WO2024073856A1

WO2024073856A1 - System, apparatus and method for improving filter efficacy during recovery of one or more metals

Info

Publication number: WO2024073856A1
Application number: PCT/CA2023/051324
Authority: WO
Inventors: Christopher James BIEDERMAN; Darcy TAIT; Olga MISIC
Original assignee: Li-Cycle Corp.
Priority date: 2022-10-07
Filing date: 2023-10-05
Publication date: 2024-04-11

Abstract

A method of separating one or more metal compounds from a feed material stream that includes one or more metals, includes: subjecting the feed material stream to a metal compound precipitation process to yield a metal compound slurry; and filtering, in the presence of a graphite filter aid, the metal compound slurry to yield a metal compound-rich solids stream and a metal-depleted stream. The graphite filter aid improves filtration efficacy.

Description

SYSTEM. APPARATUS AND METHOD FOR IMPROVING FILTER EFFICACY DURING RECOVERY OF ONE OR MORE METALS

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application No. 63/414164 filed October ?, 2022, the entire content of which is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The subject disclosure relates generally to hydrometallurgical processing, and in particular to a system, an apparatus and a method for improving filter efficacy during recovery of one or more metals.

INTRODUCTION

[0003] International PCT Application Publication No. WO1996/025361 generally describes a method for separating copper and other metals in solution comprising the steps of precipitating the copper in a reactor at a free acid range of about 0.05 to 180 grams per liter, at a temperature from about 25 °C to about 90 °C in an aqueous solution with elemental sulfur, or chalcopyrite, and material selected from the group consisting of soluble sulfites and soluble bisulfites, and separating the precipitated copper, in the form of copper sulphides, by thickening the solution, recycling part to the precipitation step, and filtering copper sulphides from the other part.

[0004] U.S. Patent No. 3,740,331 generally describes how heavy metal pollutant ions can be removed from an aqueous solution in a sulfide precipitation process that avoids generation of noxious amounts of hydrogen sulfide and the formation of soluble complexes of sulfide ions. Sulfide ion and a heavy metal ion that forms a sulfide having a higher equilibrium sulfide ion concentration than the sulfide of the heavy metal pollutant are added to the solution. The added heavy metal acts as a scavenger for excess sulfide. In some cases the added heavy metal and the heavy metal pollutant form co-precipitates which result in more complete removal of the pollutant ion than could be achieved by sulfide precipitation of the pollutant alone. [0005] U.S. Patent No. 9,312,581 generally describes a method for recycling lithium batteries and more particularly batteries of the Li-ion type and the electrodes of such batteries. This method for recycling lithium battery electrodes and/or lithium batteries comprises the following steps: a) grinding of said electrodes and/or of said batteries, b) dissolving the organic and/or polymeric components of said electrodes and/or of said batteries in an organic solvent, c) separating the undissolved metals present in the suspension obtained in step b), d) filtering the suspension obtained in step c) through a filter press, e) recovering the solid mass retained on the filter press in step d), and suspending this solid mass in water, f) recovering the material that sedimented or coagulated in step e), resuspending this sedimented material in water and adjusting the pH of the suspension obtained to a pH below 5, preferably below 4, g) filtering the suspension obtained in step f) on a filter press, and h) separating, on the one hand, the iron by precipitation of iron phosphates, and on the other hand the lithium by precipitation of a lithium salt. The method finds application in the field of recycling of used batteries, in particular.

[0006] International PCT Application Publication No. W02005/101564 generally describes a method for treating all types of lithium anode batteries and cells via a hydrometallurgical process at room temperature. Said method is used to treat, under safe conditions, cells and batteries including a metallic lithium anode or an anode containing lithium incorporated in an anode inclusion compound, whereby the metallic casings, the electrode contacts, the cathode metal oxides and the lithium salts can be separated and recovered.

[0007] U.S. Patent Application Publication No. 2010/0230518 generally describes a method of recycling sealed batteries, the batteries are shredded to form a shredded feedstock. The shredded feedstock is heated above ambient temperature and rolled to form a dried material. The dried material is separated by screening into a coarse fraction and a powder fraction and the powder fraction is output. A system for recycling sealed cell batteries comprises an oven with a first conveyor extending into the oven. A rotatable tunnel extends within the oven from an output of the first conveyor. The tunnel has a spiral vane extending from its inner surface which extends along a length of the tunnel. A second conveyor is positioned below an output of the rotatable tunnel. [0008] U.S. Patent No. 8,858,677 generally describes a valuable-substance recovery method that includes: a solvent peeling step of dissolving a resin binder included in an electrode material by immersing crushed pieces of a lithium secondary battery into a solvent, so as to peel off the electrode material containing valuable substances from a metal foil constituting the electrode; a filtering step of filtering a suspension of the solvent, so as to separate and recover the electrode material containing the valuable substances and a carbon material; a heat treatment step of heating the recovered electrode material containing the valuable substances and the carbon material, under an oxidative atmosphere, so as to burn and remove the carbon material; and a reducing reaction step of immersing the resultant electrode material containing the valuable substances into a molten salt of lithium chloride containing metal lithium, so as to perform a reducing reaction.

SUMMARY

[0009] In one of its aspects, the present disclosure relates generally to a system and method for processing a feed stream obtained from batteries, including lithium-ion batteries (ternary, Lithium Iron Phosphate batteries "LFP", lithium solid state batteries "SSB" and the like) and other suitable batteries, and more particularly to systems and methods for improving filter efficacy during recovery of one or more metals, such as copper, lithium and/or other target metals, from battery materials.

[0010] More broadly, the feed stream may alternatively be obtained from other sources not including battery materials. Such other sources may be, for example, and by no means limited to, sources from mining processing, metallurgical processing, oil and gas processing, chemical processing, and the like. Still other feed streams not obtained from batteries may also be used.

[0011] Accordingly, in one aspect there is provided a metal compound precipitation apparatus comprising: a metal compound precipitation vessel configured to combine a feed material stream comprising one or more target metals with at least one reagent to yield a metal compound slurry, and a filter press configured to separate the metal compound slurry into a metal compound-rich solids stream and metal-depleted stream, the filter press having a graphite filter aid to improve filtration efficacy.

[0012] The graphite filter aid may comprise internally-sourced graphite powder obtained from upstream processing of the feed material stream. The graphite filter aid may comprise externally-sourced graphite powder. The graphite filter aid may comprise: internally-sourced graphite powder, the internally-sourced graphite powder obtained from upstream processing of the feed material stream; and externally- sourced graphite powder. [0013] The graphite powder may be combined with one or more of: the feed material stream, the at least one reagent, and the metal compound slurry. The graphite powder may be added as a separate feed into the metal compound precipitation vessel. The graphite powder may be combined with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation vessel. The graphite powder may be combined with the metal compound slurry downstream of the metal compound precipitation vessel.

[0014] The graphite powder may be added as a precoating layer onto a surface of a filter medium of the filter press. The graphite powder may be mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto the surface of the filter medium of the filter press.

[0015] The graphite powder may be both: combined with one or more of: the feed material stream, the at least one reagent, and the metal compound slurry; and added as a precoating layer onto a surface of a filter medium of the filter press.

[0016] The graphite filter aid may comprise graphite powder combined with one or more of the feed material stream, the at least one reagent, and the metal compound slurry. The graphite powder may be added as a separate feed into the metal compound precipitation vessel. The graphite powder may be combined with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation vessel. The graphite powder may be combined with the metal compound slurry downstream of the metal compound precipitation vessel.

[0017] The graphite filter aid may comprise graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of a filter medium of the filter press.

[0018] The graphite filter aid may comprise both: graphite powder combined with one or more of the feed material stream, the at least one reagent, and the metal compound slurry; and graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of a filter medium of the filter press.

[0019] In another aspect, there is provided a method of separating one or more metal compounds from a feed material stream comprising one or more metals, the method comprising: subjecting the feed material stream to a metal compound precipitation process to yield a metal compound slurry; and filtering, in the presence of a graphite filter aid, the metal compound slurry to yield a metal compound-rich solids stream and a metal-depleted stream, the graphite filter aid improving filtration efficacy.

[0020] The graphite filter aid may comprise internally-sourced graphite powder obtained from upstream processing of the feed material stream . The graphite filter aid may comprise externally-sourced graphite powder. The graphite filter aid may comprise: internally-sourced graphite powder obtained from upstream processing of the feed material stream; and externally-sourced graphite powder.

[0021] The method may further comprise: combining the graphite powder with one or more of: the feed material stream, at least one reagent, and the metal compound slurry. The combining may comprise: adding the graphite powder as a separate feed during the metal compound precipitation process. The combining may comprise: combining the graphite powder with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation process. The combining may comprise: combining the graphite powder with the metal compound slurry downstream of the metal compound precipitation process.

[0022] The filtering may be carried out using a filter press, and method may further comprise: adding the graphite powder as a precoating layer onto a surface of a filter medium of the filter press. The method may further comprise: mixing the graphite powder with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being added onto the surface of the filter medium as the precoating layer. The adding may be carried out prior to the filtering. The adding may be carried out during the filtering. The filtering may be carried out using a filter press, and the method may further comprise: both: combining the graphite powder with one or more of: the feed material stream, at least one reagent, and the metal compound slurry; and adding the graphite powder as a precoating layer onto a surface of a filter medium of the filter press.

[0023] The method may further comprise: combining graphite powder with one or more of the feed material stream, at least one reagent, and the metal compound slurry, to yield the graphite filter aid. The combining may comprise: adding graphite powder as a separate feed during the metal compound precipitation process. The combining may comprise: combining the graphite powder with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation process. The combining may comprise: combining the graphite powder with the metal compound slurry downstream of the metal compound precipitation process. [0024] The filtering may be carried out using a filter press, and the method may further comprise: adding graphite powder as a precoating layer onto a surface of a filter medium of the filter press, to yield the graphite filter aid. The method may further comprise: mixing the graphite powder with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being added onto the surface of the filter medium as the precoating layer. The adding may be carried out prior to the filtering. The adding may be carried out during the filtering.

[0025] The filtering may be carried out using a filter press, and the method may further comprise::combining graphite powder with one or more of the feed material stream, at least one reagent, and the metal compound slurry, and adding graphite powder as a precoating layer onto a surface of a filter medium of the filter press, to yield the graphite filter aid. The method may further comprise: mixing at least some of the graphite powder with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being added onto the surface of the filter medium as the precoating layer.

[0026] In another aspect, there is provided a system for processing size-reduced battery materials comprising copper, aluminum, iron, graphite and black mass, the system comprising: a leaching apparatus configured to leach the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; a copper precipitation apparatus comprising: a copper sulfide precipitation vessel configured to combine the conditioned leach stream with at least one reagent to yield a copper sulfide slurry, and a filter press configured to separate the copper sulfide slurry into a copper rich solids stream and copper-depleted stream comprising the remaining leached metals from the black mass, the filter press having a graphite filter aid to improve filtration efficacy.

[0027] The graphite added to the filter press may comprise the graphite-rich product. The graphite added to the filter press may further com prise externally-sourced graphite powder.

[0028] The graphite added to the filter press may comprise externally-sourced graphite powder.

[0029] The graphite filter aid may comprise graphite powder mixed with one or more of: the conditioned leach stream, at least one reagent, and the copper sulfide slurry. The graphite powder may be mixed with one or more of: the conditioned leach stream, at least one reagent, and the copper sulfide slurry within the copper sulfide precipitation vessel. [0030] The graphite filter aid may comprise graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of the filter medium of the filter press.

[0031] The graphite filter aid may comprise: graphite powder mixed with one or more of: the conditioned leach stream, at least one reagent, and the copper sulfide slurry; and graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of the filter medium of the filter press.

[0032] The system may further comprise: an aluminum and/or iron precipitation system comprising: a gypsum precipitation vessel configured to combine the copper-depleted stream with at least one gypsum precipitation reagent to yield a gypsum slurry, and a second filter press configured to separate the gypsum slurry into a gypsum solids stream and an aluminum-depleted and/or iron-depleted stream comprising the remaining leached metals from the black mass, the second filter press having a second graphite filter aid to improve filtration efficacy.

[0033] The graphite added to the second filter press may comprise the graphite-rich product. The graphite added to the second filter press may further comprise externally- sourced graphite powder.

[0034] The graphite added to the second filter press may comprise externally-sourced graphite powder.

[0035] The second graphite filter aid may comprise graphite powder mixed with one or more of: the copper-depleted stream, the at least one gypsum precipitation reagent, and the gypsum slurry. The graphite powder may be mixed with one or more of: the copper-depleted stream, the at least one gypsum precipitation reagent, and the gypsum slurry within the gypsum precipitation vessel.

[0036] The graphite filter aid may comprise graphite powder mixed with a second slurry liquid to form a second graphite coating slurry, the second graphite coating slurry being applied onto a filter surface of the second filter press.

[0037] The graphite filter aid may comprise: graphite powder mixed with one or more of: the copper-depleted stream, the at least one gypsum precipitation reagent, and the gypsum slurry; and graphite powder mixed with a second slurry liquid to form a second graphite coating slurry, the second graphite coating slurry being applied onto a filter surface of the second filter press. [0038] In another aspect, there is provided a method of separating one or more metal species from size-reduced battery materials comprising copper, graphite and black mass, the method comprising: leaching the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; subjecting the conditioned leach stream to a copper sulfide precipitation process to yield a copper sulfide slurry; and filtering, in the presence of a graphite filter aid, the copper sulfide slurry to yield a copper rich solids stream and a copper-depleted stream, the graphite filter aid improving filtration efficacy.

[0039] The method may further comprise mixing graphite powder with one or more of the conditioned leach stream and the copper sulfide slurry to provide the graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally-sourced graphite powder.

[0040] The method may further comprise adding graphite powder during said subjecting step to provide the graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally-sourced graphite powder.

[0041] The method may further comprise mixing graphite powder with a slurry liquid to form a graphite coating slurry; and applying the graphite coating slurry onto a filter surface of a filter press carrying out said filtering to provide the graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally- sourced graphite powder.

[0042] The method may further comprise at least two of: mixing graphite powder with one or more of: the conditioned leach stream and the copper sulfide slurry to provide the graphite filter aid; adding graphite powder during said subjecting step to provide the graphite filter aid; and mixing graphite powder with a slurry liquid to form a graphite coating slurry, and applying the graphite coating slurry onto a filter surface of a filter press carrying out said filtering to provide the graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally-sourced graphite powder.

[0043] The method may further comprise subjecting the copper-depleted stream to a gypsum precipitation process to yield a gypsum slurry; and second filtering, in the presence of a second graphite filter aid, the gypsum slurry to yield gypsum solids stream and an aluminum-depleted and/or iron-depleted stream comprising the remaining leached metals from the black mass, the second graphite filter aid improving filtration efficacy. [0044] The method may further comprise mixing graphite powder with one or more of the copper-depleted stream and the gypsum slurry to provide the second graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally-sourced graphite powder.

[0045] The method may further comprise adding graphite powder during said step of subjecting the copper-depleted stream to the gypsum precipitation process, to provide the second graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally-sourced graphite powder.

[0046] The method may further comprise: mixing graphite powder with a second slurry liquid to form a second graphite coating slurry; and applying the second graphite coating slurry onto a filter surface of a second filter press carrying out said second filtering to provide the second graphite filter aid. The graphite powder may be at least one of: the graphite-rich product; and externally-sourced graphite powder.

[0047] The method may further comprise at least two of: mixing graphite powder with one or more of the copper-depleted stream and the gypsum slurry to provide the second graphite filter aid; adding graphite powder during said step of subjecting the copper-depleted stream to the gypsum precipitation process, to provide the second graphite filter aid; and mixing graphite powder with a second slurry liquid to form a second graphite coating slurry, and applying the second graphite coating slurry onto a filter surface of a second filter press carrying out said second filtering to provide the second graphite filter aid. The graphite powder may be at least one of: the graphiterich product; and externally-sourced graphite powder.

[0048] In another aspect, there is provided a system for processing size-reduced battery materials comprising one or more metals, graphite and black mass, the system comprising: a leaching apparatus configured to leach the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; a metal compound precipitation apparatus comprising: a metal compound precipitation vessel configured to combine the conditioned leach stream with at least one reagent to yield a metal compound slurry, and a filter press configured to separate the metal compound slurry into a metal compound-rich solids stream and metal-depleted stream comprising the black mass, the filter press having a graphite filter aid to improve filtration efficacy. [0049] In another aspect, there is provided a method of separating one or more metal compounds from size-reduced battery materials comprising one or more metals, graphite and black mass, the method comprising: leaching the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; subjecting the conditioned leach stream to a metal compound precipitation process to yield a metal compound slurry; and filtering, in the presence of a graphite filter aid, the metal compound slurry to yield a metal compound-rich solids stream and a metal- depleted stream, the graphite filter aid improving filtration efficacy.

[0050] Other advantages of the invention will become apparent to those of skill in the art upon reviewing the present specification.

BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Embodiments of the present invention will be described with reference to the accompanying drawings, wherein like reference numerals denote like parts, and in which:

[0052] Figure 1 is a schematic representation of one example of a system that can be used to recover one or more metals from battery materials;

[0053] Figure 2 is a schematic representation of a primary size reduction apparatus forming part of the system of Figure 1 ;

[0054] Figure 3 is a schematic representation of a precipitation apparatus forming part of the system of Figure 1 ;

[0055] Figure 4 is an example of a method for recovering one or more metals from battery materials using the system of Figure 1 ;

[0056] Figure 5 is a schematic representation of another example of a system that can be used to recover one or more metals from battery materials;

[0057] Figure 6 is a schematic representation of a precipitation apparatus forming part of the system of Figure 5;

[0058] Figure 7 is a schematic representation of still another example of a system that can be used to recover one or more metals from battery materials;

[0059] Figure 8 is a schematic representation of a precipitation apparatus forming part of the system of Figure 7;

[0060] Figure 9 is a schematic representation of yet another example of a system that can be used to recover one or more metals from battery materials;

[0061] Figure 10 is a schematic representation of a precipitation apparatus forming part of the system of Figure 9;

[0062] Figure 11 is an example of a method for recovering one or more metals from battery materials using the system of Figure 9; [0063] Figure 12 is a schematic representation of another embodiment of a precipitation apparatus forming part of a hydrometallurgical process system;

[0064] Figure 13 is an example of a method for recovering one or more metals from an incoming feed material stream using the apparatus of Figure 12;

[0065] Figure 14 is a schematic representation of still another embodiment of a precipitation apparatus forming part of a hydrometallurgical process system;

[0066] Figure 15 is a schematic representation of still yet another embodiment of a precipitation apparatus forming part of a hydrometallurgical process system;

[0067] Figure 16 is a photographic view of an experimental filtration apparatus used in accordance with examples described herein; and

[0068] Figure 17 is a graphical plot of calculated filtrate flux as a function of cake thickness in accordance with examples described herein.

DETAILED DESCRIPTION

[0069] Various apparatuses or processes will be described below to provide an example of an embodiment of each claimed invention. No embodiment described below limits any claimed invention and any claimed invention may cover processes or apparatuses that differ from those described below. The claimed inventions are not limited to apparatuses or processes having all of the features of any one apparatus or process described below or to features common to multiple or all of the apparatuses described below. It is possible that an apparatus or process described below is not an embodiment of any claimed invention. Any invention disclosed in an apparatus or process described below that is not claimed in this document may be the subject matter of another protective instrument, for example, a continuing patent application, and the applicants, inventors, or owners do not intend to abandon, disclaim, or dedicate to the public any such invention by its disclosure in this document.

[0070] Lithium-ion batteries are a type of rechargeable battery in which lithium ions drive an electrochemical reaction. Lithium has a high electrochemical potential and a high energy density. Lithium-ion battery cells have four key components: a. Positive electrode/cathode: including differing formulations of metal oxides or metal phosphate depending on battery application and manufacturer, deposited on to a cathode backing foil/current collector (e.g. aluminum) - for example: LiNixMn_yCo_zO2 (NMC); LiCoC (LCO); LiFePC (LFP); LiMn₂O₄ (LMO); LiNiCoAIO₂ (NCA); b. Negative electrode/anode: generally, comprises graphite deposited on to an anode backing foil/current collector (e.g. copper); c. Electrolyte: for example, lithium hexafluorophosphate (LiPFe), lithium tetrafluoroborate (UBF4), lithium perchlorate (LiCIC ), lithium hexafluoroarsenate monohydrate (LiAsFe W), lithium trifluoromethanesulfonate (UCF3SO3), lithium bis(bistrifluoromethanesulphonyl) (LiC₂F₆NO₄S₂), lithium organoborates, or lithium fluoroalkylphosphates dissolved in an organic solvent (e.g., mixtures of alkyl carbonates, e.g. C1-C6 alkyl carbonates such as ethylene carbonate (EC, generally required as part of the mixture for sufficient negative electrode/anode passivation), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC)); and d. Separator between the cathode and anode: for example, polymer or ceramic based. [0071] As noted above, "black mass", as used herein refers to a combination of cathode and/or anode electrode powders from lithium-ion batteries. The chemical composition of black mass varies based on the battery type and composition being processed. Lithium cathode and anode (graphite) powders are expected to be the primary components of black mass. Other materials may also be present in black mass, including, residual organic electrolyte (e.g. C1-C6 alkyl carbonates, such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate (PC), and mixtures thereof), iron, aluminum, cadmium, cobalt, nickel, copper, plastics, and/or possibly both iron and phosphorous if the batteries include LFP batteries.

[0072] The systems and processes for obtaining the black mass from batteries can generally include one or more suitable, size reduction operations in which incoming batteries in the form of whole batteries, cells and/or portions thereof, along with any associated leads, housings, wires and the like (collectively referred to as battery materials) are at least physically processed to liberate the black mass materials within the battery cell for further processing. This can include physically shredding the incoming battery materials, such as using a suitable comminuting apparatus, in an operation that can break open the battery cells and can convert the incoming battery materials into a plurality of relatively small, size-reduced battery materials that can be further processed. The black mass material, and some other materials, can be formed into a slurry that travels downstream from the comminuting apparatus, and is optionally subjected to one or more separation or further processing steps to help separate the various materials present in the slurry into one or more relatively pure product streams. For example, further processing, if appropriate, can include using one or more suitable process steps and/or apparatuses including washing, screening, filtering, leaching and the like to separate the desired black mass product material (including one or more potentially valuable, target metals) from the other materials (such as plastics, other metals, other packaging materials, at least a portion of the electrolyte and other such materials). The desired black mass materials can contain the outputs/products from these processing steps.

[0073] For example, Figure 1 shows a schematic representation of an example of a system 100 for recovering one or more metals from battery materials. In the example shown, the system 100 includes at least a primary size reduction apparatus 102 that is configured to receive incoming batteries and/or battery materials 104. One example of a suitable apparatus that can be used as part of the apparatus 102 can be described as an immersion comminuting apparatus that can include a housing that has at least one battery inlet through which battery materials can be introduced into the housing.

[0074] The size reduction apparatus 102 preferably has at least a first, submergible comminuting device that can be disposed within the housing and is preferably configured to cause a first or primary size reduction of the battery materials to form reduced-size battery materials (which can include a mixture of size-reduced plastic material, size-reduced metal material and other materials) and to help liberate metal, including lithium or other metals depending on the type of battery being processed, and cathode materials and other metals from within the battery materials.

[0075] The size reduction apparatus may include two or more separate comminuting apparatuses in series in some examples, and each immersion comminuting apparatus may itself have one, two or more submerged comminuting devices contained therein and arranged in series, such that the size reduction apparatus may include two or more size-reduction steps in series, and may allow for intervening process steps between the size-reduction steps.

[0076] For the purposes of the teachings herein, the overall operations of the first, or primary size reduction apparatus can be described as a first or primary size reduction process or generally as a size-reduced stream, where generally raw or unprocessed incoming battery materials can enter the size reduction apparatus 102 and then one or more streams of size-reduced material that are sent to other process steps are obtained. The content of these post-size reduction apparatus 102 material can be described has having size-reduced or primary-reduced materials (i.e. fragments of the incoming battery materials), along with black mass and organic electrolytes and other materials entrained regardless of the number of internal size-reduction steps employed in the size reduction apparatus 102.

[0077] For example, a size reduction apparatus 102 with a single shredding stage can receive incoming battery materials 104, conduct at least a first size reduction and produce primary-reduced materials that are sent for further processing. Similarly, a size reduction apparatus 102 that includes two separate immersion comminuting apparatuses arranged in series (each with at least one submerged comminuting device) and with some product take-off streams between them can also be described as receiving the incoming battery materials, conducting at least a first size reduction process and producing primary-reduced materials for the purposes of the teachings herein.

[0078] The immersion liquid may be provided within the housing of the immersion comminuting apparatus and preferably is configured to submerge at least the first comminuting device, and optionally may also cover at least some of the battery materials. The first size reduction of the battery materials using this apparatus can thereby be conducted under the immersion material (and under immersion conditions) whereby the presence of oxygen is supressed, absorption of heat and the chemical treatment of electrolyte by the immersion liquid. This may also cause the electrolyte materials, the black mass material and the reduced-size plastic and metal materials to become at least partially entrained within the immersion liquid to form a blended material or slurry. Some of the size-reduced material may also float on the immersion liquid. The immersion comminuting apparatus may therefore include a plastics outlet that is positioned toward its upper end and through which a plastics slurry can be extracted, and one or more metal outlets that are provided toward the lower end of the immersion comminuting apparatus and through which a metals slurry/ outlet stream can be extracted. The metals slurry/ outlet stream will likely include a majority of the metal pieces and a mixture of the metallic foils, the cathode materials, electrolyte and immersion material. The plastics slurry may contain a majority of the plastic and other buoyant material, but can also include a relatively small amount of the size-reduced metal, black mass material and electrolyte materials as described herein.

[0079] The incoming battery materials 104 can be large format batteries or small format batteries, and can include complete battery cells, battery packs and other combinations of batteries, packaging, housings and the like. Large format lithium-ion batteries can be, for example, batteries measuring from about 370 mm x about 130 mm x about 100 mm to about 5000 mm x about 2000 mm x about 1450 mm in size (or volume equivalents; expressed as a rectangular prism for simplification of geometry), and can include electric car batteries or batteries used in stationary energy storage systems. Small format batteries can be, for example, batteries measuring up to about 370 mm x about 130 mm x about 100 mm in size (or volume equivalents; expressed as a rectangular prism for simplification of geometry), and can include portable batteries such as those from cell phones, laptops, power tools or electric bicycles. Large format batteries are generally known in the art to be larger than small format batteries. In another embodiment, the battery materials can comprise battery parts as opposed to whole batteries or battery packs; however, the apparatus, system, and process described herein may be particularly suited to processing whole batteries.

[0080] The primary size reduction apparatus 102 is preferably configured so that it can produce at least two, and optionally more output streams that include different components that have been liberated from the incoming battery materials. For example, the primary size reduction apparatus 102 is preferably configured so that plastics can be withdrawn via at least one plastic recovery stream and non-plastics, including optionally the black mass material and other materials, such as copper and aluminium foils, can be withdrawn via at least one non-plastic or metals recovery stream. This can allow the plastic material to be processed generally separately from the metal or other non-plastic materials.

[0081] The size reduction apparatus is preferably configured so that it can complete at least the first size reduction step on the incoming battery materials under immersion conditions. That is, a size reduction apparatus can have a housing containing at least one comminuting device (e.g. a shredder) that is submerged in a suitable immersion liquid (or other suitable immersion material) while shredding the battery materials. The size reduction apparatus can be any suitable apparatus, including those described herein and those described in PCT Application Publication No. WO 2018/218358, and PCT Application Publication No. WO 2021/174348, the entire contents of which are incorporated herein by reference.

[0082] The immersion liquids may be basic and are preferably at least electrically conductive to help absorb/dissipate any residual electric charge from the incoming battery materials. The immersion liquid may be selected such that it reacts with lithium salt (e.g. LiPFe) that may be produced via the liberation of the electrolyte materials during the size reduction process, whereby the evolution of hydrogen fluoride during the size reduction is inhibited. The immersion liquid may include a salt, whereby the immersion liquid is electrically conductive to help at least partially dissipate a residual electrical charge within the battery materials that is released during the size reduction. The salt may include at least one of sodium hydroxide, calcium hydroxide and lithium hydroxide.

[0083] The immersion liquid within the housing of the primary immersion apparatus 102 may preferably be at an operating temperature that is less than 70 degrees Celsius to inhibit chemical reactions between the electrolyte materials and the immersion liquid, and optionally the operating temperature may be less than 60 degrees Celsius. Preferably, the immersion liquid may have a pH that is greater than or equal to 8, and optionally may include at least one of sodium hydroxide, and calcium hydroxide.

[0084] The immersion comminuting apparatus is preferably configured so that the immersion liquid is at substantially atmospheric pressure (i.e. less than about 1.5 bar) when the system is in use and does not require a sealed gas handling system or other mechanism for capturing or sequestering gases escaping from the immersion liquid, which can simplify the design and operation of the apparatus and system.

[0085] Particles that are liberated from the battery materials by the comminuting apparatus 102 during the first size reduction may be captured and entrained within the immersion liquid and may be inhibited from escaping the housing into the surrounding atmosphere. The first comminuting device may be configured as a shredder that is configured to cause size reduction of the battery materials by at least one of compression and shearing. The black mass material obtained using these processes, including at least some residual amounts of the immersion liquid and any electrolytes entrained therein can form the black mass feed materials as described herein. In these configurations, the size reduction can be conducted on batteries that have at least some partial or residual charge, and optionally on batteries that are more than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% charged and may be fully charged. Preferably, the primary size reduction process can be executed without having to first discharge the incoming batteries or otherwise reduce the charge state of the incoming batteries, because the immersion conditions can help suppress the heat generation and sparking that would otherwise be problematic when shredding batteries with a residual electrical charge. This can help simplify the method and can eliminate the need for a separate discharging step prior to the size reduction in the processes. [0086] In the illustrated example shown schematically in Figure 2, the primary size reduction apparatus 102 is configured so that it can carry out a first size reduction and shred the incoming battery materials 104 via at least one shredding/comminuting device submerged in a suitable immersion liquid, whereby plastics and other relatively light materials will float in the immersion liquid and metals and other relatively heavy materials will tend to sink. The plastic materials can be skimmed or otherwise extracted as a plastics slurry from the shredding/comminuting device via a plastic recovery stream 204. The materials as shredded via this first comminuting apparatus 102 can also be described as primary-reduced metal material, primary-reduced plastic material herein.

[0087] The primary sized-reduced battery materials can form a metals stream 106 that exits the primary size reduction apparatus 102, and can include a majority of the black mass materials liberated in the primary size reduction apparatus 102 and/or copper and aluminum foils that have been separated from the plastics. For example, the metals slurry exiting via the metals stream 106 may include at least 60%, 70%, 80%, 90%, 95% wt. or more of the liberated black mass materials, which may be advantageous if the metals stream 106 is to be sent for further processing to separate the metals and preferably recover at least some of the lithium from the black mass.

[0088] Conversely, a relatively smaller, minority amount of the liberated black mass material, such as less than 15%, or less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1 % wt. of the expected/liberated black mass material may be captured in the plastics slurry. As this black mass material that escapes via the plastics slurry may be commercially valuable, it may be advantageous to recover at least some of the black mass material that escapes the primary comminuting apparatus 102 via the plastics slurry.

[0089] The size reduction apparatus 102 may have any suitable configuration and may include one, two or more physical/mechanical processing steps (in two or more separate apparatuses or physical structures shown schematically as sub-apparatuses 210 in Figure 2) that can be help convert the incoming battery materials to suitable size-reduced battery materials that can then form at least part of the metals stream 106 that exits the size reduction apparatus 102 for further processing. For example, the size reduction apparatus 102 may include one or more suitable comminuting apparatus that can grind/shred the battery materials, thereby liberating materials from within the battery cells and reducing the physical size of the battery materials. A single stage comminuting apparatus may be configured so that the battery materials only pass through one comminuting device 210 before exiting the apparatus 102, although there may be several comminuting devices arranged in parallel within a single housing/apparatus or in separating housings/apparatuses to accommodate a desired volume of incoming battery materials. Alternatively, the apparatus 102 may include two or more comminuting devices 210 arranged in series, such that the incoming battery materials undergo at least two, and optionally more, size reduction processes in series. It is also possible that in some examples of the systems and processes described herein that other materials could be added as part of the disassembly processes and one or more chemical or physical reactions could also occur within the apparatus 102.

[0090] Whether a single or multiple processing steps are used within the apparatus 102, and/or whether any other processes or reactions occur, the metal materials exiting the apparatus 102 via stream 106 can be further processed via a suitable a separation system/ apparatus, described below, in which the materials can be processed using one or more suitable process steps and/or apparatus (including washing, screening, filtering and the like) to separate the desired black mass product material from the other materials. The plastic recovery stream 204 can be described as the plastics slurry that is understood to include both plastic material pieces as well as the mixture of immersion liquid, black mass material and other inadvertently captured metals and cells as used herein. After leaving the size reduction apparatus 102, the plastics slurry in the plastic recovery stream 204 can be processed via a plastic recovery circuit 212 that can include multiple sub-steps and assemblies.

[0091] The sized-reduced battery materials exiting the size reduction apparatus 102, in stream 106, may be fed directly into a suitable precipitation apparatus. Alternatively, as illustrated schematically in Figure 1 , the extracted metals stream 106 can then be further processed, if appropriate, using one or more suitable process steps and/or apparatuses including washing, screening, filtering, leaching and the like to separate the desired black mass product material from the other materials (such as plastics, other metals, other packaging materials, at least a portion of the electrolyte and other such materials). The desired black mass materials can be obtained as one of the outputs/products from the separation apparatus.

[0092] For example, the exemplary system 100 includes an optional processing system 108 that can receive the metals stream 106 and process it to produce a conditioned material stream that is relatively rich in copper, and possibly other target metals (including cobalt, nickel and others described herein), as compared to the composition of the untreated metals stream 106, and also contains quantities of lithium, aluminum, graphite and other materials. The composition of this conditioned material stream 110 that exits the processing system 108, may vary based on the type of treatment process that is used, even if processing the same incoming black mass material.

[0093] Preferably, the processing system 108 may include hardware suitable for at least partially leaching the metals stream 106 so that a conditioned material stream 110 in the form of a pregnant leach solution (PLS) is provided. For example, the black mass material may be leached using suitable reagents (such as sulfuric acid or other acids, hydrogen peroxide, oxygen and a combination thereof and other reagents) to generate the PLS. At the conclusion of the leaching step the resulting stream can be filtered to separate the solids as a graphite rich product 220, and produce a pregnant leach solution that is relatively rich in at least lithium and copper amongst other minor components and/or solvents and that is the conditioned material stream 110 in this example. The processing system 108 is preferably configured so that the conditioned material stream 110 (e.g. the PLS in this example) is relatively more suitable for further processing using the via the method and systems described herein than the native pre-processed metals stream 106 would have been.

[0094] The graphite rich product 220 may include at least a portion of any graphite that was in the black mass material, anode and/or cathode binder, residual solid cathode and the like. In one example, the graphite rich product 220 can be between about 65 and about 80 weight % graphite (carbon), with the large part of the difference being moisture at between about 15 to about 25 weight %. The remainder may be made up of trace constituents, such as for example cobalt, nickel, lithium, aluminum, and copper.

[0095] As will be described below, it has been discovered that the graphite rich product 220, which primarily consists of graphite, can be used as a filter aid in one or more downstream apparatuses and methods to improve filtration efficacy, namely to increase average filtrate flux during the filtration period and/or reduce filtration cycle time (namely, the length of time to form, wash, and discharge a filter cake) required for separating various products by filter. It has also been discovered that some examples of products that do not filter well (namely, easily and/or quickly) without such a graphite filter aid are copper sulphide, calcium sulphate (gypsum) and metal hydroxides. These products can exhibit low flux rates and, correspondingly, very long filtration cycle times, sometimes longer than 6 hours, to form a proper filter cake. Generally, acceptable (namely, cost-effective) flux rates are about 200 L/m²hr, depending on the product being filtered. Low flux rates and corresponding long cycle times required to filter certain products would otherwise require uncharacteristically large filter presses, which creates equipment sourcing issues and increases equipment costs.

[0096] Advantageously, utilizing the graphite rich product 220, which can otherwise be regarded as a low-value product, as a filter aid downstream obviates these concerns, and can be used to increase filtration flux from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and 250 L/m²h. As will be understood, as used herein the graphite filter aid may comprise an accumulation of graphite on the surface of a filter medium of the filter press. The filter medium of the filter press may be any suitable medium used for filtering, such as for example filter paper, filter cloth, a fine mesh screen, and the like.

[0097] Alternatively, and in this and other examples described below, at least a portion of the graphite rich product 220 can include additional graphite powder that may be supplied from an external supply of graphite powder, such as for example externally- sourced “pure” or relatively pure graphite powder. In one such embodiment, the graphite rich product 220 may be combined with the additional graphite powder after exiting the processing system 108, for use as a filter aid downstream. In another embodiment, the additional graphite powder can be used instead of the graphite rich product 220, for use as a filter aid downstream.

[0098] To conduct the sulphide precipitation, the system 100 includes a schematic representation of a precipitation apparatus 112 that receives the incoming feed material stream (optionally the metals stream 106, the conditioned material stream 110 or from another suitable source) and can also receive a supply of a desired sulphide reductant 114, as well as at least a portion of the graphite rich product 220 (and/or optional additional graphite powder) exiting the processing system 108. In this example, the relative proportion of incoming feed material stream (optionally the metals stream 106, the conditioned material stream 110) to the graphite rich product 220 can range from about 20 to about 100 grams of graphite rich product 220 (and/or optional additional graphite powder) per litre of slurry 106 or 110. The precipitation apparatus 112 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein. Referring to Figure 3, in one schematic representation the precipitation apparatus 112 includes a primary precipitation vessel 120 that can receive the incoming metals stream 106 or 110 (or other), the sulphide reductant 114, and the graphite rich product. This vessel 120 can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).

[0099] A solid/liquid separator 122 is, in this example, provided downstream from the precipitation vessel 120 and can receive a copper sulphide slurry 124 exiting the precipitation vessel 120. In this example the separator 122 can be a filter press, and the separated metal sulphide solids, which include at least some of the graphite solids introduced via the graphite rich product 220 (and/or optional additional graphite powder), can be extracted in the form of a filter cake as solids stream 126, while the now copper-depleted stream 128 can be sent for further processing. The copper- depleted stream 128 can be held in an optional storage tank 130 until needed, and can then exit the precipitation apparatus 112 as the copper-depleted stream 128.

[00100] As will be understood, the graphite solids within the copper sulphide slurry 124, which includes at least some of the graphite solids introduced via the graphite rich product 220 (and/or optional additional graphite powder), provide a filter aid, and improve filtration efficacy by increasing the average filtrate flux during the filtration period in the separator 122 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00101] Referring again to Figure 1 , the copper-depleted stream 128 can be sent for further processing via a downstream hydrometallurgical processing system 140 that can include any suitable processes and systems, including leaching, precipitation, filters and other operations that can help separate and extract the various target products, including utilizing the processes and systems described in PCT Application Publication No. WO 2018/218358, and PCT Application Publication No. WO 2021/174348, the entire contents of which are incorporated herein by reference.

[00102] In this schematic illustration, the downstream hydrometallurgical processing system 140 can include an aluminum and/or iron precipitation system 142 via which the copper-depleted stream 128 can be processed to remove iron and aluminum that may be contained in the copper-depleted stream 128. This may include apparatus for the separation of iron from othertarget metals (such as cobalt and nickel, for example) and may help facilitate other downstream processing, via stream 144, or other materials from copper-depleted stream 128. Other suitable separation systems 146 can be used to further process the process slurries and material streams and can be configured to recover at least the target lithium as a lithium output stream 148.

[00103] Referring to Figure 4, a flow chart illustrates an example of a method 300 for recovering metal from battery materials that can be exemplified by the systems, including system 100 described herein. This method 300 includes, at step 302, receiving incoming batteries and/or battery materials (such as stream 104) to produce a metals stream.

[00104] At step 304, the metals stream is subjected to a processing step (such as using processing system 108) to separate out a graphite rich product therefrom, and to produce a conditioned material stream in the form of a pregnant leach solution (PLS).

[00105] At step 306, the conditioned material stream is subjected to a copper sulphide precipitation step (such as using precipitation apparatus 112), in which the conditioned material stream is combined with the desired sulphide reductant in a precipitation apparatus, and then subjected to separation using a filter press, to yield the copper-depleted stream, and the solids stream which comprises the copper sulphide precipitate.

[00106] During step 306, the graphite rich product from step 304 (and/or optional additional graphite powder) is utilized as a filter aid (as indicated by the additional arrow) to yield the copper-depleted stream and the solids stream which comprises the copper sulphide precipitate. In this example, the graphite rich product from step 304 is combined with the conditioned material stream and desired sulphide reductant in a precipitation apparatus, and then subjected to the separation using the filter press, to yield the copper-depleted stream and the solids stream which comprises the copper sulphide precipitate.

[00107] Other examples are contemplated, some of which are described below. For example, in other examples, alternatively, or additionally, the graphite rich product from step 304 (and/or optional additional graphite powder) may be combined with a suitable slurry liquid in a graphite slurry vessel to yield a graphite coating slurry, which is then applied directly onto a surface of the filter medium of the filter press. The conditioned material stream is combined with the desired sulphide reductant in the precipitation apparatus, and then subjected to separation using the filter press, to yield the copper-depleted stream, and the solids stream which comprises the copper sulphide precipitate.

[00108] At step 308, the copper-depleted stream is subjected to further processing (such as using downstream hydrometallurgical processing system 140), in which other target materials, including lithium and/or gypsum, may be extracted from the filtrate stream. Some examples of suitable systems and separation processes that can be used to help separate at least the lithium from the filtrate stream, at step 308, can include those used by and available from Li-Cycle Corp, (of Toronto, Canada) and are described in PCT Application Publication No. WO 2018/218358 entitled A Process, Apparatus, And System For Recovering Materials From Batteries, PCT Application Publication No. WO 2022/246566 entitled System And Method For Recovering Plastic From Battery Materials, and PCT Application Publication No. WO 2021/174348 entitled A Method for Processing Lithium Iron Phosphate Batteries, the entire contents of which are incorporated herein by reference.

[00109] Variations are contemplated. For example, Figure 5 shows another embodiment of a system, which is generally indicated by reference numeral 400. System 400 is generally similar to system 100 described above and with reference to Figures 1 to 3, and comprises the primary size reduction apparatus 102, the processing system 108, a precipitation apparatus 412, and the downstream hydrometallurgical processing system 140.

[00110] The precipitation apparatus 412 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein. Referring to Figure 6, in one schematic representation the precipitation apparatus 412 includes the primary precipitation vessel 120 that can receive the incoming metals stream 106 or 110 (or other) and the sulphide reductant 114.

[00111] The precipitation apparatus 412 also includes a graphite slurry vessel 430 that can receive the graphite rich product 220 (and/or optional additional graphite powder), in addition to a suitable slurry liquid via an incoming slurry liquid supply stream 432, and can include suitable mixing apparatus (such as a mixer, agitator, and the like) to combine the graphite and slurry liquid therein and thereby output a graphite coating slurry 434. In the example shown, the slurry liquid delivered via incoming slurry liquid supply stream 432 may be water. The graphite slurry vessel 430 can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).

[00112] The solid/liquid separator 122 is, in this example, provided downstream from the precipitation vessel 120 can receive the copper sulphide slurry 124 exiting the precipitation vessel 120. The solid/liquid separator 122 is, in this example, also provided downstream from the graphite slurry vessel 430, and can receive the graphite coating slurry 434 exiting the graphite slurry vessel 430. In this example the separator 122 can be a filter press, and can include or be operably coupled to suitable devices and/or apparatus (not shown) to apply the graphite coating slurry 434 directly onto a surface of the filter medium of the filter press. The graphite coating slurry 434 can be applied prior to filtration (namely, as a precoating), during filtration, or both prior to and during filtration, of the copper sulfide slurry 124 by the solid/liquid separator 122.

[00113] As will be understood, the graphite solids within the graphite coating slurry 434, which includes at least some of the graphite solids introduced via the graphite rich product 220 (and/or optional additional graphite powder), provide a filter aid on a surface of the filter medium of the filter press, and improve filtration efficacy by increasing the average filtrate flux during the filtration period in the separator 122 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00114] The separated metal sulphide solids can be extracted via the solids stream 126, while the now copper-depleted stream 128 can be sent for further processing. The copper-depleted stream 128 can be held in an optional storage tank 130 until needed, and can then exit the precipitation apparatus 412 as the copper- depleted stream 128.

[00115] In the example shown, the slurry liquid conveyed via slurry liquid supply stream 432 to the graphite slurry vessel 430 may be water, however in other examples, other suitable slurry liquids may alternatively be used. In still another example (not shown), the slurry liquid conveyed via slurry liquid supply stream 432 may be a portion of the copper-depleted stream 128 used as a recycle stream. As will be understood, using a portion of the copper-depleted stream 128 as the slurry liquid to yield the graphite coating slurry advantageously reduces or prevents dilution of the liquids and streams within the precipitation apparatus 412, and of the liquids and streams downstream in the system 400.

[00116] Still other variations are contemplated. For example, Figure 7 shows another embodiment of a system, which is generally indicated by reference numeral 500. System 500 is generally similar to system 100 described above and with reference to Figures 1 to 3, and comprises the primary size reduction apparatus 102, the processing system 108, a precipitation apparatus 512, and the downstream hydrometallurgical processing system 140.

[00117] The precipitation apparatus 512 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein. Referring to Figure 8, in one schematic representation the precipitation apparatus 512 includes the primary precipitation vessel 120 that can receive the incoming metals stream 106 or 110 (or other), the sulphide reductant 114, and a first portion of the graphite rich product 220 (and/or optional additional graphite powder).

[00118] The precipitation apparatus 512 also includes the graphite slurry vessel 430 that can receive a second portion of the graphite rich product 220 (and/or optional additional graphite powder), in addition to the suitable slurry liquid via the incoming slurry liquid supply stream 432, and can include the suitable apparatus to combine the graphite and slurry liquid therein and thereby output the graphite coating slurry 434.

[00119] The solid/liquid separator 122 is, in this example, provided downstream from the precipitation vessel 120 and can receive the copper sulphide slurry 124 exiting the precipitation vessel 120. The separator 122 can be the filter press, and the separated metal sulphide solids. As will be understood, the graphite solids within the separated metal sulphide solids, which include at least some of the graphite solids introduced via the first portion of the graphite rich product 220 (and/or optional additional graphite powder), provide a first filter aid, and improve filtration efficacy by increasing the average filtrate flux during the filtration period in the separator 122 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00120] The solid/liquid separator 122 is, in this example, also provided downstream from the graphite slurry vessel 430, and can also receive the graphite coating slurry 434 exiting the graphite slurry vessel 430. In this example the separator 122, can include or be operably coupled to suitable devices and/or apparatus (not shown) to apply the graphite coating slurry 434 directly onto a surface of the filter medium of the filter press. The graphite coating slurry 434 can be applied prior to filtration (namely, as a precoating), during filtration, or both prior to and during filtration, of the copper sulfide slurry 124 by the solid/liquid separator 122

[00121] As will be understood, the graphite solids within the graphite coating slurry 434, which includes at least some of the graphite solids introduced via the second portion of the graphite rich product 220 (and/or optional additional graphite powder), provide a second filter aid on a surface of the filter medium of the filter press, and also and improve filtration efficacy by increasing the average filtrate flux during the filtration period and/or reducing filtration cycle time in the separator 122 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00122] The separated metal sulphide solids can be extracted via the solids stream 126, while the now copper-depleted stream 128 can be sent for further processing. The copper-depleted stream 128 can be held in an optional storage tank 130 until needed, and can then exit the precipitation apparatus 512 as the copper- depleted stream 128.

[00123] In the example shown, the slurry liquid conveyed via slurry liquid supply stream 432 to the graphite slurry vessel 430 may be water, however in other examples, other suitable slurry liquids may alternatively be used. In still another example (not shown), the slurry liquid conveyed via slurry liquid supply stream 432 may be a portion of the copper-depleted stream 128 used as a recycle stream. As will be understood, using a portion of the copper-depleted stream 128 as the slurry liquid to yield the graphite coating slurry advantageously reduces or prevents dilution of the liquids and streams within the precipitation apparatus 512, and of the liquids and streams downstream in the system 500.

[00124] Still other variations are contemplated. Forexample, Figure 9 shows still another embodiment of a system, which is generally indicated by reference numeral 600. System 600 is generally similar to system 100 described above and with reference to Figures 1 to 3, and comprises the primary size reduction apparatus 102, the processing system 108, the precipitation apparatus 112, an aluminum and/or iron precipitation system 642, and a downstream hydrometallurgical processing system 640. [00125] In this example, and as shown Figure 9, the graphite rich product 220 exiting the processing system 108 (and/or optional additional graphite powder) is divided into two quantities, namely a first quantity that is fed to the precipitation apparatus 112, and a second quantity that is fed to the aluminum and/or iron precipitation system 642.

[00126] To conduct the aluminum and/or iron precipitation, the aluminum and/or iron precipitation system 642 receives the incoming copper-depleted stream 128 and can also receive a supply of a desired reagent and/or slurry a supply of a desired liquid, as well as at least a portion of the graphite rich product 220 (and/or optional additional graphite powder) exiting the processing system 108. The aluminum and/or iron precipitation system 642 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein.

[00127] Referring to Figure 10, in one schematic representation the aluminum and/or iron precipitation system 642 includes a primary precipitation vessel 660 that can receive the incoming copper-depleted stream 128, a gypsum precipitation reagent 662, and a first portion of the second quantity of the graphite rich product 220 (and/or optional additional graphite powder). The gypsum precipitation reagent 662 may be, for example, calcium hydroxide (Ca(OH)2), which may be added in an amount of for example from about 1 to about 30 % by weight of the incoming copper-depleted stream 128. Other suitable gypsum precipitation reagents, such as for example calcium carbonate (CaCOa) may alternatively, or additionally be used. In one example, the gypsum precipitation reagent 662 may react with aluminum sulfate species and iron sulfate species present in the copper-depleted stream 128 to form metal hydroxide species and to precipitate gypsum, in accordance with the following formulas:

AI₂(SO4)3 + 3Ca(OH)₂ + 2H₂O 2AI(OH)₃ + 3CaSO4.2H₂O

Fe₂(SO₄)3 + 3Ca(OH)₂ + 2H₂O 2Fe(OH)₃ + 3CaSO4.2H₂O

[00128] This vessel 660 can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).

[00129] The aluminum and/or iron precipitation system 642 can also include a graphite slurry vessel 670 that can receive a second portion of the second quantity of the graphite rich product 220 (and/or optional additional graphite powder), in addition to a suitable slurry liquid via an incoming slurry liquid supply stream 672, and can include the suitable apparatus to combine the graphite and slurry liquid therein and thereby output a graphite coating slurry 674. In the example shown, the slurry liquid delivered via incoming slurry liquid supply stream 672 may be water. The graphite slurry vessel 670 can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).

[00130] A solid/liquid separator 682 is, in this example, provided downstream from the precipitation vessel 660 and can receive a gypsum slurry 684 exiting the precipitation vessel 660. The separator 682 can be the filter press, and the separated metal sulphide solids, which include at least some of the graphite solids introduced via the first portion of the second quantity of graphite rich product 220 (and/or optional additional graphite powder). As will be understood, the graphite solids within the gypsum slurry 684, which include at least some of the graphite solids present in the first portion of the second quantity of the graphite rich product 220 (and/or optional additional graphite powder), provide a first filter aid, and improve filtration efficacy by increasing the average filtrate flux during the filtration period in the separator 682 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00131] The solid/liquid separator 682 is, in this example, also provided downstream from the graphite slurry vessel 670, and can also receive the graphite coating slurry 674 exiting the graphite slurry vessel 670. In this example the separator 682, can include or be operably coupled to suitable devices and/or apparatus (not shown) to apply the graphite coating slurry 674 directly onto a surface of the filter medium of the filter press. The graphite coating slurry 674 can be applied prior to filtration (namely, as a precoating), during filtration, or both priorto and during filtration, of the gypsum slurry 684 by the solid/liquid separator 682.

[00132] As will be understood, the graphite solids within the graphite coating slurry 674, which includes at least some of the graphite solids introduced via the second portion of the second quantity of the graphite rich product 220 (and/or optional additional graphite powder), provide a second filter aid on a surface ofthe filter medium of the filter press, and improve filtration efficacy by increasing the average filtrate flux during the filtration period in the separator 682 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr. [00133] The separated metal sulphide solids can be extracted via the solids stream 144, while a now aluminum-depleted and/or iron-depleted stream 688 can be sent for further processing. The aluminum-depleted and/or iron-depleted stream 688 can be held in an optional storage tank 690 until needed, and can then exit the aluminum and/or iron precipitation system 642 as the aluminum-depleted and/or iron- depleted stream 688.

[00134] In the example shown, the slurry liquid conveyed via slurry liquid supply stream 672 to the graphite slurry vessel 670 may be water, however in other examples, other suitable slurry liquids may alternatively be used. In still another example (not shown), the slurry liquid conveyed via slurry liquid supply stream 672 may be a portion of the aluminum-depleted and/or iron-depleted stream 688 used as a recycle stream. As will be understood, using a portion of the aluminum-depleted and/or iron-depleted stream 688 as the slurry liquid to yield the graphite coating slurry advantageously reduces or prevents dilution of the liquids and streams within the aluminum and/or iron precipitation system 642, and of the liquids and streams downstream in the system 600.

[00135] Referring again to Figure 9, the aluminum-depleted and/or iron-depleted stream 688 can be sent for further processing via a downstream hydrometallurgical processing system 640, which can include any suitable processes and systems, including leaching, precipitation, filters and other operations that can help separate and extract the various target products, including utilizing the processes and systems described in PCT Application Publication No. WO 2018/218358, and PCT Application Publication No. WO 2021/174348, the entire contents of which are incorporated herein by reference.

[00136] Referring to Figure 11 , a flow chart illustrates an example of a method 700 for recovering metal from battery materials that can be exemplified by the systems, including system 600 described herein. This method 700 includes, at step 702, receiving incoming batteries and/or battery materials (such as stream 104) to produce a metals stream.

[00137] At step 704, the metals stream is subjected to a processing step (such as using processing system 108) to separate out a graphite rich product therefrom, and to produce a conditioned material stream in the form of a pregnant leach solution (PLS).

[00138] At step 706, the conditioned material stream is subjected to a copper sulphide precipitation step (such as using precipitation apparatus 112), in which a first quantity of the graphite rich product from step 704 (and/or optional additional graphite powder) is combined (as indicated by the additional arrow) with the conditioned material stream and desired sulphide reductant in a precipitation apparatus, and then subjected to separation using a filter press, to yield the copper-depleted stream, and the solids stream which comprises the copper sulphide precipitate.

[00139] At step 708, the copper-depleted stream is subjected to an aluminum and/or iron precipitation step (such as using aluminum and/or iron precipitation system 642), in which a first portion of a second quantity of the graphite rich product from step 704 (and/or optional additional graphite powder) is combined (as indicated by the additional arrow) with the copper-depleted stream and a desired reagent in a precipitation apparatus, and then subjected to separation using a filter press, to yield an aluminum-depleted and/or iron-depleted stream, and a solids stream which comprises the gypsum precipitate. Additionally, a second portion of the second quantity of the graphite rich product from step 704 (and/or optional additional graphite powder) is combined (as indicated by the additional arrow) with a suitable slurry liquid in a graphite slurry vessel to yield a graphite coating slurry, which is then applied directly onto a surface of the filter medium of the filter press.

[00140] Variations are contemplated. For example, in other examples, alternatively, the entire second quantity of the graphite rich product from step 704 (and/or optional additional graphite powder) may either be combined with the copper- depleted stream and the desired reagent in the precipitation apparatus, or alternatively may be combined with the suitable slurry liquid in the graphite slurry vessel to yield the graphite coating slurry, which is then applied directly onto a surface of the filter medium of the filter press.

[00141] At step 710, the aluminum-depleted and/or iron-depleted stream is subjected to further processing (such as using downstream hydrometallurgical processing system 740), in which other target materials, including lithium, may be extracted from the filtrate stream. Some examples of suitable systems and separation processes that can be used to help separate at least the lithium from the filtrate stream, at step 710, can include those used by and available from Li-Cycle Corp, (of Toronto, Canada) and are described in international patent publication no. WO2018/218358 entitled A Process, Apparatus, And System For Recovering Materials From Batteries, international patent publication no. WO2022/246566 entitled System And Method For Recovering Plastic From Battery Materials, and international patent publication no. WO202 1/174348 entitled A Method for Processing Lithium Iron Phosphate Batteries, each of which are incorporated herein by reference.

[00142] Still other variations of broader scope, and which utilize the same general principles of the graphite filter aid described above, are contemplated. For example, Figure 12 shows a precipitation apparatus 812 that may form part of a larger processing system (not shown), such as a hydrometallurgical processing system, or may alternatively be operated as a standalone apparatus. It will be understood that one or more components of the precipitation apparatus 812 may also be operated in a standalone manner. The precipitation apparatus 812 is configured to receive an incoming feed material stream 810 comprising one or more target metals. The feed material stream 810 may be obtained from battery materials, or may alternatively be obtained from other sources not including battery materials, such as for example, and by no means limited to, sources from mining processing, metallurgical processing, oil and gas processing, chemical processing, and the like.

[00143] The precipitation apparatus 812 receives an incoming graphite feed 820 that comprises any form of graphite obtained from one or more sources. For example, the incoming graphite feed 820 may comprise any of externally-sourced graphite obtained from one or more external sources, internally-sourced graphite obtained from upstream processing of the incoming feed stream 810 (assuming the upstream form of the incoming feed stream 810 contains graphite), or a combination of externally- sourced graphite and internally-sourced graphite.

[00144] To conduct the precipitation, the precipitation apparatus 812 receives the incoming feed material stream 810 and can also receive a supply of a desired reagent 814, as well as the graphite feed 820. The reagent 814 may be any substance capable of reacting with at least one of the one or more target metals in the incoming feed material stream 810, to produce a metal compound precipitate. The reagent 814 may be, for example, a sulphide, a phosphate (e.g. sodium phosphate), a hydroxide (e.g. calcium hydroxide, magnesium hydroxide, sodium hydroxide, etc.), and mixtures thereof. Still other suitable reagents may be used. [00145] In this example, the relative proportion of incoming feed material stream 810 to the graphite feed 820 can range from about 20 to about 100 grams of graphite feed 820 per litre of incoming feed material stream 810. The precipitation apparatus 812 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein. In the schematic representation shown in Figure 12, the precipitation apparatus 812 includes a primary precipitation vessel 818 that can receive the incoming feed material stream 810, the reagent 814, and the graphite feed 820. This vessel 818 can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).

[00146] A solid/liquid separator 822 is, in this example, provided downstream from the precipitation vessel 818 and can receive a metal compound precipitate slurry 824 exiting the precipitation vessel 818. In this example the separator 822 can be a filter press, and the separated metal compound precipitate solids, which include at least some of the graphite solids introduced via the graphite feed 820, can be extracted in the form of a filter cake as solids stream 826, while a filtrate stream 828, which is depleted in one or more target metals extracted via the solids stream 826, can be sent for further processing. The filtrate stream 828 can be held in an optional storage tank 830 until needed, and can then exit the precipitation apparatus 812 as the filtrate stream 828.

[00147] As will be understood, the graphite solids within the metal compound precipitate slurry 824 provide a filter aid, and improve filtration efficacy by increasing the average filtrate flux during the filtration period and/or reducing filtration cycle time in the separator 822 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00148] Referring to Figure 13, a flow chart illustrates an example of a method 900 for recovering metal from an incoming feed material stream that can be exemplified by the apparatuses, including precipitation apparatus 812, described herein. This method 900 includes, at step 902, receiving an incoming feed material stream (such as incoming feed material stream 810).

[00149] At step 906, the incoming feed material stream is subjected to a metal compound precipitation step (such as using precipitation apparatus 812), in which the incoming feed material stream is combined with the desired reagent in a precipitation apparatus, and then subjected to separation using a filter press, to yield the filtrate stream, and the solids stream which comprises the metal compound precipitate solids. [00150] During step 906, a graphite feed is utilized as a filter aid to yield the filtrate stream and the solids stream which comprises the metal compound precipitate solids. In this example, the graphite feed is combined with the incoming feed material stream and desired reagent in a precipitation apparatus, and then subjected to the separation using the filter press, to yield the filtrate stream and the solids stream which comprises the metal compound precipitate solids.

[00151] Other examples are contemplated, some of which are described below. For example, in other examples, alternatively, or additionally, the graphite feed (and/or optional additional graphite powder) may be combined with a suitable slurry liquid in a graphite slurry vessel to yield a graphite coating slurry, which is then applied directly onto a surface of the filter medium of the filter press.

[00152] Still other variations are contemplated. For example, Figure 14 shows a precipitation apparatus 1012. Precipitation apparatus 1012 is generally similar to precipitation apparatus 812 described above, and may form part of a larger processing system (not shown), such as a hydrometallurgical processing system, or may alternatively be operated as a standalone apparatus. It will be understood that one or more components of the precipitation apparatus 1012 may also be operated in a standalone manner. The precipitation apparatus 1012 is configured to receive the incoming feed material stream 810 comprising the one or more target metals. As described above, feed material stream 810 may be obtained from battery materials, or may alternatively be obtained from other sources not including battery materials, such as for example, and by no means limited to, sources from mining processing, metallurgical processing, oil and gas processing, chemical processing, and the like [00153] The precipitation apparatus 1012 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein. In the schematic representation shown in Figure 14, the precipitation apparatus 1012 includes the precipitation vessel 818 that can receive the incoming feed material stream 810 and the reagent 814.

[00154] The precipitation apparatus 1012 also includes a graphite slurry vessel 1030 that can receive the incoming graphite feed 820, in addition to a suitable slurry liquid via an incoming slurry liquid supply stream 1032, and can include suitable mixing apparatus (such as a mixer, agitator, and the like) to combine the graphite and slurry liquid therein and thereby output a graphite coating slurry 1034. In the example shown, the slurry liquid delivered via incoming slurry liquid supply stream 1032 may be water. The graphite slurry vessel 1030 can be a tank or other suitable vessel that can be operated at the conditions described herein, and can include any suitable agitators, valves, pumps, spargers and other flow control devices. It can be controlled via a suitable controller (such as a computer, PLC or the like).

[00155] As described above, the incoming graphite feed 820 may comprise any of externally-sourced graphite obtained from one or more external sources, internally- sourced graphite obtained from upstream processing of the incoming feed stream 810 (assuming the upstream form of the incoming feed stream 810 contains graphite), or a combination of externally-sourced graphite and internally-sourced graphite.

[00156] The solid/liquid separator 822 is, in this example, provided downstream from the precipitation vessel 818 and can receive the metal compound precipitate slurry 824 exiting the precipitation vessel 818. The solid/liquid separator 822 is, in this example, also provided downstream from the graphite slurry vessel 1030, and can receive the graphite coating slurry 1034 exiting the graphite slurry vessel 1030. In this example the separator 822 can be a filter press, and can include or be operably coupled to suitable devices and/or apparatus (not shown) to apply the graphite coating slurry 1034 directly onto a surface of the filter medium of the filter press. The graphite coating slurry 1034 can be applied prior to filtration (namely, as a precoating), during filtration, or both prior to and during filtration, of the metal compound precipitate slurry 824 by the solid/liquid separator 822.

[00157] As will be understood, the graphite solids within the graphite coating slurry 1034, which includes at least some of the graphite solids introduced via the graphite feed 820, provide a filter aid on a surface of the filter medium of the filter press, and improve filtration efficacy by increasing the average filtrate flux during the filtration period and/or reducing filtration cycle time in the separator 822 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00158] The separated metal compound precipitate solids can be extracted via the solids stream 826, while the filtrate stream 828, which is depleted in one or more target metals that extracted via the solids stream 826, can be sent for further processing. The filtrate stream 828 can be held in an optional storage tank 830 until needed, and can then exit the precipitation apparatus 1012 as the filtrate stream 828. [00159] In the example shown, the slurry liquid conveyed via slurry liquid supply stream 1032 to the graphite slurry vessel 1030 may be water, however in other examples, other suitable slurry liquids may alternatively be used. In still another example (not shown), the slurry liquid conveyed via slurry liquid supply stream 1032 may be a portion of the filtrate stream 828 used as a recycle stream. As will be understood, using a portion of the filtrate stream 828 as the slurry liquid to yield the graphite coating slurry advantageously reduces or prevents dilution of the liquids and streams within the precipitation apparatus 1012, and of the liquids and streams downstream therefrom.

[00160] Still other variations are contemplated. For example, Figure 15 shows a precipitation apparatus 1112 that may form part of a larger hydrometallurgical processing system (not shown). Precipitation apparatus 1112 is generally similar to precipitation apparatus 812 described above, and may form part of a larger processing system (not shown), such as a hydrometallurgical processing system, or may alternatively be operated as a standalone apparatus. It will be understood that one or more components of the precipitation apparatus 1112 may also be operated in a standalone manner. The precipitation apparatus 1112 is configured to receive the incoming feed material stream 810 comprising the one or more target metals. As described above, feed material stream 810 may be obtained from battery materials, or may alternatively be obtained from other sources not including battery materials, such as for example, and by no means limited to, sources from mining processing, metallurgical processing, oil and gas processing, chemical processing, and the like.

[00161] The precipitation apparatus 1112 can include any suitable combination of hardware (including tanks, vessels, conduits, flow control hardware or the like), including as described herein. Referring to Figure 15, in one schematic representation the precipitation apparatus 1112 includes the primary precipitation vessel 818 that can receive the incoming feed material stream 810, the reagent 814, and a first portion of the graphite feed 820.

[00162] As described above, the incoming graphite feed 820 may comprise any of externally-sourced graphite obtained from one or more external sources, internally- sourced graphite obtained from upstream processing of the incoming feed stream 810 (assuming the upstream form of the incoming feed stream 810 contains graphite), or a combination of externally-sourced graphite and internally-sourced graphite. [00163] The precipitation apparatus 1112 also includes the graphite slurry vessel 1030 that can receive a second portion of the graphite feed 820, in addition to the suitable slurry liquid via the incoming slurry liquid supply stream 1032, and can include the suitable apparatus to combine the graphite and slurry liquid therein and thereby output the graphite coating slurry 1034.

[00164] The solid/liquid separator 822 is, in this example, provided downstream from the precipitation vessel 818 and can receive the metal compound precipitate slurry 824 exiting the precipitation vessel 818. The separator 822 can be the filter press. As will be understood, the graphite solids within the separated metal solids, which include at least some of the graphite solids introduced via the first portion of the graphite feed 820, provide a first filter aid, and improve filtration efficacy by increasing the average filtrate flux during the filtration period and/or reducing filtration cycle time in the separator 822 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00165] The solid/liquid separator 822 is, in this example, also provided downstream from the graphite slurry vessel 1030, and can also receive the graphite coating slurry 1034 exiting the graphite slurry vessel 1030. In this example the separator 822, can include or be operably coupled to suitable devices and/or apparatus (not shown) to apply the graphite coating slurry 1034 directly onto a surface of the filter medium of the filter press. The graphite coating slurry 1034 can be applied prior to filtration (namely, as a precoating), during filtration, or both prior to and during filtration, of the metal compound precipitate slurry 824 by the solid/liquid separator 822 [00166] As will be understood, the graphite solids within the graphite coating slurry 1034, which includes at least some of the graphite solids introduced via the second portion of the graphite feed 820, provide a second filter aid on a surface of the filter medium of the filter press, and also improve filtration efficacy by increasing the average filtrate flux during the filtration period in the separator 822 from less than 200 L/m²hr to greater than 200 L/m²hr, and for example to between about 200 L/m²hr and about 250 L/m²hr.

[00167] The separated metal compound precipitate solids, which include at least some of the graphite solids introduced via the graphite feed 820, can be extracted in the form of a filter cake as solids stream 826, while a filtrate stream 828, which is depleted in one or more target metals extracted via the solids stream 826, can be sent for further processing. The filtrate stream 828 can be held in an optional storage tank 830 until needed, and can then exit the precipitation apparatus 1112 as the filtrate stream 828.

[00168] In the example shown, the slurry liquid conveyed via slurry liquid supply stream 1032 to the graphite slurry vessel 1030 may be water, however in other examples, other suitable slurry liquids may alternatively be used. In still another example (not shown), the slurry liquid conveyed via slurry liquid supply stream 1032 may be a portion of the filtrate stream 828 used as a recycle stream. As will be understood, using a portion of the filtrate stream 828 as the slurry liquid to yield the graphite coating slurry advantageously reduces or prevents dilution of the liquids and streams within the precipitation apparatus 1112, and of the liquids and streams downstream therefrom.

[00169] For the purposes of describing operating ranges and other such parameters herein the phrase "about" or "approximately" means a difference from the stated values or ranges that does not make a material difference in the operation of the systems and processes described herein, including differences that would be understood a person of skill in the relevant art as not having a material impact on the present teachings. For pressures and temperatures about may, in some examples, mean plus or minus 10% of the stated value but is not limited to exactly 10% or less in all situations. For example, a pH of about 2 may be understood to include a pH between 1.8 and 2.2. Similarly, "substantially all" can be understood to mean practically and/or materially all of the substance has been removed from the solution, and may mean separation efficiencies of at least 90%, or higher in some instance as would be understood by a person skilled in the art.

[00170] The following examples illustrate various applications of the abovedescribed embodiments.

[00171] EXAMPLE 1

[00172] An experimental, laboratory bench-scale filtration apparatus comprised a 90 mm diameter Buchner funnel fitted with a 90 mm filter paper, and a Caframo™ BDC2002 agitator installed with its impeller positioned in the approximate center of the volume of the Buchner funnel. A controller of the BDC2002 agitator was set to rotate the agitator shaft at 350 rpm. The Buchner funnel was connected to a vacuum pump. Vacuum applied to the Buchner funnel was measured to be -0.76 bar. A graduated flask was situated under the Buchner funnel to collect filtrate. A photographic view of the experimental, laboratory bench-scale filtration apparatus is shown in Figure 16.

[00173] A 469 mL volume of a pregnant leach solution (PLS) slurry comprising approximately 58 g/L copper sulfide solids was added to the Buchner funnel, and the vacuum and agitator were turned on once the level of the slurry exceeded the level of the agitator impeller. The time elapsed after turning on the vacuum and agitator was recorded when the filtrate volume reached 150 mL, and at every 50 mL increment thereafter. Once filtrate flow had ceased, a final time was recorded and the filter cake was removed from the filter paper and its thickness was measured using a caliper. The filtrate volume, time and final thickness measurements were then used to calculate, by interpolation, the approximate cake thickness and the approximate filtrate flux at each instance of time recordation.

[00174] The results of the filtration test are shown in Table 1 , below.

TABLE 1

[00175] In total, 469 mL of slurry was added to the Buchner funnel to reach a filter cake thickness of 7 mm. The total time to reach the cake thickness of 7 mm was about 29 minutes. The average filtrate flux during the filtration period was calculated to be 131 L/m²hr.

[00176] EXAMPLE 2

[00177] The experimental, laboratory bench-scale filtration apparatus of

Example 1 was also used for this example. A 381 mL volume of slurry was prepared by combining approximately 377 mL of pregnant leach solution (PLS) slurry having approximately 52 g/L copper sulfide solids, with 5 g of diatomaceous earth (DE) solids, supplied by Dicalite Management Group, to yield a DE-containing PLS slurry comprising approximately 15 g/L DE solids. Prior to filtration, the filter paper was precoated with a separately prepared precoat slurry comprising 40 g/L of DE in water. Filtrate from the precoating procedure was discarded

[00178] With the filter paper coated by the DE “pre-coat” slurry, the DE- containing PLS slurry was added to the Buchner funnel, and the vacuum and agitator were turned on once the level of the slurry exceeded the level of the agitator impeller. The time elapsed after turning on the vacuum and agitator was recorded when the filtrate volume reached 150 mL, and at every 50 mL increment thereafter. Once filtrate flow had ceased, a final time was recorded and the filter cake was removed from the filter paper and its thickness was measured using a caliper. The filtrate volume, time and final thickness measurements were then used to calculate, by interpolation, the approximate cake thickness and the approximate filtrate flux at each instance of time recordation.

[00179] In total, 381 mL of DE-containing PLS slurry was added to the Buchner funnel to reach a filter cake thickness of 7 mm. The total time to reach the cake thickness of 7 mm was 780 seconds (13 minutes). The average filtrate flux during the filtration period was calculated to be 250 L/m²hr.

[00180] EXAMPLE 3

[00181] The experimental, laboratory bench-scale filtration apparatus of

Example 1 was also used for this example. A 381 mL volume of slurry was prepared by combining approximately 377 mL of pregnant leach solution (PLS) slurry having approximately 52 g/L copper sulfide solids, with 5 g graphite, supplied by Asbury Carbons Inc. and purchased from McMaster Carr Supply Company, to yield a graphitecontaining PLS slurry comprising approximately 15 g/L graphite solids. Prior to filtration, the filter paper was precoated with a separately prepared precoat slurry comprising 40 g/L of graphite in water. Filtrate from the precoating procedure was discarded.

[00182] With the filter paper coated by the graphite “pre-coat” slurry, the graphitecontaining PLS slurry was added to the Buchner funnel, and the vacuum and agitator were turned on once the level of the slurry exceeded the level of the agitator impeller. The time elapsed after turning on the vacuum and agitator was recorded when the filtrate volume reached 150 mL, and at every 50 mL increment thereafter. Once filtrate flow had ceased, a final time was recorded and the filter cake was removed from the filter paper and its thickness was measured using a caliper. The filtrate volume, time and final thickness measurements were then used to calculate, by interpolation, the approximate cake thickness and the approximate filtrate flux at each instance of time recordation.

[00183] In total, 381 mL of graphite-containing PLS slurry was added to the Buchner funnel to reach a filter cake thickness of 7 mm. The total time to reach the cake thickness of 7 mm was 780 seconds (13 minutes). The average filtrate flux during the filtration period was calculated to be 250 L/m²hr.

[00184] Figure 17 shows a graphical plot of calculated filtrate flux as a function of cake thickness for the slurries of Example 1 (namely, without a filter aid) and Example 2 or 3 (namely, with a filter aid). As can be seen, the presence of the filter aid clearly increases the filtrate flux.

[00185] All publications, patents, and patent applications referred to herein are incorporated by reference in their entirety to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference in its entirety. It is understood that the teachings of the present application are exemplary embodiments and that other embodiments may vary from those described. Such variations are not to be regarded as a departure from the spirit and scope of the teachings and may be included within the scope of the following claims.

Claims

What is claimed is:

1 . A metal compound precipitation apparatus comprising: a metal compound precipitation vessel configured to combine a feed material stream comprising one or more target metals with at least one reagent to yield a metal compound slurry, and a filter press configured to separate the metal compound slurry into a metal compound-rich solids stream and metal-depleted stream, the filter press having a graphite filter aid to improve filtration efficacy.

2. The apparatus of claim 1 , wherein the graphite filter aid comprises internally- sourced graphite powder obtained from upstream processing of the feed material stream.

3. The apparatus of claim 1 , wherein the graphite filter aid comprises externally- sourced graphite powder.

4. The apparatus of claim 1 , wherein the graphite filter aid comprises: internally-sourced graphite powder, the internally-sourced graphite powder obtained from upstream processing of the feed material stream; and externally-sourced graphite powder.

5. The apparatus of any one of claims 2 to 4, wherein the graphite powder is combined with one or more of: the feed material stream, the at least one reagent, and the metal compound slurry.

6. The apparatus of claim 5, wherein the graphite powder is added as a separate feed into the metal compound precipitation vessel.

7. The apparatus of claim 5, wherein the graphite powder is combined with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation vessel.

8. The apparatus of claim 5, wherein the graphite powder is combined with the metal compound slurry downstream of the metal compound precipitation vessel.

9. The apparatus of any one of claims 2 to 4, wherein the graphite powder is added as a precoating layer onto a surface of a filter medium of the filter press.

10. The apparatus of claim 9, wherein the graphite powder is mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto the surface of the filter medium of the filter press.

11 . The apparatus of any one of claims 2 to 4, wherein the graphite powder is both: combined with one or more of: the feed material stream, the at least one reagent, and the metal compound slurry; and added as a precoating layer onto a surface of a filter medium of the filter press.

12. The apparatus of claim 1 , wherein the graphite filter aid comprises graphite powder combined with one or more of the feed material stream, the at least one reagent, and the metal compound slurry.

13. The apparatus of claim 12, wherein the graphite powder is added as feed into the metal compound precipitation vessel.

14. The apparatus of claim 12, wherein the graphite powder is combined with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation vessel.

15. The apparatus of claim 12, wherein the graphite powder is combined with the metal compound slurry downstream of the metal compound precipitation vessel.

16. The apparatus of claim 1 , wherein the graphite filter aid comprises graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of a filter medium of the filter press.

17. The apparatus of claim 1 , wherein the graphite filter aid comprises both: graphite powder combined with one or more of the feed material stream, the at least one reagent, and the metal compound slurry; and graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of a filter medium of the filter press.

18. A method of separating one or more metal compounds from a feed material stream comprising one or more metals, the method comprising: subjecting the feed material stream to a metal compound precipitation process to yield a metal compound slurry; and filtering, in the presence of a graphite filter aid, the metal compound slurry to yield a metal compound-rich solids stream and a metal-depleted stream, the graphite filter aid improving filtration efficacy.

19. The method of claim 18, wherein the graphite filter aid comprises internally- sourced graphite powder obtained from upstream processing of the feed material stream.

20. The method of claim 18, wherein the graphite filter aid comprises externally- sourced graphite powder.

21. The method of claim 18, wherein the graphite filter aid comprises: internally-sourced graphite powder obtained from upstream processing of the feed material stream; and externally-sourced graphite powder.

22. The method of any one of claims 19 to 21 , further comprising: combining the graphite powder with one or more of: the feed material stream, at least one reagent, and the metal compound slurry.

23. The method of claim 22, wherein the combining comprises: adding the graphite powder as a separate feed during the metal compound precipitation process.

24. The method of claim 22, wherein the combining comprises: combining the graphite powder with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation process.

25. The method of claim 22, wherein the combining comprises: combining the graphite powder with the metal compound slurry downstream of the metal compound precipitation process.

26. The method of any one of claims 19 to 21 , wherein said filtering is carried out using a filter press, and further comprising: adding the graphite powder as a precoating layer onto a surface of a filter medium of the filter press.

27. The method of claim 26, further comprising: mixing the graphite powder with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being added onto the surface of the filter medium as the precoating layer.

28. The method of claim 26 or 27, wherein said adding is carried out prior to said filtering.

29. The method of any one of claims 26 to 28, wherein said adding is carried out during said filtering.

30. The method of any one of claims 19 to 21 , wherein said filtering is carried out using a filter press, and further comprising both: combining the graphite powder with one or more of: the feed material stream, at least one reagent, and the metal compound slurry; and adding the graphite powder as a precoating layer onto a surface of a filter medium of the filter press.

31 . The method of claim 18, further comprising: combining graphite powder with one or more of the feed material stream, at least one reagent, and the metal compound slurry, to yield the graphite filter aid.

32. The method of claim 31 , wherein the combining comprises: adding graphite powder as a separate feed during the metal compound precipitation process

33. The method of claim 31 , wherein the combining comprises: combining the graphite powder with one or both of the feed material stream and the at least one reagent upstream of the metal compound precipitation process.

34. The method of claim 31 , wherein the combining comprises: combining the graphite powder with the metal compound slurry downstream of the metal compound precipitation process.

35. The method of claim 18, wherein said filtering is carried out using a filter press, and further comprising: adding graphite powder as a precoating layer onto a surface of a filter medium of the filter press, to yield the graphite filter aid.

36. The method of claim 35, further comprising: mixing the graphite powder with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being added onto the surface of the filter medium as the precoating layer.

37. The method of claim 35 or 36, wherein said adding is carried out prior to said filtering.

38. The method of any one of claims 35 to 37, wherein said adding is carried out during said filtering.

39. The method of claim 18, wherein said filtering is carried out using a filter press, and further comprising: combining graphite powder with one or more of the feed material stream, at least one reagent, and the metal compound slurry, and. adding graphite powder as a precoating layer onto a surface of a filter medium of the filter press, to yield the graphite filter aid.

40. The method of claim 39, further comprising: mixing at least some of the graphite powder with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being added onto the surface of the filter medium as the precoating layer.

41 . A system for processing size-reduced battery materials comprising copper, graphite and black mass, the system comprising: a leaching apparatus configured to leach the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; a copper precipitation apparatus comprising: a copper sulfide precipitation vessel configured to combine the conditioned leach stream with at least one reagent to yield a copper sulfide slurry, and a filter press configured to separate the copper sulfide slurry into a copper rich solids stream and copper-depleted stream comprising the black mass, the filter press having a graphite filter aid to improve filtration efficacy.

42. The system of claim 41 , wherein the graphite added to the filter press comprises the graphite-rich product.

43. The system of claim 42, wherein the graphite added to the filter press further comprises externally-sourced graphite powder.

44. The system of claim 41 , wherein the graphite added to the filter press comprises externally-sourced graphite powder.

45. The system of claim 41 , wherein the graphite filter aid comprises graphite powder mixed with one or more of: the conditioned leach stream, at least one reagent, and the copper sulfide slurry.

46. The system of claim 45, wherein the graphite powder mixed with one or more of: the conditioned leach stream, at least one reagent, and the copper sulfide slurry within the copper sulfide precipitation vessel.

47. The system of claim 41 , wherein the graphite filter aid comprises graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of the filter medium of the filter press.

48. The system of claim 41 , wherein the graphite filter aid comprises: graphite powder mixed with one or more of: the conditioned leach stream, at least one reagent, and the copper sulfide slurry; and graphite powder mixed with a slurry liquid to form a graphite coating slurry, the graphite coating slurry being applied onto a surface of the filter medium of the filter press.

49. The system of any one of claims 41 to 48, further comprising: an aluminum and/or iron precipitation system comprising: a gypsum precipitation vessel configured to combine the copper- depleted stream with at least one gypsum precipitation reagent to yield a gypsum slurry, and a second filter press configured to separate the gypsum slurry into a gypsum solids stream and an aluminum-depleted and/or iron-depleted stream comprising the remaining leached metals from the black mass, the second filter press having a second graphite filter aid to improve filtration efficacy.

50. The system of claim 49, wherein the graphite added to the second filter press comprises the graphite-rich product.

51 . The system of claim 50, wherein the graphite added to the second filter press further comprises externally-sourced graphite powder.

52. The system of claim 49, wherein the graphite added to the second filter press comprises an externally-sourced graphite powder.

53. The system of claim 49, wherein the second graphite filter aid comprises graphite powder mixed with one or more of: the copper-depleted stream, the at least one gypsum precipitation reagent, and the gypsum slurry.

54. The system of claim 53, wherein the graphite powder mixed with one or more of: the copper-depleted stream, the at least one gypsum precipitation reagent, and the gypsum slurry within the gypsum precipitation vessel.

55. The system of claim 49, wherein the graphite filter aid comprises graphite powder mixed with a second slurry liquid to form a second graphite coating slurry, the second graphite coating slurry being applied onto a filter surface of the second filter press.

56. The system of claim 49, wherein the graphite filter aid comprises: graphite powder mixed with one or more of: the copper-depleted stream, the at least one gypsum precipitation reagent, and the gypsum slurry; and graphite powder mixed with a second slurry liquid to form a second graphite coating slurry, the second graphite coating slurry being applied onto a filter surface of the second filter press.

57. A method of separating one or more metal species from size-reduced battery materials comprising copper, graphite and black mass, the method comprising: leaching the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; subjecting the conditioned leach stream to a copper sulfide precipitation process to yield a copper sulfide slurry; and filtering, in the presence of a graphite filter aid, the copper sulfide slurry to yield a copper rich solids stream and a copper-depleted stream, the graphite filter aid improving filtration efficacy.

58. The method of claim 57, further comprising mixing graphite powder with one or more of the conditioned leach stream and the copper sulfide slurry to provide the graphite filter aid.

59. The method of claim 58, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

60. The method of claim 57, further comprising adding graphite powder during said subjecting step to provide the graphite filter aid.

61 . The method of claim 60, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

62. The method of claim 57, further comprising: mixing graphite powder with a slurry liquid to form a graphite coating slurry; and applying the graphite coating slurry onto a filter surface of a filter press carrying out said filtering to provide the graphite filter aid.

63. The method of claim 62, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

64. The method of claim 57, further comprising at least two of: mixing graphite powder with one or more of: the conditioned leach stream and the copper sulfide slurry to provide the graphite filter aid; adding graphite powder during said subjecting step to provide the graphite filter aid; and mixing graphite powder with a slurry liquid to form a graphite coating slurry, and applying the graphite coating slurry onto a filter surface of a filter press carrying out said filtering to provide the graphite filter aid.

65. The method of claim 64, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

66. The method of any one of claims 57 to 65, further comprising: subjecting the copper-depleted stream to a gypsum precipitation process to yield a gypsum slurry; and second filtering, in the presence of a second graphite filter aid, the gypsum slurry to yield gypsum solids stream and an aluminum-depleted and/or iron-depleted stream comprising the remaining leached metals from the black mass, the second graphite filter aid improving filtration efficacy.

67. The method of claim 66, further comprising mixing graphite powder with one or more of the copper-depleted stream and the gypsum slurry to provide the second graphite filter aid.

68. The method of claim 67, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

69. The method of claim 66, further comprising adding graphite powder during said step of subjecting the copper-depleted stream to the gypsum precipitation process, to provide the second graphite filter aid.

70. The method of claim 69, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

71 . The method of claim 66, further comprising: mixing graphite powder with a second slurry liquid to form a second graphite coating slurry; and applying the second graphite coating slurry onto a filter surface of a second filter press carrying out said second filtering to provide the second graphite filter aid.

72. The method of claim 71 , wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

73. The method of claim 66, further comprising at least two of: mixing graphite powder with one or more of the copper-depleted stream and the gypsum slurry to provide the second graphite filter aid; adding graphite powder during said step of subjecting the copper-depleted stream to the gypsum precipitation process, to provide the second graphite filter aid; and mixing graphite powder with a second slurry liquid to form a second graphite coating slurry, and applying the second graphite coating slurry onto a filter surface of a second filter press carrying out said second filtering to provide the second graphite filter aid.

74. The method of claim 73, wherein the graphite powder is at least one of: the graphite-rich product; and externally-sourced graphite powder.

75. A system for processing size-reduced battery materials comprising one or more metals, graphite and black mass, the system comprising: a leaching apparatus configured to leach the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; a metal compound precipitation apparatus comprising: a metal compound precipitation vessel configured to combine the conditioned leach stream with at least one reagent to yield a metal compound slurry, and a filter press configured to separate the metal compound slurry into a metal compound-rich solids stream and metal-depleted stream comprising the black mass, the filter press having a graphite filter aid to improve filtration efficacy.

76. A method of separating one or more metal compounds from size-reduced battery materials comprising one or more metals, graphite and black mass, the method comprising: leaching the size-reduced battery materials to yield a conditioned leach stream and a solid, graphite-rich product; subjecting the conditioned leach stream to a metal compound precipitation process to yield a metal compound slurry; and filtering, in the presence of a graphite filter aid, the metal compound slurry to yield a metal compound-rich solids stream and a metal-depleted stream, the graphite filter aid improving filtration efficacy.