from a feed containing

one or more lithium-ion battery types. In this particular embodiment, the feed comprises copper

metal and metal oxides of at least lithium, and nickel.

[0091] The method includes an initial leaching step in which lithium-ion battery waste (which

first leach solution comprising ammonium sulphate. In this particular embodiment, the first

leach solution additionally comprises ammonia which is found to enhance the leach process by

promoting the formation of stable soluble Ni and Co complexes. The leach is carried out at

atmospheric pressure and at ambient temperatures. However, the leach may be carried out at

elevated temperatures, for example, at temperatures of less than the boiling point of the leach

solution.

[0092] The alkaline leach oxidises elemental copper contained in the lithium-ion batteries into

soluble copper ions, and thus provides a source of electrons to reduce or otherwise liberate

nickel and lithium ions contained in the batteries. Thus, the leach results in the formation of a

first leachate comprising soluble ions of copper, lithium, and nickel, and a first solid residue.

[0093] The first leachate is then separated from the first solid residue.

[0094] The first solid residue comprises low value materials such as iron and aluminium but

depending on the types of lithium-ion battery waste, can also contain residual lithium and nickel

compounds.

[0095] The quantities of lithium and nickel may be in amounts sufficient that warrant further

treatment for the recovery of these metals. If so, the first solid residue may be subjected to a

further leaching step with a second leach solution comprising ammonium sulfate and preferably ammonium chloride. The inventors have found that ammonium chloride advantageously stabilizes Cu(I) ions. The second leach is carried out at atmospheric pressure and at ambient temperature. However, as above, the second leach may be carried out at elevated temperature, such as at temperatures of less than the boiling point of the leach solution. The second leach may be an oxidative leach. That is, an oxidant such as air, hydrogen peroxide, hypochlorite and the like may be used during the leach to aid in the recovery of metals. If the redox half-cell potential was less than 100 mV, such as is typically the case with a feed of LFP battery waste, then an oxidant is useful to aid or enhance the leaching process.

[0096] The second leach provides a second leachate comprising soluble ions of lithium and

nickel, and a second solid residue.

[0097] The second leachate is then separated from the second solid residue.

[0098] The first and second leachates are then be combined to form a combined leachate which

may then be subjected to a number of steps for the selective recovery of copper, lithium, and

nickel.

[0099] The

[0099] Thecombined combinedleachate can be leachate cansubjected to a solvent be subjected extraction to a solvent step for the extraction extraction step for the of extraction of

copper and/or nickel. In alternative embodiments in which the leachate includes Mn ions, the

leachate would first be subjected to treatment to remove Mn, e.g. through an oxidation and

precipitation process as generally discussed above. In addition, in embodiments in which the

leachate includes Co ions, the leachate would first be subjected to an oxidation process (e.g.

during Mn recovery) to convert the Co ions to Co(III) to prevent the solvent extractant from

being poisoned with Co ions. In any case, the solvent, loaded with copper and/or nickel can then

be separated from the combined leachate, with copper and/or nickel subsequently being

recovered from the solvent. Copper and nickel may be recovered from the solvent via stripping

with a stripping agent, such as sulfuric acid. Generally, nickel can be selectively stripped with a

lower residual acid concentration than for copper, e.g., in the pH range of about 1-4 with copper

being subsequently stripped by increasing the acid concentration e.g., to greater than about 50

g/L H2SO4.This g/L H2SO4. This two-stage two-stage stripping stripping allows allows the copper the copper andtonickel and nickel to be selectively be selectively separated. separated.

[0100] The combined leachate, now substantially depleted of copper and nickel can be further

treated to recover ammonia, ammonium salts, and lithium.

[0101] Ammonia is steam stripped from the leachate and the recovered ammonia is recycled and

form of lithium sulfate. This lithium sulfate can be crystallised with ammonium sulfate (e.g., via via

an evaporation process) in the form of lithium ammonium sulfate and separated from the

leachate. The lithium ammonium sulfate can then be subjected to thermal treatment to

decompose the lithium ammonium sulfate to a lithium sulfate solid, ammonia gas, and sulfur

trioxide gas. The ammonia and sulfur trioxide gases can be captured and reacted together with

water, such as in a wet scrubber, to form ammonium sulfate which can then be recycled to the

first and/or second leaching steps.

[0102] Figure 1 is a process flow diagram illustrating a method in accordance with the above-

described embodiment. The method of Figure 1 describes the recovery of a copper product 18

and a lithium product 30. In this embodiment, a feed stream 1 is subjected to a pre-treatment

process, for example shredding 100, to render the feed stream 1 suitable for further processing,

which is typically <5mm. The resulting shredded feed stream 2 is then passed to an alkaline

leach circuit 110, in which it is contacted with a liquor containing ammonia, ammonium sulfate

with/without ammonium chloride 19, and ammonia top-up 3 and 22 to solubilise copper. The

alkaline leach circuit is operated, for example, at about 50 °C, atmospheric pressure, about pH

9.0, at about 10% solids. The resultant alkaline leached slurry 4 is subjected to a solid liquid

separation step 120, such as a thickener, or number of thickeners with washing, and the

ammonia leach liquor 6, is directed to the solvent extraction circuit 160.

[0103] Thickener underflow 5 is directed to an ammonium sulfate leach circuit 130, where it is

contacted with a solution containing ammonium sulfate 24 and 32 and ammonium sulfate top-up

7. Air 8 is sparged to the leach circuit 130. The ammonium sulfate leach is operated at about 100

°C, about Eh 120 mV (Ag/AgCl electrode) and at about 10% solids. The ammonium sulfate

leach discharge 9 is directed to a thickener 140. Thickener underflow 11 is directed to a filter

150, whereby the thickened slurry is filtered. The resulting filter cake is washed with water 12

and the filtrate and wash filtrate are combined with the thickener overflow 10 and ammonia

leach liquor 6.

[0104] The pregnant leach liquor is directed to a copper solvent extraction circuit 160 where it is

contacted with a copper extractant, such as a commercially available oxime extractant, for

example LIX84ITM. Copper is loaded onto the copper extractant and a loaded extractant 14 is separated from a raffinate 19. The loaded extractant 14 is contacted with dilute sulfuric acid 16 or anolyte from a copper electrowinning stage 180 in a copper strip stage 170 to produce a loaded stripliquor loaded strip liquor 15 15 containing containing copper copper and a and a copper copper depleteddepleted extractant. extractant. A stripped Aorganic stripped organic

(not shown) is recycled (not shown) to the extraction circuit 160 to extract more copper. A

copper product 18 is recovered from the copper loaded strip liquor 15 in a copper

electrowinning stage 180.

[0105] The copper depleted raffinate 19, which contains ammonia and ammonium sulfate, is

directed to the ammonia leach circuit 110 to recover more metal. The remaining filtrate 29 is

directed to an ammonia recovery circuit 190, in which steam 21 is used to strip ammonia 22.

Recovered ammonia 22 is re-used in the process, specifically for example in the ammonia leach

110. 110.

[0106] Ammonia free liquor 24 is directed to the ammonium sulfate leach 130 and also to a

crystalliser 200 in which condensate 25 is removed by forced evaporation and lithium

ammonium sulfate 26 is crystallised. The crystalliser discharge is subjected to solid liquid

separation using a centrifuge 210 and the centrate 27 is directed to the ammonium sulfate leach

130. The lithium ammonium sulfate 28 is subjected to calcination in a kiln 220 in which the

solids, lithium sulfate 30, are collected for sale and an off-gas 29 is collected in a wet scrubber,

utilising scrub water 31, to recover ammonium sulfate solution 32. This liquor is directed to the

ammonium sulfate leach 130.

Embodiment 3

[0107] This embodiment describes a method for the recovery of metals from a feed containing

metal and metal oxides of at least cobalt, lithium, manganese, and nickel.

[0108] The method includes an initial leaching step in which lithium-ion battery waste (which

leach solution additionally comprises ammonia which is found to enhance the leach process as

described previously. The leach is carried out at atmospheric pressure and at ambient

temperatures. However, the leach may be carried out at elevated temperatures, for example, at

temperatures of less than the boiling point of the leach solution.

[0109] The alkaline leach oxidises elemental copper contained in the lithium-ion batteries into

soluble copper ions, and reduces or otherwise liberates nickel, cobalt, manganese and lithium

ions contained in, for example nickel manganese cobalt (NMC), lithium cobalt oxide (LCO),

and lithium-ion manganese oxide (LMO) batteries. Thus, the leach results in the formation of a

first leachate comprising soluble ions of cobalt, copper, lithium, manganese, and nickel, and a

first solid residue.

[0110] The first leachate is then separated from the first solid residue.

[0111] The first solid residue comprises low value materials such as iron and aluminium but

depending on the types of lithium-ion battery waste, can also contain residual cobalt, lithium,

manganese and nickel compounds. For example, where the feed comprises lithium iron

phosphate (LFP) and lithium nickel cobalt aluminium oxide (NCA) batteries, some of the

cobalt, lithium, and nickel is retained in the first solid residue.

[0112] The quantities of cobalt, lithium, manganese, and nickel may be in amounts sufficient

that further recovery of these metals is economically viable and thus desirable. If so, the first

solid residue may be subjected to a further leaching step with a second leach solution

comprising ammonium sulfate and preferably ammonium chloride. The second leach is carried

out at atmospheric pressure and at ambient temperature. However, as above, the second leach

may be carried out at elevated temperature, such as at temperatures of less than the boiling point

of the leach solution. The second leach may be an oxidative leach. That is, an oxidant such as

air, hydrogen peroxide, hypochlorite and the like may be used during the leach to aid in the

recovery of metals. Generally, with a feed that comprises NCA and/or NMC battery materials an

oxidant is not required since cobalt, nickel, and manganese are present in sufficient quantities to

provide a sufficiently high redox half-cell potential of >100 > 100mV. mV.However, However,if ifthe theredox redoxhalf-cell half-cell

potential was less than 100 mV, such as is typically the case with a feed of LFP battery waste,

then an oxidant is useful to aid or enhance the leaching process.

[0113] The second leach provides a second leachate comprising soluble ions of cobalt, lithium,

manganese, and nickel, and a second solid residue.

[0114] The second leachate is then separated from the second solid residue. As above,

depending on the types of batteries present, the second solid residue may contain residual cobalt,

lithium, manganese, and nickel in commercially recoverable amounts.

[0115] To further recover these metals, the second solid residue is subjected to a size separation

process to classify the first solid residue into a coarse fraction and a fine fraction. The fine

fraction contains >80% of the residual nickel and also contains some residual cobalt, lithium,

and manganese. The fine fraction is subjected to an acid leach, such as with sulfuric acid, to

provide a third leachate comprising ions of cobalt, lithium, manganese, and nickel, and a third

solid residue. The third leach is carried out at atmospheric pressure and at ambient temperature.

However, as above, the third leach may be carried out at elevated temperature, such as at

temperatures of less than the boiling point of the leach solution.

[0116] The third leachate is then separated from the third solid residue.

[0117] It will be appreciated that in alternative embodiments, the third acid leach step is

omitted.

[0118] Aluminium, iron, and phosphate are not extracted to significant amounts and are

generally retained in the first, second, and/or third solid residues. Given this, the leaching

process is selective for higher value metals such as copper, cobalt, lithium, manganese, and

nickel.

[0119] The first, second, and third leachates may then be combined to form a combined leachate

which maythen which may thenbe be subjected subjected to ato a number number of for of steps steps thefor the selective selective recovery recovery of cobalt, of cobalt, copper, copper,

lithium, manganese, and nickel.

[0120] To recover manganese, the combined leachate is subjected to an oxidation step in the

presence of ammonia to precipitate manganese in the form of manganese oxides such as Mn2O3, MnO,

Mn3O4 and/or MnO2 (but not MnO (but not MnO). MnO). The The inventors inventors have have found found that that where where the the leachate leachate

additionally comprises cobalt ions, the presence of ammonia is important to complex with the

cobalt ions to retain these in the form of soluble Co(III) ions and prevent the formation of a CoO

precipitate. The manganese oxide precipitate can then be recovered from the combined leachate

using any solid-liquid separation process generally known to those skilled in the art, such as

filtration.

[0121] The combined leachate can then be subjected to a solvent extraction step for the

extraction of copper and/or nickel. The solvent, loaded with copper and/or nickel can then be

separated from the combined leachate, with copper and/or nickel subsequently being recovered from the solvent. Copper and nickel may be recovered from the solvent via stripping with a stripping agent, such as sulfuric acid. Generally, nickel can be selectively stripped with a lower residual acid concentration than for copper, e.g., in the pH range of about 1-4 with copper being subsequently stripped by increasing the acid concentration e.g., to greater than about 50 g/L

H2SO4. This two-stage stripping allows the copper and nickel to be selectively separated.

[0122] In alternative embodiments, Cu and Ni can be recovered prior to Mn recovery.

[0123] The combined leachate can then be subjected to further treatment to recover cobalt. In

this embodiment, cobalt is recovered via a cobalt precipitation process whereby the combined

leachate is treated with a sulfide, such as hydrogen sulfide gas or ammonium sulfide, to

precipitate cobalt precipitate cobalt sulfide. sulfide. The The cobalt cobalt sulfide sulfide can can then be then be recovered recovered from theleachate from the combined combined leachate

filtration.

[0124] The combined leachate, now substantially depleted of cobalt, copper, manganese, and

nickel can be further treated to recover ammonia, ammonium salts, and lithium.

[0125] Ammonia is steam stripped from the leachate and the recovered ammonia is recycled and

first and/or second leaching steps.

[0126] Theprocess

[0126] The processis is described described in more in more detaildetail with reference with reference to Figureto 2. Figure 2.isFigure Figure 2 2 is a process a process

flow diagram illustrating the method of the invention according to the embodiment generally

described above.

[0127] The method of Figure 2 describes the recovery of a nickel product 27, a copper product

32, a cobalt product 37 and a lithium product 48. In this embodiment, feed stream 1 is subjected

to a pre-treatment process, for example shredding 100 to <5mm, for example <1mm, to render the feed stream 1 suitable for further processing. The resulting shredded feed stream 2 is then passed to an alkaline leach circuit 110, in which it is contacted with a liquor containing ammonia, ammonium sulfate with/without ammonium chloride 39, and ammonia top-up 3 and

40 to solubilise metal species. Conditions in the alkaline leach circuit 110 include about 5-10%

solids, about 50°C, atmospheric pressure, about a 12 hour residence time, a pH of about 9 with

ammonia about 200 g/L ammonium sulfate, and about 20 g/L ammonium chloride if present.

[0128] The resultant alkaline leached slurry 4 is subjected to a solid liquid separation step 120,

such as a thickener, or number of thickeners with washing, and the ammonia leach liquor 6, is

directed to the manganese oxide precipitation circuit 180.

[0129] The thickener underflow 5 is directed to an ammonium sulfate leach circuit 130, where

it is contacted with a solution containing ammonium sulfate 47 and ammonium sulfate top-up 7.

Conditions in the ammonium sulfate leach circuit 130 include about 5-10% solids, about 100 -

105°C, atmospheric pressure, about 4 - 12 hours residence time, about 200 g/L ammonium

sulfate and 20 g/L ammonium chloride.

[0130] The ammonium sulfate leach discharge 8 is directed to a screen 140, for example of

um, for example about 180 µm, between 75 - 500 µm, um, to separate a coarse fraction and a fine

fraction of particles. The coarse fraction 9 is stored and the fine fraction 10 is directed to a

thickener 150. The thickener overflow, for example ammonium sulfate leach liquor 11, is

directed to a manganese oxide precipitation circuit 180.

[0131] The thickener underflow 12 is directed to an acid leach circuit 160, where it is contacted

with sulfuric acid 13. The conditions for the acid leach circuit 160 included a temperature in the

range of about 20 to 100°C, for example 70°C, a pH of less than about 3, for example a pH of

about 1.5, a residence time of between about 4 - 12 hours, 30% solids and 98% acid addition.

[0132] An acid leach discharge 14 is subjected to filtration 170 and the solids are washed to

produce a leach residue 15, which is stored, and an acid leach liquor 17, that is directed to the

manganese oxide precipitation circuit 180.

[0133] The leach liquors 6, 11 and 17 are directed to the manganese oxide precipitation circuit

180 in which air 18 is sparged into the liquor to force the precipitation of manganese oxides. A precipitation slurry 19 is subject to solid liquid separation by thickening and filtration 190. A manganese product 20 is washed and stored.

[0134] A pregnant leach liquor post manganese precipitation 21 is directed to a copper and

nickel solvent extraction circuit 200 where it is contacted with a copper and nickel extractant,

such as a commercially available oxime extractant, for example LIX84ITM. Copper and nickel

are loaded onto the copper extractant and a loaded extractant 23 is separated from a raffinate 22.

The loaded extractant 23 is contacted with dilute sulfuric acid 24, for example 150 g/L sulfuric

acid, in a nickel strip stage 210 to produce a loaded strip liquor containing nickel 25 and a nickel

depleted extractant 28. The nickel depleted extractant 28 is contacted with dilute sulfuric acid

liquor 29, for example 200 g/L sulfuric acid, in the copper strip stage 220 to produce a loaded

strip liquor 30 containing copper. A stripped organic (not shown) is recycled (not shown) to the

extraction circuit 200 to extract more copper and nickel. A nickel product 27 (ostensibly in the

form of nickel sulfate) is recovered from the nickel loaded strip liquor 25 in a nickel

crystallisation stage 230. A copper product 32 (ostensibly in the form of copper sulfate) is

recovered from the copper loaded strip liquor 30 in a copper electrowinning stage 240.

[0135] The copper and nickel depleted raffinate 22 is directed to a cobalt recovery circuit 250 in

which a precipitation reagent, for example hydrogen sulfide gas 33, is added to force the

precipitation of cobalt sulfide. A resulting slurry 34 is subjected to solid liquid separation, for

example by way of a thickener and filter 260, and washed with water 35 to produce a cobalt

product 37.

[0136] Most of a resulting filtrate 39, which contains ammonia and ammonium sulfate, is

directed to the ammonia leach circuit 110 to recover more metal. The remaining filtrate 38 is

directed to an ammonia recovery circuit 270, in which steam 41 is used to strip ammonia 40. A

recovered ammonia 40 is re-used in the process, specifically for example in the ammonia leach

110.

[0137] An ammonia free liquor 42 is directed to the ammonium sulfate leach 130 and also to a

crystalliser 280 in which a condensate 43 is removed by forced evaporation and lithium

ammonium sulfate 46 is crystallised. The crystalliser discharge is subjected to solid liquid

separation using a centrifuge 290 and the centrate 45 is directed to the ammonium sulfate leach

130. The lithium ammonium sulfate 46 intermediate is subjected to calcination in a kiln 300 in which the solids, lithium sulfate 48, are collected for sale and an off-gas 47 is collected in a wet scrubber, utilising scrub water 49, to recover ammonium sulfate solution 50.

Examples

Example 1

[0138] This example reports a single stage alkaline leach of raw lithium-ion nickel manganese

cobalt 622 (NMC622) battery shreds with a leach solution of ammonium sulfate, ammonia, and

ammonium chloride.

[0139] The NMC battery shreds contained 22.9 wt% Cu, 12.5 wt% Ni, 4.9 wt% Co, 6.2 wt%

Mn and 2.94 wt% Li on an elemental basis. Elemental copper was present in sufficient amount

to provideananoxidation to provide oxidation reduction reduction potential potential of lessofthan less than mV - -150 - (Ag/AgCl 150 mV (Ag/AgCl electrode)electrode) during the during the

leach.

[0140] The NMC battery shreds were reacted with an aqueous leach solution containing 169 g/L

ammonium sulfate, 46g/L ammonia and 14.5 g/L ammonium chloride at a loading of 3.8 wt%

solids. The leach was carried out at a pH of 9.5, at atmospheric pressure, and a temperature of

50 °C for 2 hours.

[0141] The extraction of nickel, cobalt, copper, lithium and manganese into the leachate was

found to be 97.5%, 96.4%, 99.3%, 95.5% and 96.1%, respectively.

[0142] Although not reported in this example, nickel, cobalt, copper, lithium and manganese

can be selectively recovered from the leachate using methods disclosed herein. Likewise, the

ammonium sulfate, ammonia, and ammonium chloride can be recovered for reuse using the

methods disclosed herein.

Example 2

[0143] This example reports a three-stage leach of a blended feed of raw lithium-ion nickel

manganese cobalt 622 (NMC622), lithium-ion nickel manganese cobalt 811 (NMC811), lithium

nickel cobalt aluminum oxide (NCA), and lithium iron phosphate (LFP) battery shreds with a

leach solution of ammonium sulfate, ammonia, and ammonium chloride.

[0144] An equal weight blend of NMC811, NMC622, NCA and LFP battery shreds was

prepared containing 7.01 wt% Cu, 14.5 wt% Ni, 2.48 wt% Co, 2.16 wt% Mn and 2.69 wt% Li.

Elemental copper was present in sufficient amount to provide an oxidation reduction potential of

less than -150 mV (Ag/AgCl electrode) during the leach.

[0145] The battery shred blend was first subjected to an alkaline leach in a solution containing

215g/L ammonium sulfate, 105g/L ammonia and 21g/L ammonium chloride at loading of 9.8

wt% solids. The leach was carried out at a pH range of 9.4-9.9, at atmospheric pressure, and at a

temperature of 50 °C for 6 hours.

[0146] The extraction of nickel, cobalt, copper, lithium and manganese into the leachate was

37.6%, 57.6%, 81.5%, 47.8% and 67.9%, respectively. The metals were extracted mainly from

NMC622 and NMC811 batteries.

[0147] The solid residue from the first leach was found to contain 1.46 wt% Cu, 10.2 wt% Ni,

1.19 wt% Co, 0.78 wt% Mn and 1.59 wt% Li.

[0148] This solid residue was separated from the leachate and subjected to a second leach with a

solution containing 343g/L ammonium sulfate and 34g/L ammonium chloride at a loading of 6.9

wt% solids. The leach was carried out in a solution such that the natural pH was in the range of

5.1-5.3 and the natural oxidation reduction potential was 165mV (Ag/AgCl electrode). The

leach was conducted at atmospheric pressure and at a temperature of 100 °C for a period of 6

hours.

[0149] The extraction of nickel, cobalt, copper, lithium and manganese reached 59.4%, 82.2%,

33.8%, 94.3% and 94.7%, respectively. The metals, with the exception of nickel, were extracted

from all battery types. Nickel was extracted mainly from NMC811 and NMC622 material that

was not leached in the preceding alkaline leach.

[0150] The extraction of nickel, cobalt, copper, lithium and manganese in the leachate across

both leach stages reached 74.7%, 92.5%, 87.7%, 97.0% and 98.3%, respectively.

[0151] The solid residue from the second leach was initially screened at 180 micron to remove

coarse material, in particular steel and aluminium foil. The screen undersize contained 1.27 wt%

Cu, 5.44 wt% Ni, 0.28 wt% Co, 0.95 wt% Mn and 0.12 wt% Li.

[0152] The solid residue was re-pulped in water to 30% solids then sulfuric acid was added to a

target pH 1.50. After 6 hours of leaching at 70 °C the extraction of nickel, cobalt, copper,

lithium and manganese reached 99.5%, 99.0%, 98.8%, 96.3% and 92.6%, respectively. The acid

consumption was significantly lower (<200kg/t) than an equivalent sulfuric acid only flowsheet

(> 1200kg/t). (>1200kg/t).

[0153] The extraction of nickel, cobalt, copper, lithium and manganese into the leachate across

all three leach stages and including metal losses associated with screening, reached 96.8%,

98.2%, 97.7%, 98.6% and 93.0%, respectively.

[0154] The leachates from the three leach steps can be combined and subsequently treated for

the selective recovery of nickel, cobalt, copper, lithium and manganese using methods disclosed

herein. Likewise, the ammonium sulfate, ammonia, and ammonium chloride can be recovered

for reuse using the methods disclosed herein.

Example 3

[0155] This example reports the oxidative leach of raw lithium iron phosphate (LFP) battery

shreds with a single stage aqueous leach solution of ammonium sulfate and ammonium chloride.

[0156] The LFP battery shreds contained 6.7 wt% Cu and 1.99 wt% Li on an elemental basis.

[0157] The LFP battery shreds were reacted with an aqueous leach solution containing 350 g/L

ammonium sulfate and 17.7 g/L ammonium chloride at a loading of 4.0 wt% solids. Air was

added as an oxidant to a target oxidation reduction potential of +150 mV (Ag/AgCl electrode).

[0158] The leach was carried out at the natural pH which was in the range of 4.9-5.2, at

atmospheric pressure, and a temperature of 100 °C for 4 hours.

[0159] The extraction of copper and lithium into the leachate was found to be 83.4% and 92.5%

respectively. Only 0.5% Fe was co-extracted.

[0160] Although not reported in this example, copper and lithium can be selectively recovered

from the leachate using methods disclosed herein. Likewise, the ammonium sulfate and

ammonium chloride can be recovered for reuse using the methods disclosed herein.

Example 4

[0161] This example reports the leach of raw lithium-ion nickel manganese cobalt 811

(NMC811) battery shreds with a single stage aqueous leach solution of ammonium sulfate and

ammonium chloride.

[0162] The NMC811 battery shreds contained 2.46 wt% Cu, 22.2 wt% Ni, 2.72 wt% Co, 1.72

wt% Mn and 2.83 wt% Li on an elemental basis.

[0163] The NMC811 battery shreds were reacted with an aqueous leach solution containing 355

g/L ammonium sulfate and 17.7 g/L ammonium chloride at a loading of 4.0 wt% solids.

Additional copper metal was added at an amount of 250 kg/t, which may be introduced in the

form of scrap electronics e.g., printed circuit boards and the like.

[0164] The leach was carried out at the natural pH which was in the range of 4.7-5.5, a natural

redox potential of about 15-150 mV (Ag/AgCl electrode), at atmospheric pressure, and a

temperature of 100 °C for 4 hours.

[0165] The extraction of copper, nickel, cobalt, manganese and lithium into the leachate was

60.1%, 67.0%, 79.3%, 94.8% and 95.5%, respectively.

[0166] Although not reported in this example, copper, nickel, cobalt, manganese and lithium

ammonium sulfate and ammonium chloride can be recovered for reuse using the methods

disclosed herein.

Example 5

[0167] This example reports the leach of raw lithium nickel cobalt aluminum Oxide (NCA)

battery shreds with a single stage aqueous leach solution of ammonium sulfate and ammonium

chloride.

[0168] The NCA battery shreds contained 0.95 wt% Cu, 24.3 wt% Ni, 2.77 wt% Co, 0.02 wt%

Mn and 3.20 wt% Lion an elemental basis.

[0169] The NCA battery shreds were reacted with an aqueous leach solution containing 355 g/L

ammonium sulfate and 17.7 g/L ammonium chloride at a loading of 4.0 wt% solids. Additional

copper metal was added at an amount of 250 kg/t, which may be introduced in the form of scrap

electronics e.g., printed circuit boards and the like.

[0170] The leach was carried out at the natural pH which was in the range of 4.5-4.9, a natural

redox potential of about - -16-30mV -16-30 (Ag/AgCl electrode), mV (Ag/AgCl electrode), at at atmospheric atmospheric pressure, pressure, and and aa

temperature of 100 °C for 4 hours.

[0171] The extraction of copper, nickel, cobalt, manganese and lithium into the leachate was

87%, 33.4%, 58.9%, 58.2% and 94.6%, respectively.

[0172] Although not reported in this example, copper, nickel, cobalt, manganese and lithium

disclosed herein.

Example 6

[0173] This example reports the alkaline leach of raw lithium-ion manganese oxide (LMO)

battery shreds with a single stage aqueous leach solution of ammonia, ammonium sulfate, and

ammonium chloride.

[0174] The LMO battery shreds contained 3.28 wt% Cu, 3.65 wt% Ni, 1.24 wt% Co, 27.9 wt%

Mn and 2.52 wt% Li on an elemental basis.

[0175] The LMO battery shreds were reacted with an aqueous leach solution containing 45g/L

ammonia, 180g/L ammonium sulfate and 18g/L ammonium chloride at a loading of 4.0 wt%

solids. Additional copper metal was added at an amount of 250 kg/t, which may be introduced in

the form of scrap electronics e.g., printed circuit boards and the like.

[0176] The leach was carried out at the natural pH which was in the range of 8.8 -9.1, a redox

potential potential ofofabout about - 123 - -123 to to -250 -250 mV (Ag/AgCl mV (Ag/AgCl electrode), electrode), at atmospheric at atmospheric pressure, pressure, and a and a

temperature of 50 °C for 4 hours.

[0177] The extraction of copper, nickel, cobalt, manganese and lithium into the leachate was

84.0%, 89.7%, 93.3%, 71.8% and 97.3% respectively.

[0178] Although not reported in this example, copper, nickel, cobalt, manganese and lithium

ammonia, ammonium sulfate and ammonium chloride can be recovered for reuse using the

methods disclosed herein.

Example 7

[0179] This example reports the alkaline leach of raw lithium cobalt oxide (LCO) battery shreds

with a single stage aqueous leach solution of ammonia, ammonium sulfate, and ammonium

chloride.

[0180] The LCO battery shreds contained 5.42 wt% Cu, 28.6 wt% Co and 3.46 wt% Li on an

elemental basis.

[0181] The LCO battery shreds were reacted with an aqueous leach solution containing 45g/L

solids.

[0182] The

[0182] Theleach leachwaswas carried out at carried outthe at natural pH of 9.2, the natural a redox pH of 9.2, potential of - -150 mV a redox potential of -150 mV

(Ag/AgCl electrode), at atmospheric pressure, and a temperature of 50 °C for 2 hours. After 2

hours, the extraction of copper, cobalt and lithium into the leachate was 93.8%, 24.1% and

25.9%, respectively.

[0183] 100kg/t of copper was then added and the leaching was carried out for an additional 2

hours. After the additional 2 hours of leaching, the extraction of copper, cobalt and lithium into

the leachate reached 97.6%, 67.5% and 68.9%, respectively.

[0184] This example demonstrates that higher metal extraction occurs with the addition of

copper.

[0185] Although not reported in this example, copper, cobalt, and lithium can be selectively

recovered from the leachate using methods disclosed herein. Likewise, the ammonia, ammonium sulfate and ammonium chloride can be recovered for reuse using the methods disclosed herein.

Example 8

[0186] This example reports a three-stage leach of a blended feed of raw lithium-ion nickel

leach solution of ammonium sulfate and ammonia. No ammonium chloride was added.

[0187] An equal weight blend of NMC811, NMC622, NCA and LFP battery shreds, containing

7.01% Cu, 14.5% Ni, 2.48% Co, 2.16% Mn and 2.69% Li was reacted in a solution containing

220g/L ammonium sulfate and 110g/L ammonia at 9.1% solids and 50C. After 6 hours of

leaching at pH 9.5-9.9 and an oxidation reduction potential of less than -90 mV (Ag/AgCl

electrode), the extraction of nickel, cobalt, copper, lithium and manganese reached 58.8%,

45.8%, 49.4%, 47.4% and 78.3%, respectively. The metals were extracted mainly from

NMC622 and NMC811 batteries.

[0188] The solid residue from the first leach was found to contain 6.17% Cu, 8.55% Ni, 0.468%

Co, 0.67% Mn and 2.10% Li.

[0189] This solid residue was reacted in a solution containing 354g/L ammonium sulfate at

5.1% solids and 100C. After 6 hours of leaching, in which the natural pH was 4.2-5.4 and the

natural oxidation reduction potential was 360-530mV (Ag/AgCl electrode), the extraction of

nickel, cobalt, copper, lithium and manganese reached 15.1%, 77.6%, 67.7%, 75.5% and 8.5%,

respectively. The metals, with the exception of nickel, were extracted from all battery types.

Nickel was extracted mainly from NMC811 and NMC622 material that was not leached in the

primary leach.

[0190] The extraction of nickel, cobalt, copper, lithium and manganese across both leach stages

reached 64.5%, 85.5%, 87.5%, 86.1% and 79.8%, respectively.

[0191] The solid residue from the second leach was initially screened at 180 micron to remove

coarse material, in particular steel and aluminium foil. The screen undersize contained 1.61%

Cu, 8.2% Ni, 0.49% Co, 0.69% Mn and 0.59% Li.

[0192] The solid residue was re-pulped in water to 30% solids then sulfuric acid was added to a

target pH 1.90. After 6 hours of leaching at 70 °C the extraction of nickel, cobalt, copper,

lithium and manganese reached 58.9%, 98.3%, 37.1%, 64.9% and 7.0%, respectively. The acid

consumption was significantly lower (<100kg/t) than an equivalent sulfuric acid only flowsheet

(> 1200kg/t). Higher (>1200kg/t). Highermetal extraction metal is expected extraction with higher is expected acid addition. with higher acid addition.

[0193] The extraction of nickel, cobalt, copper, lithium and manganese across all three leach

stages and including metal losses associated with screening, reached 85.7%, 92.3%, 99.7%,

95.5% and 80.0%, respectively.

Example 9

[0194] This example reports the leach of a mixture of lithium iron phosphate (LFP) and nickel

cobalt aluminum (NCA) battery shreds at an LFP:NCA mass ratio of 4:1 with a single stage

aqueous leach solution of ammonium sulfate and ammonium chloride.

[0195] The battery shreds contained 0.26 wt% Cu, 4.39 wt% Ni, 0.50 wt% Co, 19.0 wt% Fe and

1.99 wt% Li on an elemental basis.

[0196] The battery shreds were reacted with an aqueous leach solution containing 230g/L

ammonium sulfate, 23g/L ammonium chloride and 5.5 g/L Cu (as copper sulfate) at a loading of

4.9 wt% solids. Copper sulfate was added due to the low copper grade of the battery shreds.

[0197] The leach was carried out at natural pH which was in the range of 4.80-5.13, a redox

potential of +123 to +180 mV (Ag/AgCl electrode), at atmospheric pressure, and a temperature

of 100 °C for 8 hours.

[0198] Theextraction

[0198] The extraction of nickel, of nickel, cobalt, cobalt, iron iron and and lithium lithium into the into the was leachate leachate 44.0%, was 44.0%, 75.7%, 75.7%,

0.43% and 94.7%, respectively.

[0199] Although not reported in this example, copper, nickel, cobalt and lithium can be

selectively recovered from the leachate using methods disclosed herein. Likewise, the

disclosed herein.

Example 10

[0200] This example reports the leach of a mixture of lithium iron phosphate (LFP) and nickel

aqueous leach solution of ammonium sulfate. No ammonium chloride was added to the leach.

[0201] The battery shreds contained 0.26 wt% Cu, 4.39 wt% Ni, 0.50 wt% Co, 19.0 wt% Fe and

1.99 wt% Li on an elemental basis.

[0202] The battery shreds were reacted with an aqueous leach solution containing 230g/L

ammonium sulfate and 5.5 g/L Cu (as copper sulfate) at a loading of 4.9 wt% solids. Copper

sulfate was added due to the low copper grade of the battery shreds.

[0203] The leach was carried out at natural pH which was in the range of 4.22-5.05, a redox

potential of +91 to +126 (Ag/AgCl electrode), mV (Ag/AgCl at atmospheric electrode), pressure, at atmospheric and and pressure, a temperature a temperature

of 100°C for 8 hours.

[0204] The

[0204] Theextraction extractionof nickel, cobalt, of nickel, iron and cobalt, lithium iron into the into and lithium leachate the was 20.5%, was leachate 43.4%, 20.5%, 43.4%,

0.26% and 81.6%, respectively.

[0205] Although not reported in this example, copper, nickel, cobalt, manganese and lithium

disclosed herein.

[0206] It will be understood that the invention disclosed and defined in this specification

extends to all alternative combinations of two or more of the individual features mentioned or

evident from the text or drawings. All of these different combinations constitute various

alternative aspects of the invention.

Claims

34 CLAIMS: 05 Aug 2025 2023350690 05 Aug 2025 CLAIMS:

1. 1. A methodfor A method forrecovering recoveringmetals metalsfrom from electronicwaste electronic wasteorora aleach leachresidue residuethereof, thereof, the the electronic waste electronic waste or or leach leach residue residue comprising elemental copper comprising elemental copperand andone oneorormore morelithium lithium compounds,thethemethod compounds, method comprising: comprising:

leaching the electronic waste or leach residue with a leach solution comprising leaching the electronic waste or leach residue with a leach solution comprising

ammonium sulphate ammonium sulphate in in thethe presence presence of of an an oxidant oxidant to to provide provide a leachatecomprising a leachate comprising Cu Cu ionsions 2023350690

and Liions and Li ionsand and a solid a solid residue; residue;

separating theleachate separating the leachate andand the the solid solid residue; residue;

recovering Cu recovering Cuions ionsfrom fromthe theleachate; leachate; and and after after the step of the step of recovering recoveringCu Cu ionsions fromfrom the leachate, the leachate, the method the method further comprises further comprises

recovering Li ions from the leachate. recovering Li ions from the leachate.

2. 2. The method The methodofofclaim claim1,1,wherein: wherein:the theelemental elementalcopper copperisispresent presentininan an amount amount sufficient to provide sufficient to provideanan oxidation oxidation reduction reduction potential potential ofmV-100 of -100 mVasordetermined or less less as determined using using an an Ag/AgCl referenceelectrode. Ag/AgCl reference electrode.

3. 3. Themethod The methodofofclaim claim1 1oror2,2,wherein: wherein: the oxidant is present in an amount sufficient to provide an oxidation-reduction the oxidant is present in an amount sufficient to provide an oxidation-reduction

potential of potential of +50 +50 mV ormore mV or moreasasdetermined determined using using an an Ag/AgCl Ag/AgCl reference reference electrode; electrode; and/or and/or

the temperature is from about 0 °C and up to a temperature at or less than the boiling the temperature is from about 0 °C and up to a temperature at or less than the boiling

point of the leach solution at operating conditions of the leach; and/or point of the leach solution at operating conditions of the leach; and/or

the leach the leach is isconducted conducted at at atmospheric pressure; and/or atmospheric pressure; and/or

the leach is conducted for up to 24 hours; and/or the leach is conducted for up to 24 hours; and/or

the leach solution comprises no vegetable and/or fruit and/or animal biomatter. the leach solution comprises no vegetable and/or fruit and/or animal biomatter.

4. 4. Themethod The methodofofany anyone oneofofthe thepreceding precedingclaims, claims,wherein whereinthethe stepofofrecovering step recoveringLiLiions ions from the from the leachate leachate comprises: comprises:

crystallising ammonium crystallising lithiumsulfate ammonium lithium sulfatefrom fromthe theleachate, leachate,and and thermally decomposing thermally decomposing thethe crystallisedammonium crystallised ammonium lithium lithium sulfate sulfate to form to form a gas a gas

comprising ammonia comprising ammonia andand sulfur sulfur oxides, oxides, andand solid solid lithiumsulfate. lithium sulfate.

35

5. The method methodofofclaim claim4,4,wherein whereinprior priortotothe the step step of of crystallising crystallisingammonium lithium 05 Aug 2025 2023350690 05 Aug 2025

5. The ammonium lithium

sulfate, sulfate, the leachateisistreated the leachate treatedsuch such that that thethe leachate leachate is ammonia-, is an an ammonia-, Cu-, Cu-, Ni-, Ni-, Co-, Co-, Mn-lean Mn-lean

leachate and/or leachate and/or the the leachate leachate comprises substantially no comprises substantially no ammonia, Al,Cu, ammonia, Al, Cu,Fe, Fe,Ni, Ni, Co, Co,or or Mn. Mn.

6. 6. Themethod The methodofofany anyone oneofofthe thepreceding precedingclaims, claims,wherein wherein theelectronic the electronicwaste wastefurther further comprises comprises oneone or more or more transition transition metals, metals, the oxidant the oxidant is the is the one one transition or more or more transition metal metal oxides, andthetheleachate oxides, and leachate comprises comprises ions ions of theof theorone one moreor more transition transition metals. metals. 2023350690

7. 7. The method The methodofofclaim claim6,6,wherein whereinthe theone oneorormore more transitionmetals transition metalsare areselected selectedfrom from the group the consisting of: group consisting of: Co, Co, Mn, and/or Ni. Mn, and/or Ni.

8. 8. The method The methodofofany anyone oneofofthe thepreceding precedingclaims, claims,wherein wherein theelectronic the electronicwaste wastefurther further comprisesNi, comprises Ni, and andthe the leach leach solution solution further further comprises ammonia comprises ammonia in in anan amount amount that that thethe pHpH of of the leach solution is from about 8.5 to about 10.5, and wherein the leachate comprises at least the leach solution is from about 8.5 to about 10.5, and wherein the leachate comprises at least

Cu, Li,and Cu, Li, andNiNiions. ions.

9. 9. Themethod The methodofofclaim claim8,8,wherein: wherein: the leach the leach solution solution comprises ammonia comprises ammonia and and ammonium ammonium sulfate sulfate in a in a ratio ratio of from of from about about

1:2 to about 1:2 to about1:20; 1:20;and/or and/or the method the further comprises method further comprisescontemporaneously contemporaneously recovering recovering Cu ions Cu ions and and Ni ions Ni ions

from the leachate via a solvent extraction process. from the leachate via a solvent extraction process.

10. 10. The The method method ofone of any anyofone of claims claims 1 to 1 7,towherein 7, wherein the electronic the electronic waste waste further further

comprisesCo, comprises Co,and andthe theleach leachsolution solution further further comprises ammonia comprises ammonia in in an an amount amount thatthat thethe pH pH of of the leach solution is from about 8.5 to about 10.5, and wherein the leachate comprises at least the leach solution is from about 8.5 to about 10.5, and wherein the leachate comprises at least

Cu, Li, and Cu, Li, and Co ions. Co ions.

11. 11. The The method method of claim of claim 10, wherein 10, wherein the method the method further further comprises comprises recovering recovering Cu ionsCu ions from theleachate, from the leachate,andand after after removal removal of Cu of Cu precipitating ions, ions, precipitating Co from Co the from the leachate. leachate.

12. 12. The The method method of claim of claim 11, wherein 11, wherein the step the step of precipitating of precipitating Co from Co from the leachate the leachate

comprises precipitating comprises precipitating cobalt cobalt sulfide sulfide from from the leachate. the leachate.

36

13. The The method ofone anyofone of claims 1 to 1 7,towherein 7, wherein the electronic waste further 05 Aug 2025 2023350690 05 Aug 2025

13. method of any claims the electronic waste further

comprisesMn, comprises Mn,and andthe theleach leachsolution solutionfurther further comprises comprisesleachate leachatecomprises comprisesMnMn ions, ions, andand thethe

methodfurther method furthercomprises: comprises: treating the treating theleachate leachatewith withan anoxidant oxidantto toform formaaprecipitate precipitateofof MnMnand andprovide provide an an Mn- Mn-

lean leachate lean leachate comprising Cuions comprising Cu ionsand andLiLiions; ions; and and separating separating the the precipitate precipitateofofMn Mn from from the the Mn-lean leachate. Mn-lean leachate. 2023350690

14. 14. The The method method of claim of claim 13, wherein 13, wherein the oxidant the oxidant is air. is air.

15. 15. The The method method ofone of any anyofone ofpreceding the the preceding claims, claims, wherein wherein the electronic the electronic wastewaste further further

comprises Fe and Al, the solid residue comprises Fe and Al, and the leachate is an Fe-, Al- comprises Fe and Al, the solid residue comprises Fe and Al, and the leachate is an Fe-, Al-

lean leachateand/or lean leachate and/orthethe leachate leachate comprises comprises substantially substantially no Fe orno Fe or Al. Al.

16. 16. The The method method of claim of claim 1, wherein 1, wherein electronic electronic wastewaste comprises comprises elemental elemental copper, copper, and and one one or or more compounds more compounds of of Co,Co, Li,Li, andand Ni,Ni, andand wherein wherein thethe leach leach solution solution furthercomprises further comprises ammonia, andthetheleachate ammonia, and leachatecomprises comprisesCoCo ions, ions, CuCu ions, ions, LiLi ions,and ions, andNiNiions; ions;and andafter after the the step of separating step of separatingthetheleachate leachate from from the solid the solid residue, residue, the method the method further further comprises: comprises:

subjecting theleachate subjecting the leachate to to a solvent a solvent extraction extraction step step to remove to remove Cu ions Cu and ions and Ni ions Ni ions

from the from the leachate leachate and formaa Cu-,Ni-lean and form Cu-,Ni-leanleachate; leachate; subjecting theCu-,Ni-lean subjecting the Cu-,Ni-lean leachate leachate to a to a precipitation precipitation step step to to remove remove Co ions Co ions from the from the

Cu-,Ni-lean leachate and Cu-,Ni-lean leachate and form formaaCo-,Cu-,Ni-lean Co-,Cu-,Ni-leanleachate; leachate;and and recovering Li recovering Li from fromthe the Co-,Cu-,Ni-lean Co-,Cu-,Ni-leanleachate, leachate, wherein prior wherein prior to to the the step step of of recovering recovering Li, leachate Li, the the leachate is subjected is subjected to an ammonia to an ammonia

recovery step such that during the recovery of Li, the Co-,Cu-,Ni-lean leachate is recovery step such that during the recovery of Li, the Co-,Cu-,Ni-lean leachate is

substantially substantially free freeofofammonia. ammonia.

17. 17. The The method method of claim of claim 16, wherein 16, wherein the Cothe Co comprise ions ions comprise Co2+and Co² ions, ions, andtoprior prior the to the step step of subjectingthe of subjecting theleachate leachate to to thethe solvent solvent extraction extraction step, step, the method the method further further comprises comprises treating treating

2+ ions to Co³3+ions. the leachate the leachate with with an an oxidant oxidant to to oxidise oxidise the theCo Co² ions to Co ions.

18. 18. The The method method of claim of claim 1, wherein 1, wherein electronic electronic wastewaste comprises comprises elemental elemental copper, copper, and and one one or or more compounds more compounds of of Co,Co, Li,Li, Mn,Mn, andand Ni,Ni, andand wherein wherein leach leach solution solution further further comprises comprises

ammonia, andthetheleachate ammonia, and leachatecomprises comprisesCoCo ions, ions, CuCu ions, ions, LiLi ions,MnMn ions, ions,and ions, and NiNi ions;and ions; and after after the step of the step of separating separatingthethe leachate leachate fromfrom the solid the solid residue, residue, the method the method further comprises: further comprises:

37

treating the leachate with an oxidant to form a precipitate of Mn and to provide an 05 Aug 2025 2023350690 05 Aug 2025

treating the leachate with an oxidant to form a precipitate of Mn and to provide an

3+ Mn-leanleachate Mn-lean leachatecomprising comprisingCoCo ions ions in in theform the formofofCo³ Coions, ions, Cu Cu ions, ions, Li Li ions,and ions, andNiNi ions; ions;

and and

separating separating the the precipitate precipitateofofMn Mn from the Mn-lean from the leachate. Mn-lean leachate.

subjecting the subjecting the Mn-lean leachate to Mn-lean leachate to aa solvent solvent extraction extraction step stepto toremove remove Cu ions and Cu ions Ni and Ni

ions from ions the Mn-lean from the leachateand Mn-lean leachate andform forma aCu-,Mn-,Ni-lean Cu-,Mn-,Ni-lean leachate; leachate;

subjecting subjecting the the Cu-,Mn-,Ni-lean leachatetoto aa precipitation Cu-,Mn-,Ni-lean leachate precipitation step stepto toremove remove Co ions Co ions 2023350690

from the Cu-,Mn-,Ni-lean from the Cu-,Mn-,Ni-leanleachate leachateand andform form a Co-,Cu-,Mn-,Ni-lean a Co-,Cu-,Mn-,Ni-lean leachate; leachate; and and

recovering Li recovering Li from fromthe the Co-,Cu-,Mn-,Ni-lean Co-,Cu-,Mn-,Ni-lean leachate leachate

wherein prior wherein prior to to the the step step of of recovering recovering Li, leachate Li, the the leachate is subjected is subjected to an ammonia to an ammonia

substantially substantially free freeofofammonia. ammonia.

19. 19. The The method method of claim of claim 1, wherein 1, wherein the leach the leach solution solution further further comprises comprises ammonia, ammonia, the the leachate is a first leachate, and the solid residue is a first solid residue, and after the step of leachate is a first leachate, and the solid residue is a first solid residue, and after the step of

separating thefirst separating the firstleachate leachatefrom from the the first first solid solid residue residue the the method method furtherfurther comprises: comprises:

leaching the leaching the solid solid residue residue with with aasecond second leach leach solution solution comprising comprising ammonium sulfate ammonium sulfate

to provide to provide a a second leachate and second leachate a second and a solid residue; second solid residue; and and

separating thesecond separating the second leachate leachate andsecond and the the second solid residue. solid residue.

leaching the second solid residue with an acid to provide a third leachate and a third leaching the second solid residue with an acid to provide a third leachate and a third

solid residue; solid residue;

separating the third leachate and the third solid residue; and separating the third leachate and the third solid residue; and

combining combining thethe first first leachate, leachate, the the second second leachate, leachate, and and the theleachate third third leachate to form a to form a

combinedleachate. combined leachate.

20. The The 20. method method of claim of claim 19, wherein 19, wherein the electronic the electronic wastewaste comprises comprises elemental elemental copper, copper,

and one or and one or more morecompounds compounds of Co, of Co, Li,Li, Mn,Mn, and and Ni, Ni, and and the the method method comprises comprises recovering recovering one one

or or more of Co, more of Co, Cu, Cu, Li, Li, Mn, andNiNifrom Mn, and fromthe thecombined combined leachate. leachate.

Accepted Replacement Sheet received on 22 September 2023

wo 2024/064995 1/2 PCT/AU2023/050771

liquor Scrub 32 32 Scrub liquor

water Scrub 31 water Scrub 31 to ammonium to ammonium

leach sulfate Scrubber 230 Scrubber 230 sulfate leach

29

Calcination Calcination

product product

30 Li 30 Li

220 220

13 Leach 13 Leach

Residue Residue

28 28

to Centrate 27 to Centrate 27 Centrifuge 210 Centrifuge 210 leach suffate leach sulfate ammonium ammonium

12 Water 12 Water 150 Filter 150 Filter

26

Condensate 25 Condensate 25 Crystalliser 200 Crystalliser 200 11 Thickener 140 Thickener 140 ammonium To 24 ammonium To 24 leach sulfate leach sulfate Figure Figure 11

1010Ammonium Ammonium leach sulfate leach sulfate liquor liquor 23

9 Product Cu 18 Product Cu 18 88 Air Air Electrowinning Electrowinning leach to solution leach to solution Ammonia 190 St Cu SX 170 Ammonium 130 Ammonium 130 170 SX Cu St 190 Ammonia Leach sultate Leach sullate 180 Cuso. 180 CuSO,

22Ammonia Ammonia 21 Steam 21 Steam 16 H2SO4 H2SO4 22 16 recovery recovery

77 Ammonia Ammonia

Sulfate Sulfate

17 15 15 leachliquor leach liquor

66 Ammonia Ammonia

14 5 29Bleed 29 Bleed Ex Cu SX 160 Ex Cu SX 160 Thickener 120 Thickener 120 4 Raffinate 19 19 Raffinate 100Shredding 100 Shredding 110 Ammonia 110 Ammonia

Leach Leach

2 stream Feed 1 stream Feed 1 (LFPshreds) (LFP shreds) 33 Ammonia Ammonia

SUBSTITUTE SHEET (RULE 26)

Accepted Replacement Sheet received on 22 September 2023

WO 2024/064995 2/2 PCT/AU2023/050771

liquor Scrub 50 50 Scrub liquor

water Scrub 49 water Scrub 49 ammonium to to ammonium

leach sulfate sulfate leach

Scrubber 310 Scrubber 310 47

Calcination Calcination product product

48 Li 48 Li 300 300

46 15 15 Leach Leach

to Centrate 45 to Centrate 45 Residue Residue

Centrifuge 290 Centrifuge 283 leach sulfate leach sulfate ammonium ammonium

leach liquor leach liquor

17 17 Acid Acid

44

Condensate 43 Condensate 43 16 Water 16 Water Filter 170 Filters 170 Crystalliser 280 Crystalliser 380 ToToammonium ammonium

leach sulfate leach sulfate 14 teach Acid 160 teach Acks 160 13 H2SO4 13 H2SO4

42 leach to solution leach to solution 1111Ammonium Ammonium 4040Ammonia Ammonia leach sulfate Ammonia 270 leach sulfate Ammonia 270 41 Steam 41 Steam recovery recovery

liquor liquor

Figure Figure 22 12 3232CuCuproduct product Thickener 150 Thickener 150 Electronioning Electrowing St Cu SX 220 St Co SX 220 240Cuso, 240 CuSO,

29 H2SO4 29 H2SO4

38Bleed 38 Bleed

30 30 31 31

10 28 water Wash 35 water Wash 35 37 37Co Coproduct product 27 Ni product 27 Ni product XLS NISO. 230 XLS NISO 230 St N SX 210 St N SX 210 Screen 140 140 Screen

24H2SO4 24 H2SO4 Filter 260 9 9Coarse Coarse 260 Filter residue residue

25 26 36

23 34 8 liquor sulfate ammonium / Ammonia 39 liquor sulfate ammonium / Ammonia 39 77Ammonia Ammonia Ammonium 130 Ammonium 130 Cu/Ni SX 200 Cu/NE SX 200 Leach sultate - issuan 260Co 260 Coppt per

Sulfate Sulfate

Ex Ex Raffinate Raffinate

66 Ammonia Ammonia

22

21 5 leach leach Thickener 120 Manganess 11362 Thickener 120 33 H2S 33 HS presipitation procipitation Filter 380 product Filter 190 product

20 Mn 20 Mn oxide oxides 19

160

4 18Air 18 Air Shredding 180 100 Shindding Ammonia 110 Ammonia 110 Leach Leach

2 stream Feed 1 stream Feed 1 3 3Ammonía Ammonia

(LIBshreds) (LIB shreds)

SUBSTITUTE SHEET (RULE 26)