Electrochemical metal deposition system and method

Abstract

Electrochemical deposition apparatus and method for selective recovery of metals. The electrochemical deposition apparatus comprises a porous cathode material, an anode, an interelectrode region formed by the anode and the cathode, and a gas release channel. The method can include passing a solution containing the metal through the cavity, changing the oxidation state of the metal, and selectively depositing the metal on the porous cathode material. The electrochemical deposition apparatus can recover the metal from a metal supply in the form of a metal hydroxide. The recovered metal can be from any source, including but not limited to minerals, electronic waste, and black nuggets.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 195,567, entitled "Electrochemical Metal Deposition Apparatus and Method," filed June 1, 2021, and U.S. Provisional Patent Application No. 63 / 273,840, entitled "Electrochemical Metal Deposition Apparatus and Method," filed October 29, 2021, the specifications of both of which are incorporated herein by reference.

[0002] The present invention relates to electrochemical systems, devices and methods for the selective precipitation and deposition of metals from solution. [Background technology]

[0003] Technological advances are creating an ever-increasing need for metals, materials, and compounds. Political and climate concerns are also driving the need for environmentally sound metal recovery processes. Recycling of metals and metal compounds is important for the development of green and energy transition technologies, including energy storage / batteries, electric vehicles ("electric vehicles"), wind turbines, and solar cells. Minerals and metals, including rare earth ("RE") metals, are key materials in what has been called the oil of the alternative energy era, and demand for copper and RE metals is expected to increase dramatically in the coming decades. There is also a high need for recycling end-of-life batteries and other metal-containing products. Specifically, these metals include lithium, cobalt, nickel, and manganese. Cobalt, nickel, and manganese often serve as cathode materials in lithium-ion batteries. A single electric vehicle contains more than 1 kg of RE and other metals as well as lithium-ion batteries. Furthermore, countries often rely on imports to meet their production needs, especially for critical minerals and metals.

[0004] There is a need for economical, energy efficient and climate conscious processes to enable the production of sustainable metal sources. The present invention selectively separates mixed metal resources into individual metal products at reduced cost and environmental impact. The present invention provides a high throughput electrochemical process for metal recovery and separation from conventional and unconventional domestic sources, as an alternative to classical energy intensive hydrometallurgical and pyrometallurgical processes such as electrowinning or solvent extraction. Summary of the Invention [Means for solving the problem]

[0005] The present invention relates to an electrochemical deposition system comprising at least one porous cathode material and at least one anode, the at least one porous cathode material and the at least one anode forming an interelectrode region, the electrochemical deposition system further comprising a housing disposed around the at least one porous cathode material and the at least one anode, at least one gas release channel, at least one inlet, and at least one outlet. In one embodiment, the electrochemical deposition system comprises a plurality of electrochemical deposition systems arranged in series. In one embodiment, the electrochemical deposition system comprises a plurality of electrochemical deposition systems arranged in parallel.

[0006] In another embodiment, the electrochemical deposition system further comprises a filter. In another embodiment, the electrochemical deposition system further comprises a current collector. In another embodiment, the at least one porous cathode material comprises carbon nanotubes. In another embodiment, the at least one anode is porous. In another embodiment, the at least one porous cathode material is less than about 25 cm 2 ~about 10m 2 In another embodiment, the at least one porous cathode material comprises a catalyst. In another embodiment, the electrochemical deposition system further comprises at least one selective membrane.

[0007] The invention also relates to a method for electrochemically depositing a metal, the method comprising passing a solution containing the metal into a cavity, applying an electric charge to a porous cathode material at least partially disposed in the cavity, contacting the solution with the porous cathode material with the applied electric charge, altering an oxidation state of the metal, and selectively depositing at least a portion of the metal on the porous cathode material. In one embodiment, the method further comprises contacting the solution with an anode. In another embodiment, the method further comprises contacting the porous cathode material with an acid. In another embodiment, the method further comprises contacting the porous cathode material with a buffer. In another embodiment, the method further comprises generating a gas. In another embodiment, the method further comprises leaching. In another embodiment, altering the oxidation state of the metal comprises increasing the oxidation state of the metal. In another embodiment, contacting the solution with the porous cathode material comprises passing the solution across the porous cathode material. In another embodiment, contacting the solution with the porous cathode material comprises passing the solution through the porous cathode material. In another embodiment, the method further comprises removing the selectively deposited metal from the porous cathode material.

[0008] The present invention also relates to an apparatus for the selective deposition of metals and metal compounds from a solution onto an electrically conductive porous cathode material.The present invention also relates to a method for the selective deposition of metals and metal compounds from a solution onto an electrically conductive porous cathode material.

[0009] The systems, apparatus, and methods of the present invention can be used for the selective deposition of metals from solution. The terms "system" and "apparatus" are used interchangeably throughout this specification and claims.

[0010] The solution may come from a variety of sources, including, but not limited to, recycling facilities, scrap facilities, mining operations, waste deposits from mining, oil and gas production and / or refining, chemical production facilities, e-waste facilities, manufacturing facilities, water treatment facilities, scientific research facilities, or combinations thereof. The apparatus and method of the present invention may be used to remove selected metals from a solution. The removed metals may be used in the manufacture of other products, including, but not limited to, batteries, semiconductors, refined metals, electronic components, magnets, or combinations thereof. The metals may be removed from the solution by deposition on a portion of the apparatus or as a pass-through product on which the undesired metals are deposited, leaving the metals of interest to be collected. The apparatus and method may be used as a pre- or post-treatment step in a larger process for removing, extracting, or purifying a solution or metal. One advantage of the apparatus and method is that the selectivity and collection efficiency of the desired metal from the solution is improved without the need for substantial pre-treatment of the solution, i.e., multiple chemical reaction steps. The apparatus and method of the present invention allows for selective deposition of one or more metals of interest at lower and higher efficiencies compared to other apparatus and methods.

[0011] The invention also relates to the use of the chemical deposition device and system for the selective deposition of at least one metal on a porous cathode material.The invention further relates to the use of the method for electrochemically depositing at least one metal on a porous cathode material.

[0012] The present invention may be used to extract metals from solutions and / or compounds containing one or more metals that are more readily extractable from forming metal compounds via redox reactions. The present invention may form metal hydroxides and deposit the metal hydroxides on a porous cathode material. The present invention may also be used to form metal oxides in or in close proximity to a porous anode material. The metal and / or metal compound products recovered by the present invention may be removed and collected. The present invention may be used to extract metals from materials including, but not limited to, black mass, ores, concentrates, tailings, batteries, magnets, non-ferrous scrap, and used electronics.

[0013] The present invention includes electrochemical deposition apparatus and systems. The electrochemical deposition apparatus / system may comprise a flow-through electrochemical deposition system for selectively recovering metals. The selectively recovered metals may include, but are not limited to, RE metals. The selectively recovered metals may include, but are not limited to, neodymium ("Nd"), praseodymium ("Pr"), dysprosium ("Dy"), copper ("Cu"), lithium ("Li"), sodium ("Na"), magnesium ("Mg"), potassium ("K"), calcium ("Ca"), titanium ("Ti"), vanadium ("V"), chromium ("Cr"), manganese ("Mn"), arsenic ("Ar ... ), Iron ("Fe"), Cobalt ("Co"), Nickel ("Ni"), Cadmium ("Cd"), Zinc ("Zn"), Aluminum ("Al"), Silicon ("Si"), Silver ("Ag"), Tin ("Sn"), Platinum ("Pt"), Gold ("Au"), Bismuth ("Bi"), Lanthanum ("La"), Europium ("Eu"), Gallium ("Ga"), Scandium ("Sc"), and Selenium ("Sr"). Thorthium ("Sr"), Yttrium ("Y"), Zirconium ("Zr"), Niobium ("Nb"), Molybdenum ("Mo"), Ruthenium ("Ru"), Rhodium ("Rh"), Palladium ("Pd"), Indium ("In"), Hafnium ("Hf"), Tantalum ("Ta"), Tungsten ("W"), Rhenium ("Re"), Osmium ("Os"), Iridium The metals may include uranium ("U"), plutonium ("Pu"), terbium ("Tb"), promethium ("Pm"), tellurium ("Te"), or combinations thereof. The metals may be recovered from conventional sources (e.g., virgin ores) or unconventional sources (e.g., end of life magnets and batteries or coal fly ash or tailings). The invention can be implemented with existing equipment to process metals on-site. The invention reduces operational costs, energy requirements, and CO2 emissions compared to raw ore mining. 2The present invention can reduce greenhouse gas emissions (e.g., up to about 280 kg CO per kg of manufactured metal product) compared to raw ore mining. 2 ) can be reduced.

[0014] The electrochemical deposition apparatus and system may include a porous cathode material. Metal hydroxides may be deposited on the porous cathode material using cathode alkali generation. Alternative mechanisms of metal deposition may include direct cathodic reduction or direct anodic oxidation or indirect oxidation or indirect reduction. The electrochemistry may not be limited by slow diffusive mass transport. The electrochemical deposition apparatus may include a flow-through system. The flow-through system may support rapid deposition kinetics. The deposition kinetics may be at least about 200 g hr -1 m -2 The metal to be deposited has the chemical formula M n+ (OH) n , (M n+ ) m O (n×m) / 2 , or M 0 The deposited metal may be, but is not limited to, a metal carbonate or sulfate. The electrochemical deposition apparatus and system may include a modular film-like format. There may be multiple electrochemical deposition apparatus / systems. Multiple electrochemical deposition apparatuses or systems may be operated in parallel. Multiple electrochemical deposition apparatuses or systems may be operated in series. Operating multiple electrochemical deposition apparatuses or systems in series may facilitate a continuous redox process.

[0015] Objects, advantages, and novel features, as well as further scope of applicability of the present invention, will be set forth in part in the following detailed description taken in conjunction with the accompanying drawings, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention. [Brief description of the drawings]

[0016] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate one or more embodiments of the invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating one or more embodiments of the invention and are not to be construed as limiting the invention. In the drawings:

[0017] [Figure 1] FIG. 2 is a diagram of the electrochemical deposition of the present invention showing the porous cathode material and the feed flowing through the anode.

[0018] [Diagram 2] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention with impermeable boundaries.

[0019] [Diagram 3] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention with an impermeable boundary and two porous cathode materials in a stacked configuration.

[0020] [Figure 4] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention comprising an impermeable boundary and an anode disposed between two porous cathode materials.

[0021] [Diagram 5] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention including a porous cathode material and respective permeate streams across and / or through an anode.

[0022] [Figure 6] 1 is a diagram of an electrochemical deposition apparatus of the present invention with each permeate stream first traversing and / or passing through a porous cathode material and then traversing and / or passing through an anode.

[0023] [Figure 7] 1 is a diagram of an electrochemical deposition apparatus of the present invention with each permeate stream first traversing and / or passing through the anode and then traversing and / or passing through a porous cathode material.

[0024] [Figure 8] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention showing a porous cathode material and an anode in a stacked configuration.

[0025] [Figure 9] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention showing porous cathode material and anode in a stacked configuration and with different feed and / or permeate flows.

[0026] [Figure 10] FIG. 2 is a diagram of an electrochemical deposition apparatus of the present invention showing two sources.

[0027] [Figure 11] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention with two sources that merge in a central section to form a single permeate.

[0028] [Figure 12] FIG. 2 is a diagram of an electrochemical deposition apparatus of the present invention including external input streams that mix in the inter-electrode region to form a mixed permeate.

[0029] [Figure 13] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention including external influent streams that mix in the interelectrode region to form a mixed permeate, each external influent stream traversing and / or passing through a porous cathode material and an anode.

[0030] [Figure 14] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention including external influent streams that mix in the interelectrode region to form a mixed permeate, with each external influent stream first traversing and / or passing through an anode and then traversing and / or passing through a porous cathode material.

[0031] [Figure 15] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention including external influent streams that mix in the interelectrode region to form a mixed permeate, with each external influent stream first traversing and / or passing through a porous cathode material and then traversing and / or passing through an anode.

[0032] [Figure 16] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention comprising multiple porous cathode materials and anodes operating in parallel, with multiple feeds in contact with the porous cathode materials and anodes.

[0033] [Figure 17] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention comprising multiple porous cathode materials and anodes operating in parallel, with multiple feeds in contact with either the porous cathode material or the anode.

[0034] [Figure 18] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention comprising a porous cathode material and an anode operating in series, with the feed in contact with the porous cathode material and the anode.

[0035] [Figure 19] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention comprising a porous cathode material and an anode operating in series, with the feed in contact with the porous cathode material or the anode.

[0036] [Figure 20] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for metal oxide deposition.

[0037] [Figure 21] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for non-ionic metal deposition.

[0038] [Figure 22] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention having a center flow design.

[0039] [Diagram 23] FIG. 1 is a diagram of one embodiment of an electrochemical deposition apparatus in which Ni ions are deposited and converted to nickel hydroxide.

[0040] [Figure 24] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for precipitation of manganese oxide.

[0041] [Diagram 25] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for precipitation of manganese oxide (MnO2) and extraction of NiCo mixed hydroxide precipitate ("MHP").

[0042] [Figure 26] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for precipitation and filtration of MnO2, recycling of Ni and Co, and extraction of NiCo mixed hydroxide precipitate ("MHP").

[0043] [Figure 27] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention with electrolyte and nickel-manganese-cobalt sources joining in a central compartment for precipitation of MnO2.

[0044] [Figure 28] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for precipitation and extraction of MnO2, and formation of cobalt(III) hydroxide (Co(OH)3) and cobalt(III) oxyhydroxide (CoOOH).

[0045] [Figure 29] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for precipitation and extraction of MnO2, formation of cobalt(III) hydroxide (Co(OH)3) and cobalt(III) oxyhydroxide (CoOOH), and extraction of CoOOH.

[0046] [Diagram 30] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for forming solid nickel-manganese-cobalt oxide (NMC(s)).

[0047] [Diagram 31]FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for forming iron (III) hydroxide (Fe(OH)), iron (III) oxide (FeO), and nickel hydroxide (Ni(OH)).

[0048] [Diagram 32] FIG. 1 is a diagram of an electrochemical deposition apparatus of the present invention for forming lithium carbonate (Li2CO3).

[0049] [Diagram 33] FIG. 1 is a diagram of the flow arrangement in an electrochemical deposition apparatus with a filter plate and an elongated current collector.

[0050] [Diagram 34] FIG. 1 illustrates a plate configuration in an electrochemical deposition apparatus including a filter plate and mesh.

[0051] [Diagram 35] FIG. 1 is a diagram of a flow arrangement in an electrochemical deposition apparatus with a filter plate, where either the anode or porous cathode material is disposed at least partially on either side of the filter plate in an alternating pattern.

[0052] [Diagram 36] FIG. 2 is a diagram of a flow arrangement in an electrochemical deposition apparatus with a filter plate, where an anode and a porous cathode material are at least partially disposed on each side of the filter plate.

[0053] [Figure 37] FIG. 1 shows a center-flow electrochemical deposition apparatus.

[0054] [Figure 38] FIG. 1 is a schematic diagram of a filter plate for an electrochemical deposition apparatus.

[0055] [Figure 39]FIG. 2 is a photographic flow diagram of the metal separation process of the components and apparatus of the present invention relating to each process step for black chunk recycling.

[0056] [Diagram 40] FIG. 1 is a process flow diagram of upgrading calcined Ni scrap using an electrochemical deposition apparatus.

[0057] [Diagram 41] FIG. 2 is an expanded view of one embodiment of an electrochemical deposition apparatus showing individual components.

[0058] [Diagram 42] FIG. 2 is a front cutaway view of one embodiment of an electrochemical deposition apparatus showing fluid and electrical flows.

[0059] [Diagram 43] FIG. 2 illustrates the outer housing of one embodiment of an electrochemical deposition apparatus.

[0060] [Diagram 44] FIG. 13 is a perspective side view of the center plate component showing the gas release orifices.

[0061] [Diagram 45] FIG. 2 is a view of the porous cathode material side of one embodiment of an electrochemical deposition apparatus having ports perpendicular to the porous cathode material.

[0062] [Figure 46] FIG. 2 is a view of the porous cathode material side of one embodiment of an electrochemical deposition apparatus having ports parallel to the porous cathode material.

[0063] [Figure 47] FIG. 2 is an anode side view of one embodiment of an electrochemical deposition apparatus having a gas release valve.

[0064] [Figure 48]FIG. 2 is a diagram of a porous cathode material plate of one embodiment of an electrochemical deposition apparatus having ports perpendicular to the porous cathode material.

[0065] [Figure 49] FIG. 2 is a diagram of a porous cathode material plate of one embodiment of an electrochemical deposition apparatus having ports parallel to the porous cathode material.

[0066] [Figure 50] FIG. 2 is a diagram of a framework plate of one embodiment of an electrochemical deposition apparatus.

[0067] [Figure 51] FIG. 1 is a process flow diagram illustrating the production of metal products using an electrochemical deposition apparatus.

[0068] [Figure 52] FIG. 1 is a process flow diagram illustrating a process for concentrating select metals using an electrochemical deposition apparatus.

[0069] [Diagram 53] FIG. 1 is a process flow diagram showing the production of metal products from black mass using an electrochemical deposition apparatus.

[0070] [Figure 54] FIG. 1 illustrates one embodiment of an electrochemical deposition apparatus of the present invention.

[0071] [Figure 55] FIG. 1 illustrates a plate system including plates and a housing for one embodiment of an electrochemical deposition apparatus.

[0072] [Figure 56] FIG. 1 illustrates the plates, housing, automation system, power supply, valves, flow monitor, and housing of one embodiment of an electrochemical deposition apparatus.

[0073] [Figure 57]FIG. 1 illustrates the plates, housing, automation system, power supply, valves, flow monitor, and housing of one embodiment of an electrochemical deposition apparatus.

[0074] [Figure 58] FIG. 2 shows the components of a plate.

[0075] [Figure 59] FIG. 1 is a process flow diagram for extracting Ti and Fe from ilmenite ore using an electrochemical deposition apparatus.

[0076] [Figure 60] FIG. 1 is a process flow diagram incorporating an electrochemical deposition apparatus for producing Co, Ni, and Mn products.

[0077] [Figure 61] 1 is a graph showing the electrochemical performance of the electrochemical deposition apparatus / method of the present invention on a synthetic Nd aqueous solution and real waste material (eg, actual magnet extract).

[0078] [Figure 62] 1 is a graph showing deposition rate versus permeate flux for Co deposition and recovery when the feed is a synthetic battery porous cathode material stream.

[0079] [Figure 63] 1 is a graph showing deposition rate versus permeate flux for Ni deposition and recovery when the feed is a synthetic battery porous cathode material stream.

[0080] [Figure 64] 1 is a graph showing the normalized metal atom percentage as a fraction of the total electrodeposited metal characterized by SEM and EDS when the feed is a synthetic battery porous cathode material stream.

[0081] [Figure 65] 13 is a graph showing deposition rate versus permeate flow rate for Co deposition and recovery when the feed is black mass extract.

[0082] [Figure 66] 1 is a graph showing deposition rate versus permeate flow rate for Ni deposition and recovery when the feed is black mass extract.

[0083] [Figure 67] 1 is a graph showing the normalized metal atom percentage as a fraction of the total electrodeposited metal characterized by ICP-MS, SEM, and EDS when the feed is black mass extract.

[0084] [Figure 68] 1 is a graph showing unit profit margin as a function of metal deposition rate at a constant porous cathode material life of 50 hours.

[0085] [Figure 69] 1 is a graph showing unit profit margin as a function of porous cathode material lifetime at a constant metal deposition rate.

[0086] [Figure 70] 1 is a series of SEM images showing metal oxide precipitates collected and dried on an electrochemical deposition apparatus where the feed is a synthetic battery porous cathode material stream.

[0087] [Figure 71] 1 is a series of SEM images showing metal oxide precipitates collected and dried on an electrochemical deposition apparatus when the feed is black mass extract. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0088] Detailed Description of the Invention The present invention relates to electrochemical deposition devices, systems, and methods. The present invention may be used to extract metals from solutions and / or compounds containing one or more readily extractable metals that form metal compounds via redox reactions. Redox reactions can change the charge of a given metal, for example from a 2+ charge to a 1+ or 3+ charge. The present invention can form metal hydroxides and deposit the metal hydroxides on a porous cathode material. The present invention may also be used to form metal oxides in or in close proximity to a porous anode material. Metal hydroxides or metal oxides can be selectively formed and removed as impurities, and the more valuable metals collected. The metal and / or metal compound products formed by the present invention may be removed and collected from the present invention. Removal from the present invention may be accomplished by changes in charge, flow, or chemistry in the present invention. Metals may be collected by filters, membranes, columns, or other separation methods for the specific metals. The present invention may be used to extract metals from materials including, but not limited to, black mass, ores, concentrates, tailings, batteries, magnets, non-ferrous scrap, and used electronics. The present invention can be used, for example, to extract metals from coal fly ash and lithium batteries. The lithium batteries can include, but are not limited to, lithium nickel magnesium cobalt oxide batteries. The present invention can also be used, for example, to manufacture lithium batteries from nickel, magnesium, and cobalt. The present invention can further be used to manufacture acids and bases, including, but not limited to, sulfuric acid and sodium hydroxide.

[0089] The term "metal" or "metals" is defined herein and in the claims as a compound, mixture, or material that contains a metal atom. The term "metal" or "metals" includes, but is not limited to, a metal hydroxide, a metal oxide, a metal salt, an elemental metal, a metal ion, a non-ionic metal, a mineral, or a combination thereof.

[0090] The term "acid" or "acids" is defined in this specification and claims as a solution having a pH of less than 7.

[0091] The term "buffer" or "buffers" is defined herein and in the claims as a compound that, when added to a solution, causes the solution to resist changes in pH compared to a solution without the compound.

[0092] The term "leaching" is defined herein and in the claims as a process used to liberate, extract, liberate, or remove a metal or metals from a material.

[0093] The terms "oxidation-reduction," "oxidation-reduction reaction," or "reduction-oxidation reaction" are defined herein and in the claims as chemical reactions involving the reduction and / or oxidation of a chemical species.

[0094] The present invention relates to an electrochemical deposition apparatus or system for precipitating and depositing metals. The electrochemical deposition apparatus may comprise a housing, a porous cathode material capable of acting as a cathode, where metal is deposited on the surface of the porous cathode material, an anode, an inlet, and an outlet. The porous cathode material may comprise carbon, metal, metal compound, porous polymer, porous ceramic, or a combination thereof. The porous cathode material may comprise heterogeneous materials, such as mixed carbon, metal, polymer, or ceramic materials. The porous cathode material may comprise a metal or metal oxide catalyst, a protective layer, a polymer binder, or a combination thereof. The porous cathode material may comprise a material or medium made into a porous structure, such as a particle, fiber, or flask. The housing may comprise, but is not limited to, a transparent plastic, polycarbonate, polypropylene, polyvinyl chloride, polytetrafluoroethylene, acrylic, and / or metal support to allow visual observation of the electrochemical deposition process. The electrochemical deposition apparatus may further comprise a current collector. The current collector may include, but is not limited to, Ti. The electrochemical deposition apparatus may further include an O-ring seal. The electrochemical deposition apparatus may further include a hole to prevent the current collector from destroying the O-ring seal. The electrochemical deposition apparatus may be used in combination with conventional metal extraction methods, such as calcination and / or chemical precipitation.

[0095] The method may include passing a feed through an electrochemical deposition apparatus, contacting the feed with a porous cathode material, depositing metal on a surface of the porous cathode material to form a permeate, discharging the permeate from the electrochemical deposition apparatus, removing the deposited metal from the surface of the porous cathode material to form a concentrate, and passing the concentrate through the electrochemical deposition apparatus. The method may be used in combination with conventional metal enrichment methods, such as calcination and / or chemical precipitation.

[0096] Turning now to the figures illustrating non-limiting alternative embodiments of the present invention, FIG. 1 illustrates an electrochemical deposition apparatus 10 of the present invention in which a permeate stream 12 simultaneously flows across and / or through a porous cathode material 14 and an anode 16.

[0097] FIG. 2 shows an electrochemical deposition apparatus 18 of the present invention that includes an impermeable boundary 20 that forces the feed 22 across and / or through the porous cathode material 14 and anode 16 and into a cavity 24 .

[0098] Figure 3 shows an electrochemical deposition apparatus 26 of the present invention comprising two stacked porous cathode materials 14. Although Figure 3 shows three stacked electrodes, any number of porous cathode materials 14 and anodes 16 can be stacked in any order.

[0099] Figure 4 shows an electrochemical deposition apparatus 28 of the present invention comprising alternating porous cathode materials 14 and anodes 16. Although Figure 4 shows three stacked electrodes, any number of porous cathode materials 14 and anodes 16 can be stacked in any order.

[0100] 5 shows an electrochemical deposition apparatus 30 of the present invention in which the feed 22 enters the interelectrode region 32 and contacts the porous cathode material 14 and the anode 16. Each permeate stream 12 then traverses and / or passes through the porous cathode material 14 and the anode 16.

[0101] 6 illustrates an electrochemical deposition apparatus 34 of the present invention in which the feed 22 enters the interelectrode region 32 and contacts the porous cathode material 14. The permeate stream 12 must contact, cross and / or pass through the porous cathode material 14 before contacting and passing through the anode 16.

[0102] 7 shows an electrochemical deposition apparatus 36 of the present invention in which the feed 22 enters the interelectrode region 32 and contacts the anode 16. The permeate stream 12 must contact, cross and / or pass through the anode 16 before contacting and passing through the porous cathode material 14.

[0103] 8 shows an electrochemical deposition apparatus 38 of the present invention. Multiple feeds 22 enter multiple inter-electrode regions 32. From the multiple inter-electrode regions 32, the permeate stream 12 traverses and / or passes simultaneously through multiple porous cathode materials 14 and anodes 16 arranged in series.

[0104] FIG. 9 shows an electrochemical deposition apparatus 40 of the present invention. Stream 42 shows the path of the second metal deposited on the porous cathode material 14. When multiple porous cathode materials 14 and anodes 16 are arranged in series, multiple metals may be deposited on each porous cathode material 14. Different metals may be deposited on each porous cathode material 14. As shown in FIG. 9, two different metals may be released from two different porous cathode materials 14, resulting in two different concentrates and / or extracts 44 and 46. The number of concentrates and / or raffinates containing metals or metal oxides depends on the number of porous cathode materials 14, i.e., three, four, or five (or more) porous cathode materials 14, which may facilitate the deposition of, for example, three to five (or more) different metals, producing three to five (or more) concentrates and / or raffinates. Although the diagram shows three to five metals, concentrates, and / or raffinates, any number of metals, concentrates, and / or raffinates may be extracted. Stream 48 shows the path of feed 22 freely passing through electrochemical deposition apparatus 40 which deposits metals onto porous cathode material 14. Stream 48 may also be used to indirectly recover metals by depositing undesired metals.

[0105] 10 illustrates an electrochemical deposition apparatus 50 of the present invention in which the feed 22 passes through the interelectrode region 32 simultaneously with the external influent stream 52 by flowing the feed 22 and the external influent stream 52 directly across the porous cathode material 14 into the interelectrode region 32. The external influent stream 52 may include the feed 22 or recycled concentrate 54, or any other source of metal solution.

[0106] 11 illustrates an electrochemical deposition apparatus 56 of the present invention in which the feed 22 and the external inlet stream 52 simultaneously enter and mix in the interelectrode region 32. The feed 22 and the external inlet stream 52 of the electrochemical deposition apparatus 56 may contain the same solution or different solutions.

[0107] 12 illustrates an electrochemical deposition apparatus 58 of the present invention in which the external influent streams 52 mix in the interelectrode region 32 to form a mixed permeate 60. The feed 22 also contacts the porous cathode material 14 or the anode 16 to form a concentrate and / or raffinate 54.

[0108] FIG. 13 illustrates an electrochemical deposition apparatus 62 of the present invention in which each external influent stream 52 must contact, cross and / or pass through the porous cathode material 14 and the anode 16 to enter the inter-electrode region 32 and form a mixed permeate 60.

[0109] FIG. 14 illustrates an electrochemical deposition apparatus 64 of the present invention in which the external inlet stream 52 must contact, cross and / or pass through the anode 16 before contacting and passing through the porous cathode material 14 and mixing in the interelectrode region 32.

[0110] FIG. 15 illustrates an electrochemical deposition apparatus 66 of the present invention in which the external inlet stream 52 must contact, cross and / or pass through the porous cathode material 14 before contacting and passing through the anode 16 and mixing in the interelectrode region 32.

[0111] 16 shows an electrochemical deposition apparatus 68 of the present invention where metal deposition occurs in parallel. Multiple feeds 22 enter multiple interelectrode regions 32 in parallel. Each feed 22 contacts a porous cathode material 14 and an anode 16.

[0112] FIG. 17 shows an electrochemical deposition apparatus 70 of the present invention in which multiple feeds 22 enter the electrochemical deposition apparatus 70 in parallel, with each feed 22 contacting two porous cathode materials 14 or two anodes 16 .

[0113] 18 shows an electrochemical deposition apparatus 72 of the present invention where metal deposition occurs in series. Feed 22 enters and exits multiple interelectrode regions 32 by connecting streams 74. Feed 22 contacts the porous cathode material 14 and anode 16 in each of the multiple interelectrode regions 32.

[0114] FIG. 19 shows an electrochemical deposition apparatus 76 of the present invention in which a feed 22 enters and exits multiple inter-electrode regions 32 by connecting flows 74 such that the feed 22 contacts two porous cathode materials 14 and two anodes 16 in each inter-electrode region 32.

[0115] FIG. 20 illustrates an electrochemical deposition apparatus 78 of the present invention comprising a housing 80. The feed 22 enters a cavity 82 and contacts the porous cathode material 14 to undergo a reduction-oxidation reaction. The reduction-oxidation reaction can occur in an exemplary reaction zone 84 to deposit a metal 86. In the reaction zone 84, the porous cathode material 14 acts to electrolyze water 88 via a redox reaction 90 to form hydrogen 92 and hydroxide ions 94. The hydroxide ions 94 react with metal ions 96 to form metal hydroxides 98. The metal hydroxides 98 are deposited 100 on the surface of the porous cathode material 14. The feed 22 passes along a permeate flow 12, traversing the porous cathode material 14, the interelectrode region 32, the anode 16, and a post-deposition region 102, and then exits the electrochemical deposition apparatus 78 as a permeate 104. The permeate flow 12 is the path of the feed 22 within a given electrochemical deposition apparatus. Stream 104 may be metal-depleted or metal-free. Metals 86 are released from the porous cathode material 14 to form the concentrate and / or extract 54. Optionally, the concentrate and / or raffinate 54 may be recycled to the electrochemical deposition apparatus 78 as the feed 22. The raffinate may be a solution from the electrochemical deposition apparatus 78 that has been stripped of valuable metals. Thus, the permeate in FIG. 20 may be a raffinate.

[0116] 21 shows an electrochemical deposition apparatus 106 of the present invention. In the electrochemical deposition apparatus 106, the metal ions 96 are converted to a non-ionic or zero-valent metal 108 via an oxidation-reduction reaction 90. The non-ionic metal 108 is then deposited 100 on the porous cathode material 14.

[0117] FIG. 22 shows an electrochemical deposition apparatus 110 of the present invention, where metal is deposited on the porous cathode material 14 by a central flow through the electrochemical deposition apparatus. The feed 22 enters the electrochemical deposition apparatus 110 in region 112. The feed electrolyte 114 enters region 116 and traverses the porous cathode material 14 by stream 118. Hydrogen molecules and hydroxide anions are produced by reaction 120, which react with the metal cations to form metal hydroxides. The metal hydroxides 122 exit the electrochemical deposition apparatus 110 as a metal hydroxide concentrate by stream 124. The feed electrolyte 114 also traverses the anode 16 by stream 126. Water is hydrolyzed at the anode 16 by reaction 128 to form hydrogen ions and oxygen in a cavity 131. The feed electrolyte 114 exits the electrochemical deposition apparatus 110 by stream 132 and may be recycled to acid leaching. About 50% (or other portion) of the feed electrolyte 114 may flow through and / or across the porous cathode material 14, and about 50% (or other portion) of the feed electrolyte 114 may flow through and / or across the anode 16. The flow 132 may be acidified by anodic electrolysis. The feed electrolyte 114 is forced across the porous cathode material 14 and the anode 16 by a surface 134 that prevents the feed electrolyte 114 from flowing directly out of the electrochemical deposition apparatus 110. Optionally, the surface 134 may not be present and the feed electrolyte 114 may simultaneously flow directly out of the electrochemical deposition apparatus 110 and across the porous cathode material 14 and the anode 16 into the regions 112 and 131, respectively.

[0118] FIG. 23 shows an exemplary embodiment of a chemical deposition apparatus for selective deposition of nickel oxide. Ni ions are deposited in the electrochemical apparatus as Ni(OH) 2The Ni-free permeate (raffinate) leaves the electrochemical device. The deposited Ni(OH) 2 is released from the porous cathode material (e.g., the cathode shown in FIG. 23) to form concentrated Ni(OH). 2 It may be released as a solution containing

[0119] 24 illustrates an electrochemical deposition apparatus 144 of the present invention. In the electrochemical deposition apparatus 144, a feed 146 (e.g., Ni, Mn, and Co) enters the cavity 130 and contacts the porous cathode material 14 to undergo a reduction-oxidation reaction. The reduction-oxidation reaction can occur in an exemplary reaction zone 148. In the reaction zone 148, the porous cathode material 14 electrolyzes water 88 via a redox reaction 90 to form hydrogen 92 and hydroxide ions 94. The feed 146 then passes through the interelectrode region 32 to contact the anode 16 to undergo a reduction-oxidation reaction. The reduction-oxidation reaction can occur in an exemplary reaction zone 150. In the reaction zone 150, the anode 16 electrolyzes, for example, manganese 154 via a redox reaction 158. The manganese 154 reacts with the water 88 to form hydrogen ions 152 and MnO. 2 Form 156. MnO 2 156 is deposited 160 on the surface of the anode 16. 2 may be removed from the anode 16, and dissolved MnO 2 The concentrate 54 exits the electrochemical deposition apparatus 144 through the post-deposition region 145 via a flow 162 including

[0120] 25 illustrates an electrochemical deposition apparatus 164 of the present invention. In the electrochemical deposition apparatus 164, the feed 146 (e.g., Ni, Mn, and Co) enters the cavity 130 and contacts the anode 16 to undergo a reduction-oxidation reaction. The reduction-oxidation reaction may occur in an exemplary reaction zone 150. In the reaction zone 150, the anode 16 converts, for example, manganese 154 via a redox reaction 158. The manganese 154 reacts with water 88 to produce hydrogen ions 152 and MnO. 2The feed 146 then passes through the interelectrode region 32 to contact the porous cathode material 14 and undergo a reduction-oxidation reaction. The reduction-oxidation reaction may occur in an exemplary reaction region 166. In the reaction region 166, the porous cathode material 14 electrolyzes water 88 via a redox reaction 90. The water 88 is converted to hydrogen by the addition of, for example, Ni and / or Co. 2+ 168 to form a nickel-cobalt metal hydroxide precipitate 170. The nickel-cobalt metal hydroxide precipitate 170 enters the post-deposition region 145 and the stream exits the electrochemical deposition apparatus 164 via stream 172 containing the metal hydroxide precipitate 170. The concentrate 54 exits the cavity 130.

[0121] FIG. 26 illustrates an electrochemical deposition apparatus 174 of the present invention. In the electrochemical deposition apparatus 174, a feed 176 (e.g., Ni and Co) enters the cavity 130 and contacts the porous cathode material 14 to undergo a reduction-oxidation reaction. The porous cathode material 14 electrolyzes water 88 via a redox reaction 90 to form hydrogen 92 and hydroxide ions 94. The hydroxide ions 94 are converted to Ni and / or Co. 2+ 168 to form a nickel-cobalt metal hydroxide precipitate 170. The electrolyte 114 enters the interelectrode region 32 and crosses the porous cathode material 14 into the cavity 130. The electrolyte 114 and nickel-cobalt metal hydroxide precipitate 170 exit the electrochemical deposition apparatus 174 via a stream 178 containing the nickel-cobalt metal hydroxide precipitate 170 and the electrolyte 114. The feed 180 (e.g., Ni, Mn, and Co) enters the cavity 182 and undergoes a reduction-oxidation reaction in contact with the anode 16. The anode 16 electrolyzes manganese 154 via a redox reaction 158. The manganese 154 reacts with water 88 to form hydrogen ions 152 and MnO 2 The electrolyte 114 enters the interelectrode region 32, crosses the anode 16 and enters the cavity 182. The electrolyte 114 may include, but is not limited to, NaCl. The electrolyte 114 and MnO 2 156 is MnO 2156 and electrolyte 114. Stream 186 contacts filter 188 to remove MnO from stream 186. 2 156 is removed to form feed 176, which is recycled to the electrochemical deposition apparatus 174. The anode 16 electrolyzes manganese 154 via a redox reaction 158. Manganese 154 reacts with water 88 to produce hydrogen ions 152 and MnO 2 156. The porous cathode material 14 electrolyzes water 88 via an oxidation-reduction reaction 90 to form hydrogen 92 and hydroxide ions 94.

[0122] FIG. 27 shows an electrochemical deposition apparatus 190 of the present invention. In the electrochemical deposition apparatus 190, the feed 146 (e.g., Ni, Mn, and Co) enters the cavity 182 and contacts the anode 16 to undergo a reduction-oxidation reaction. MnO 2 156 enters the interelectrode region 32 via the external inflow stream 52. The electrolyte 114 enters the cavity 130 and undergoes a reduction-oxidation reaction in contact with the porous cathode material 14. The electrolyte 114 and MnO 2 156 is MnO 2 156 exits the electrochemical deposition apparatus 190 via a stream 186 containing the electrolyte 114, nickel, and cobalt.

[0123] 28 shows an electrochemical deposition apparatus 192 of the present invention. The electrochemical deposition apparatus 192 has at least two electrochemical deposition chambers installed in series. The first electrochemical deposition chamber is configured to deposit, for example, MnO 2 156, produces a stream 186 containing electrolyte 114, nickel, and cobalt. Stream 186 contacts filter 188 to produce MnO 2 156 is removed to form Ni-Co feed 176. Ni-Co feed 176 enters cavity 182 of the second electrochemical deposition chamber and contacts anode 16 to undergo a reduction-oxidation reaction. 2+ 194 undergoes redox reaction 196 to form Co 3+ Form 198. Co 3+198 enters the interelectrode region 32 via the external inflow stream 52. The electrolyte 114 enters the cavity 130 and undergoes a reduction-oxidation reaction in contact with the porous cathode material 14. The porous cathode material 14 electrolyzes water 88 via a redox reaction 90 to form hydrogen 92 and hydroxide ions 94. The hydroxide ions 94 are converted to Co by the electrochemical reaction 90. 3+ Reacts with 198 to give Co(OH) 3 and forming a stream 200 comprising CoOOH.

[0124] 29 illustrates an electrochemical deposition apparatus 202 of the present invention. In the electrochemical deposition apparatus 202, the electrolyte 114 enters the interelectrode region 32 and traverses the porous cathode material 14 and the anode 16. The electrolyte 114 may include, but is not limited to, NaCl. The feed 146 (e.g., Ni, Mn, and Co) enters the cavity 182 as a first pass material and contacts the anode 16 to undergo redox reactions 184 and 158. In redox reaction 184, chloride ions are converted to chlorine. In redox reaction 158, manganese 154 reacts with water 88 to produce hydrogen ions 152 and MnO. 2 Form 156. MnO 2 156, Ni and Co 2+ The MnO 2 exits the electrochemical deposition apparatus 202 via stream 204 and contacts the filter 188. 2 156 was removed, and Ni and Co were left in the solution. 2+ The Ni-Co feed 206 acts as a second pass feed and enters the cavity 182 in contact with the anode 16 and undergoes redox reactions 184 and 208. In redox reaction 184, chloride ions are converted back to chlorine. In redox reaction 208, Co 2+ 194 is Co 3+ Converted to 198. 3+ 198 reacts with hydroxide ion 94 to form Co(OH) 3 and CoOOH. Ni, Co(OH) 3A stream 210 containing Ni and CoOOH exits the electrochemical deposition apparatus 202 and contacts a filter 212. The filter 212 removes the CoOOH to form a feed 214 containing Ni. The feed 214 enters the cavity 130 and contacts the porous cathode material 14 to undergo a reduction-oxidation reaction 92. In the reduction-oxidation reaction 92, water 88 is electrolyzed to form hydrogen 92 and hydroxide ions 94. The hydroxide ions 94 are converted to Ni. 2+ Reacts with 216 to give Ni(OH) 2 Forms 218. Ni(OH) 2 218 exits the electrochemical deposition apparatus 202 via flow 220 .

[0125] 30 illustrates an electrochemical deposition apparatus 222 of the present invention. In the electrochemical deposition apparatus 222, a feed 146 (e.g., Ni, Mn, and Co) enters the cavity 130 and contacts the porous cathode material 14, which undergoes a reduction-oxidation reaction. The porous cathode material 14 electrolyzes water 88 via a redox reaction 90 to form hydrogen 92 and hydroxide ions 94. The hydroxide ions 94 are reacted with the solvent Ni, Mn, and Co to form a mixture of hydrogen 92 and hydroxide ions 94. 2+ Reacts with 224 and NMC (s) Form 226. NMC (s) 226 exits the electrochemical deposition apparatus 222 via flow 228. The electrolyte 114 enters the interelectrode region 32 and traverses the porous cathode material 14 and the anode 16. The electrolyte 114 is NaHCO 3 And / or Na 2 SO 4 Water 88 is converted to oxygen 232 and hydrogen ions 152 by redox reaction 230. The acid produced by redox reaction 230 is recycled via stream 234. The acid may be recycled to the leaching.

[0126] FIG. 31 shows an electrochemical deposition apparatus 236 of the present invention. The electrochemical deposition apparatus 236 uses at least two electrochemical deposition chambers installed in series. In the electrochemical deposition apparatus 236, a feed 238 (e.g., Fe 2+ , Cu 2+ , and Ni 2+) enters the cavity 130 of the first electrochemical deposition chamber and contacts the porous cathode material 14 to undergo a reduction-oxidation reaction. The reduction-oxidation reaction may occur in an exemplary reaction region 240. In the reaction region 240, the porous cathode material 14 is converted to Cu by a redox reaction 248. 2+ The permeate 250 enters the interelectrode region 32 and contacts the anode 16 to undergo a reduction-oxidation reaction. The reduction-oxidation reaction may occur in an exemplary reaction region 252. In the reaction region 252, the anode 16 converts Fe 242 to Cu(0) 244 via a redox reaction 258. 2+ 254 to Fe 3+ Convert to 256. 3+ 256 also reacts with hydroxide ion 94 to form Fe(OH) 3 260. The concentrate 54 exits the electrochemical deposition apparatus 236 from the cavity 130. Fe(OH) 3 , Fe 2 O 3 , and Ni 2+ The stream 262 containing Fe(OH) exits the electrochemical deposition apparatus 236 and contacts the filter 188. The filter 188 filters out the Fe(OH) 3 and Fe 2 O 3 Remove Ni 2+ The feed 264 enters the cavity 130 of the second electrochemical deposition chamber and contacts the porous cathode material 14. The water 88 is converted to hydrogen 92 and hydroxide ions 94 by an oxidation-reduction reaction 90. The hydroxide ions 94 are converted to Ni 2+ Reacts with 216 to give Ni(OH) 2(s) Forms 218. Ni(OH) 2(s) 218 exits the electrochemical deposition apparatus 236 through flow 266. The electrolyte 114 enters the cavity 182 and contacts the anode 16. The electrolyte 114 is NaHCO 3 And / or Na 2 SO 4 Water 88 is converted to oxygen 232 and hydrogen ions 152 by redox reaction 230. The acid produced by redox reaction 230 is recycled via stream 234.

[0127] FIG. 32 illustrates an electrochemical deposition apparatus 268 of the present invention. In the electrochemical deposition apparatus 268, a supply 270 (e.g., Li + 272 and SO 4 2- ions) enter the intermembrane region 1417. Li + 272 is Li + Across the specific cation exchange membrane 274. Li + Specific cation exchange membrane 274 is Na + Including but not limited to, Li + It is impermeable to monovalent ions 276 except for 272. NaHCO 3 The electrolyte 114 enters the cavity 130 and contacts the porous cathode material 14. Water 88 is converted to hydrogen 92 and hydroxide 94 by an oxidation-reduction reaction 90. The hydroxide 94 is HCO 3- 278 to form carbonate 280. The carbonate 280 traverses the porous cathode material 14 and dissolves Li + Reacts with 272 to Li 2 CO 3 Forming Li 2 CO 3 The depleted Li exits the electrochemical deposition apparatus 268 as Li concentrate or precipitate-containing concentrate 54. + 272 and SO 4 2- The solution exits the electrochemical deposition apparatus 268 via stream 282. 4 2- Anions, including but not limited to, cross the anion exchange membrane 284 via exemplary stream 286 and enter region 288. A feed 290, including sodium sulfate and electrolyte, enters region 292 and contacts the anode 16. Water 88 is converted to hydrogen ions 152 and oxygen 232. The hydrogen ions 152 and oxygen 232 cross the anode 16 via stream 294 and enter region 288 to form sulfuric acid. The sulfuric acid exits the electrochemical deposition apparatus 268 via stream 296.

[0128] 33 shows a plate configuration 310 comprising a plate 312, a porous cathode material 14, an anode 16, a mesh 314, a gasket 316, a current collector 318, a collar 320, and a collar gasket 322. The pair of gasket 316, current collector 318, collar 320, and collar gasket 322 may be disposed at least partially around the plate 312. The plate 312 may be disposed at least partially around the mesh 314. Optionally, an elongated current collector 324 may be disposed at least partially beside the porous cathode material 14, as shown in FIG.

[0129] FIG. 35 shows the arrangement of the flow 326 in an electrochemical deposition apparatus with plates. Pairs of porous cathode materials 14 and anodes 16 are arranged at least partially around a plate 312, with each plate 312 being arranged at least partially between either two porous cathode materials 14 or two anodes 16. An anode permeate 327 crosses the plate 312 that is arranged at least partially between two anodes 16. A porous cathode material permeate 328 crosses the plate 312 that is arranged at least partially between two porous cathode materials 14. The arrangement of the flow 326 includes at least three plates 312 arranged in parallel, forming at least a first channel and a second channel. A metal feed 330 flows through the first channel and the second channel. There may be multiple channels, and the metal feed 330 may flow through multiple channels.

[0130] FIG. 36 shows a flow 332 arrangement in an electrochemical deposition apparatus comprising a plate. The porous cathode material 14 and the anode 16 are at least partially disposed around the plate 312. An electrolyte feed 334 crosses the plate 312. The flow 332 arrangement includes at least three plates 312 arranged in parallel to form at least a first channel and a second channel. The metal feed 330 flows through the first channel and contacts the porous cathode material 14. The anode permeate flows through the second channel and contracts the anode 16.

[0131] FIG. 37 shows a center-flow electrochemical deposition apparatus 336. A metal feed 330 enters the center-flow electrochemical deposition apparatus 336. An electrolyte feed 334, provided by an electrolyte feed reservoir 338, enters a region 340 of the center-flow electrochemical deposition apparatus 336. Hydroxide ions 342 traverse the porous cathode material 14 and metal hydroxides are formed. A metal hydroxide concentrate 344 exits the center-flow electrochemical deposition apparatus 336. The metal hydroxide concentrate 344 may include metal ions and / or electrolyte. The metal ions and / or electrolyte may be stored in a reservoir 346 and recycled to the center-flow electrochemical deposition apparatus 336 by a stream 348. The electrolyte feed 334 traverses the anode 16, exits the center-flow electrochemical deposition apparatus 336 and may be collected in a reservoir 350.

[0132] FIG. 38 illustrates an embodiment of an electrochemical deposition apparatus that includes a plate. The plate includes, for example, a plastic mesh 354 with an anode-side acrylic 352 disposed thereon. The mesh 354 (e.g., plastic mesh) is disposed next to a gasket 356 (e.g., rubber gasket). The rubber gasket 356 is disposed next to the anode 16. The anode 16 is disposed next to a current collector 318. The current collector 318 is disposed next to a frame 358. The frame 358 is disposed next to at least one mesh 354. The plastic mesh 354 is disposed next to the current collector 318. The current collector 318 is also disposed next to a cathode (e.g., a porous cathode material) 14. The cathode 14 is disposed next to the plastic mesh 354. The plastic mesh 354 may also be disposed next to the rubber gasket 356. The rubber gasket 356 is disposed next to 360.

[0133] As shown in FIG. 39, the electrochemical deposition apparatus 380 of the present invention may be incorporated into a process for recovering metals. Starting material 382 is combined with a fluid to form a solution containing the metal. The solution is formed in a mixing vessel 384. The solution is treated to remove impurities 386, such as, but not limited to, graphite, aluminosilicates, gangue materials, polymers, and other insolubles. The pH of the solution is then adjusted via a mixing vessel 388. A filter 390 is used to remove undesired metals, such as undesired metal oxides. The electrochemical deposition apparatus 380 recovers the metal from the solution by depositing the metal on the porous cathode material 14. The deposited metal is discharged from the electrochemical deposition apparatus 380 and pumped into a settling tank 392. The precipitate is collected to collect the final product 394. As shown in FIG. 40, multiple electrochemical deposition apparatuses 380 may also be used to recover a particular metal.

[0134] 41 shows an electrochemical deposition apparatus 404 of the present invention comprising a current collector 406, a porous cathode material 14, an anode 16, and a separator 408 disposed within a back housing 410 and a front housing 412. A rod 414 (e.g., a titanium rod) is partially disposed within the back housing 410 and the front housing 412 and contacts the current collector 406.

[0135] 42 shows an electrochemical deposition apparatus 416 of the present invention with electrical contacts 418, a feed inlet port 420, a permeate outlet 422, and a concentrate outlet 424. The feed can move across the electrochemical deposition apparatus 416 according to a flow 426.

[0136] 43 illustrates one embodiment of an external housing for a chemical deposition apparatus. The external housing provides a protective casing for the internal components of the chemical deposition apparatus, including but not limited to the porous cathode material, anode, electrode, current collector, or combinations thereof. The external housing can have one or more external ports for attachment of lines, including but not limited to feed lines, permeate lines, input lines, or output lines, or combinations thereof.

[0137] 44 shows a perspective side view of a central plate component 446 comprising a middle plate 448 and an extrusion 449. The middle plate 448 comprises a plurality of orifices 450. A gas release channel 452 is disposed within the central plate component 446. The gas release channel 452 includes two gas release channels parallel to the base of the central plate component 446. A hydrogen gas flow is diffused from one of the two gas release channels and an oxygen gas flow is diffused from the other.

[0138] Figures 45-50 show various embodiments of an electrochemical deposition apparatus. Figure 45 shows the porous cathode material side of an electrochemical deposition apparatus 455 with a holder 458, fastener orifice 460, pressure gauge 461, port 462, electrode port 464, gas release channel 466, cover plate 468, bleed port 470, and electrode channel 472.

[0139] 46 and 49 show the porous cathode material side of the electrochemical deposition apparatus 456, which includes a retainer 459, fastener orifice 460, pressure gauge 461, cathode side port 474, electrode port 464, cover plate 468, outlet port 470, and electrode channel 472.

[0140] 47 and 48 show the anode side of an electrochemical deposition apparatus 476, which includes a retainer 458, a fastener orifice 460, a gas release channel 466, an anode side port 475, an electrode port 464, a cover plate 468, an outlet port 470, and a gas release valve 480.

[0141] FIG. 50 shows a framework plate of one embodiment of an electrochemical deposition apparatus that includes a plurality of fastening orifices 494, mating grooves 496, and a cavity 498 for receiving a retainer 458 (see FIG. 47).

[0142] 51 illustrates a process 500 for producing a metal product using an electrochemical deposition apparatus 508. An electrolyte feed 502 and a metal feed 504 enter and / or pass through the electrochemical deposition apparatus 508 to provide a hydrogen and oxygen gas stream 506, an aqueous anode permeate 510, and a porous cathode material permeate 512. The electrochemical deposition apparatus 508 is powered by a power supply 511. The power supply may provide a voltage of about 10V. The porous cathode material permeate 512 contacts a filter 514 to produce a solid metal product 516 and an aqueous metal salt water product.

[0143] 52 shows a process 518 for concentrating a selected metal using an electrochemical deposition apparatus 536. Electrolyte from an electrolyte tank 522 is conveyed by a pump 524 to a processing unit 528 containing an electrochemical deposition apparatus 536. The metal feed from the tank 532 is conveyed by a manual peristaltic pump 534 to the processing unit 528 containing the electrochemical deposition apparatus 536. Permeate from the processing unit 528 enters a permeate tank 538. The concentrated metal feed enters an in-line bag filter 530 and is recycled to the metal feed tank 532.

[0144] FIG. 53 illustrates a black mass to metal product production process 540 using an electrochemical deposition apparatus 566. Black mass solids 542 are homogenized to form homogenized black mass 544. The homogenized black mass is contacted with, for example, sulfuric acid and hydrogen peroxide in vessel 546 to form a black mass slurry. The black mass slurry is contacted with filter 548 in vessel 552 to remove graphite 550 and form a black mass extract. The black mass extract is contacted with sodium hydroxide 554 to form a black mass extract slurry 556, which is contacted with filter 558 to remove metal precipitates collected in vessel 560. The black mass extract 562 is diluted with water in vessel 564 before entering the electrochemical deposition apparatus 566 to contact the electrolyte 570. The recycled black mass 568 may be recycled to vessel 564. The anode permeate from the electrochemical deposition apparatus 566 is collected in vessel 572. The product from the electrochemical deposition apparatus 566, e.g., NiCo 582, is contacted with a filter 574 to produce wastewater and / or Li-brine 576 and a concentrated product, which is collected in a storage vessel 584 after being homogenized in a blender 580.

[0145] Figure 54 shows an electrochemical deposition apparatus 586 with a power supply 588, a reagent and feed storage system 590, a feed port 592, a permeate port 596, a reagent port 594, and an acid and / or base port 598. Figure 55 shows a plate system 600 with a housing 602, an input and / or output array 606, a plate array 604, and a plate adjuster 608. Figures 56-57 show an electrochemical deposition apparatus 610 with a housing 602, an input and / or output array 606, a plate array 604, a plate adjuster 608, reagent and feed fluid pumps 614, and an automated control system 616.

[0146] FIG. 58 shows a plate 618 comprising a thick collar 620 , a gasket 622 , a porous cathode material 14 , a current collector 318 , a plate 626 , an anode 16 , a thin collar 628 , and an O-ring 624 .

[0147] The present invention can be utilized in a wide range of metal processing applications from virgin ores to end of life materials. Figure 59 is a process flow diagram of metal extraction from minerals (e.g. virgin ores) using the chemical deposition apparatus of the present invention. Mineral inputs; iron inputs, including but not limited to in the form of ores, concentrates, agglomerated materials, slurries, or combinations thereof; other inputs, including but not limited to in the form of acids, catalysts, surfactants, or combinations thereof, are crushed, for example by ball milling, and leached to form a solution. The solution is then processed by the chemical deposition apparatus to form a mixed iron product, for example a Ti / Fe product, and / or other metal products, for example copper, lithium, or other metals of interest. Virgin ores, such as ilmenite, may be input to the process. The ores may first be crushed and / or ground to smaller particle sizes. The crushed ores may then be beneficiated to higher grade concentrates using various methods, such as density separation, magnetic separation, flotation, etc. The ore concentrates are then leached with acid, high pressure oxidation, or processes including but not limited to the present invention. Leaching may be performed selectively to dissolve only one or more specific metals. The undissolved material is then filtered from the dissolved material. The metals in the leach solution are then reprecipitated by the electrochemical deposition process of the present invention. Metals may be selectively precipitated to obtain high purity metal products. For example, Ti may be selectively precipitated from the ilmenite leach solution.

[0148] FIG. 60 is a process flow diagram of metal extraction from minerals using the chemical deposition apparatus of the present invention. The mineral input is leached to form a leached product. The leached product is filtered to remove selected metals or materials and the pH is adjusted using reagents including, but not limited to, acids, bases, buffers, or combinations thereof. The filtered product is processed by the chemical deposition apparatus to result in a product. The product may include metals. The received material may be crushed and / or ground end-of-life material from batteries, magnets, electric motors, circuit boards, catalytic converters, etc. The material is first leached with a reducing acid, an oxidizing acid, or a process including, but not limited to, the present invention. Leaching may be selective to dissolve only the desired metals or to remove undesired metals. The undissolved material is then filtered from the dissolved metals. The filtered material may be a product such as graphite. If desired, pH adjustment can be completed using chemical methods or the present invention to precipitate either the desired or undesired metals. The precipitate is then filtered from the dissolved solution. The filtrate is then passed through electrochemical filtration to obtain an upgraded, higher value metal product. For batteries, this can be, by way of example, Ni precipitates, Co precipitates, mixed NiCo precipitates, NMC precipitates, etc. For magnets, this can be Nd precipitates, Pr precipitates, mixed NdPr precipitates, etc. For circuit boards, this can be Cu precipitates, Au precipitates, or mixed CuAu precipitates. For catalytic converters, this can be Pd precipitates, Pt precipitates, Rh precipitates, mixed PdPtRh precipitates, etc.

[0149] FIG. 61 shows a graph of synthetic Nd vs. real waste recovery using the chemical deposition apparatus of the present invention. The maximum recovery, deposition rate, and current efficiency are greater for synthetic Nd. FIG. 61 shows the results of evaluating Nd recovery from both synthetic Nd and Nd solutions produced from end-of-life magnets. End-of-life magnets were processed similarly to that described in FIG. 60 by demagnetization in an oven, grinding, dissolution in nitric acid, filtering residual solids, pH adjustment as necessary, and subsequent electrochemical deposition. The synthetic Nd was observed to have a higher recovery, deposition rate, and current efficiency compared to EOL magnet Nd, as expected due to the presence of other species in the magnet solution including Pr, Dy, and Fe, as well as the higher input Nd concentration. Operating conditions were standard flow rates (see FIG. 23).

[0150] Co recovery generally decreases with increasing permeate flow rate and decreasing deposition rate. Figure 62 shows the results of Co recovery (%) and deposition rate (g / m2 / h) from a mixed synthetic Ni / Mn / Co solution as a function of permeate flow rate in the standard flow configuration (see Figure 23). As the permeate flow rate increases, Co recovery decreases but the deposition rate increases. Less Co is recovered, but the deposition rate increases due to a larger increase in the total mass flow rate Co.

[0151] FIG. 63 shows a graph of deposition rate versus permeate flow rate for Ni deposition and recovery. Ni deposition rate generally increases with increasing permeate flow rate and increasing deposition rate. Ni recovery generally decreases with increasing permeate flow rate and decreasing deposition rate. FIG. 63 shows the results of Ni recovery (%) and deposition rate (g / m2 / h) from a mixed synthetic Ni / Mn / Co solution as a function of permeate flow rate in the standard flow configuration (see FIG. 23). As the permeate flow rate increases, Co recovery decreases but the deposition rate increases. Less Ni is recovered but the deposition rate increases due to a larger increase in the total mass flow rate Ni.

[0152] FIG. 64 shows a graph of metal fractions at various voltages for Co, Ni, and Mn. The Co metal fraction was greatest when 2.25V was applied to the chemical deposition apparatus. The Ni and Mn metal fractions were greatest when 2.5V was applied to the chemical deposition apparatus. This graph shows that there is an optimum voltage for each metal fraction. FIG. 64 shows precipitate metal composition results from an electrochemical deposition system of the present invention as a function of applied voltage. As the applied cell voltage was increased from 2.25V to 2.5V to 3.0V, the Ni:Mn:Co product ratio changed. At all voltages, Ni and Co precipitated preferentially compared to Mn. At 2.25V, there was a 3:1 selectivity for Co compared to Ni. At 2.5V, there was a 3:1 selectivity for Ni compared to Co. At 3V, there was no significant selectivity between Co and Ni. The ability to tune the system for selective metal hydroxide precipitation is related to the differences in the three metal pH-pe diagrams.

[0153] Figure 65 shows the permeation flow rate of 0 to 10 mL / min and 0 to 25 g / m 2 6 shows graphs of deposition rate vs. permeate flow rate for Co deposition and recovery for a deposition rate of 10000 Co / hr. Co deposition rate generally increases with increasing permeate flow rate and increasing deposition rate. FIG. 65 shows results for Co recovery (%) and deposition rate (g / m2 / h) from black mass, i.e., shredded end-of-life Li-ion batteries, or input to electrochemical deposition as shown in FIG. 60, and from the extract as a function of permeate flow rate for the standard flow configuration (see FIG. 23). As in FIG. 62, increasing the permeate flow rate decreases Co recovery but increases the deposition rate. Less Co is recovered, but the deposition rate increases due to a larger increase in the total mass flow rate Co.

[0154] FIG. 66 shows the permeation flow rate of 0 to 10 mL / min and the permeation flow rate of 0 to 25 g / m 26 shows graphs of deposition rate vs. permeate flow rate for Ni deposition and recovery for a deposition rate of 100000 / hr. Ni deposition rate generally increases with increasing permeate flow rate and increasing deposition rate. Ni recovery generally decreases with increasing permeate flow rate and decreasing deposition rate. FIG. 66 shows results for Ni recovery (%) and deposition rate (g / m2 / h) from black mass, i.e., shredded end-of-life Li-ion batteries, or input to the electrochemical deposition of FIG. 60, and the extract, as a function of permeate flow rate in the standard flow configuration (see FIG. 23). As in FIG. 62, as the permeate flow rate increases, Ni recovery decreases but the deposition rate increases. Less Ni is recovered, but the deposition rate increases due to a larger increase in the total mass flow rate Ni.

[0155] FIG. 67 shows a graph of metal fraction at various voltages for Co, Ni, Mn, Li, Cu, Al and Ti. Co, Ni, Mn and Li had high metal fractions when deposited using the electrochemical deposition apparatus. Cu, Al and Ti had lower metal fractions at the voltages tested compared to Ni, Mn and Li. FIG. 67 shows the results for metal composition of the precipitate from the electrochemical deposition apparatus as a function of applied voltage from the black mass, i.e., shredded end-of-life Li-ion battery or input to the electrochemical deposition of FIG. 60, the extraction solution. As the applied cell voltage was increased from 2.25V and 3.0V, the product ratio of Ni:Mn:Co:Li:Cu:Al changed. At all voltages, Ni and Co precipitated preferentially compared to Mn. At 3V, Co was selectively precipitated 2:1 over Ni. The ability to tune the system for selective metal hydroxide precipitation is related to the difference in the three metal pH-pe diagrams. At both voltages, Li did not precipitate. Since all of the Li is diverted to the electrochemical deposition apparatus effluent, this can be thought of as a Li brine by-product with Li levels similar to those present in naturally occurring Li brines.

[0156] Figure 68 shows a graph of unit margin vs. deposition rate. Deposition rates above 125 resulted in positive unit margins. Figure 68 shows unit margin (%) as a function of porous electrode lifetime (hours) based on a sensitivity analysis of a detailed technoeconometric analysis of the flow diagram in Figure 60, using black mass, i.e., shredded end-of-life batteries, as input. The assumptions were the same as in Figure 68. The sensitivity analysis shows that to achieve a positive unit margin, approaching the limit at >100 hours, the electrode lifetime needs to exceed 50 hours. These are conservative values, as we have already achieved them experimentally and industrial electrode lifetimes are typically in the range of 2000-20000 hours.

[0157] Figure 69 shows a graph of deposition rate versus permeate flow rate for Co deposition and recovery. Co deposition rate generally increases with increasing permeate flow rate and increasing deposition rate. Co recovery generally decreases with increasing permeate flow rate and decreasing deposition rate.

[0158] 70 is a series of SEM images 618 showing metal oxide precipitates collected and dried on an electrochemical deposition apparatus where the feed is a synthetic battery porous cathode material stream. SEM image 620 shows metal oxide precipitate 622 with a 10 micron scale bar 624 annotated. SEM image 620 shows metal oxide precipitate 622 with a 2 micron scale bar 626 annotated.

[0159] 71 is a series of SEM images 628 showing metal oxide precipitates collected and dried on an electrochemical deposition apparatus when the feed is black mass extract. SEM image 630 shows metal oxide precipitate 632 with a 10 micron scale bar 634 annotated. SEM image 636 shows metal oxide precipitate 632 with a 2 micron scale bar 634 annotated.

[0160] The electrochemical deposition apparatus or system may include a porous cathode material or other porous material having a high surface area. The porous cathode material allows a solution (e.g., an aqueous solution) to traverse and / or pass through the porous cathode material. The porous cathode material may be electrically conductive. The porous cathode material may be positively or negatively charged. The porous cathode material may be charged by a direct current ("DC") source, an alternating current ("AC") source, or a pulsed current. The porous cathode material may be regenerated.

[0161] Porous cathode materials may include, but are not limited to, carbon nanotubes and / or carbon fibers. Carbon nanotubes may be single-walled, multi-walled, or combinations thereof. Carbon nanotubes may have lengths including, but not limited to, at least about 0.05 mm, about 0.05 mm to about 2.0 mm, about 0.1 mm to about 1.8 mm, about 0.2 mm to about 1.5 mm, about 0.4 mm to about 1.4 mm, about 0.6 mm to about 1.2 mm, about 0.8 mm to about 1.0 mm, or about 2.0 mm. Porous cathode carbon or other materials such as metal mesh or felt may have lengths of at least about 25 mm. 2 / g, approx. 25m 2 / g~about 1000m 2 / g, approx. 50m 2 / g ~ approx. 950m 2 / g, about 100m 2 / g ~ approx. 900m 2 / g, approx. 150m 2 / g~about 850m 2 / g, approx. 200m 2 / g~about 800m 2 / g, approx. 250m 2 / g ~ approx. 750m 2 / g, approx. 300m 2 / g~about 700m 2 / g, approx. 350m 2 / g~about 650m 2 / g, approx. 400m 2 / g~about 500m 2 / g, or about 1000m 2The anode may include a high surface area compared to solid materials, including but not limited to, SiO2 / g. The anode may be porous or include a porous material. The anode may include, but is not limited to, carbon cloth or felt, Ti mesh or felt.

[0162] The electrochemical deposition apparatus and method can enable flow-through electrochemistry. The electrochemical deposition apparatus and method may not be limited by slow diffusive mass transport. The electrochemical deposition apparatus and method can maintain rapid deposition kinetics. Rapid deposition kinetics include, but are not limited to, at least about 20 g hr -1 m -2 , at least about 50g hr -1 m -2 , at least about 100 g hr -1 m -2 , at least about 200 g hr -1 m -2 , at least about 300g hr -1 m -2 , at least about 400g hr -1 m -2 , at least about 500g hr -1 m -2 , at least about 600g hr -1 m -2 , at least about 700g hr -1 m -2 , at least about 800g hr -1 m -2 , at least about 900g hr -1 m -2 , at least about 1000 g hr -1 m -2 , at least about 2000 g hr -1 m -2 , at least about 5000 g hr -1 m -2 , at least about 10000g hr -1 m -2 , or at least about 20,000 g hr -1 m -2 Rapid deposition kinetics may include, but are not limited to, deposition rates of about 20 g hr-1 m -2 ~About 1000g hr -1 m -2 , about 50g hr -1 m -2 ~about 900g hr -1 m -2 , about 100g hr -1 m -2 ~about 800g hr -1 m -2 , about 200g hr -1 m -2 ~about 700g hr -1 m -2 , about 300g hr -1 m -2 ~about 600g hr -1 m -2 , about 400g hr -1 m -2 ~about 500g hr -1 m -2 , or about 1000 g hr -1 m -2 The standard flow deposition rate can include a deposition rate including the formula R d,avg (gm -2 h -1 )=337.6×Q p (mL min -1 )×(C f -C p ) where Q p (mL min -1 ) is the permeate flow rate, and C f and C p are the molar concentrations in the feed and permeate, respectively (C f -C p (The recovery rate is greater than 100.) The maximum deposition rate is given by the formula R d,max (gm -2 h -1 )=117.4×I ss (A) can be calculated according to I ss is the steady state current.

[0163] The electrochemical deposition apparatus and method may include an electroactive area in which one or more metals are deposited. The electroactive area may be at least about 25 cm 2 , about 25cm2 ~About 1000cm 2 , about 50cm 2 ~about 900cm 2 , about 75cm 2 ~about 800cm 2 , about 100cm 2 ~about 700cm 2 , about 200cm 2 ~about 600cm 2 , about 300cm 2 ~about 500cm 2 , or about 1000 cm 2 The electroactive area may include, but is not limited to, an area of ​​approximately 93.75 cm 2 The electroactive area may include an area of ​​at least about 1.0 m 2 , about 1.0m 2 ~about 10.0m 2 , about 1.5m 2 ~about 9.5m 2 , about 2.0m 2 ~about 9.0m 2 , about 2.5m 2 ~about 8.5m 2 , about 3.0m 2 ~about 8.0m 2 , about 3.5m 2 ~about 7.5m 2 , about 4.0m 2 ~about 7.0m 2 , about 4.5m 2 ~about 6.5m 2 , about 5.0m 2 ~about 6.0m 2 , or about 10.0 m 2 The region may include, but is not limited to,

[0164] The electrochemical deposition apparatus and methods may be run in parallel to increase the electroactive area. The total electroactive area of ​​the electrochemical deposition apparatus and methods is at least about 10 m 2 , about 10m 2 ~about 20m 2 , about 11m 2 ~about 19m 2 , about 12m 2 ~about 18m 2 , about 13m 2 ~about 17m2 , about 14m 2 ~about 16m 2 , or about 20m 2 The total electroactive area of ​​the electrochemical deposition apparatus and method may include, but is not limited to, at least about 20 m 2 , about 20m 2 ~about 200m 2 , about 100m 2 ~about 190m 2 , about 110m 2 ~about 180m 2 , about 120m 2 ~ approx. 170m 2 , about 130m 2 ~about 150m 2 , about 140m 2 ~about 150m 2 , or about 200m 2 The number of individual electrochemical deposition devices operating in parallel can include, but is not limited to, at least 2, 2-200, 10-180, 20-160, 30-140, 40-120, 50-100, 60-90, 70-80, or 200.

[0165] The electrochemical deposition apparatus and method may include a total surface area calculated as the specific surface area times the weight of the electroactive material. For example, 100 m 2 50 g of electroactive material with a specific surface area of ​​5000 m 2 The electrochemical deposition apparatus and method may also include a geometric surface calculated from the actual density times the surface area. For example, 2 50m above the surface 2 50 g of electroactive material with a real density of 1000 / g will have a mass of 1 m 2 The electroactive area of ​​the electrochemical deposition device may be between the total surface area and the geometric surface area.

[0166] The electrochemical deposition apparatus and method can maintain a current density. The current density can be a steady state current density. The current density can be at least about 1 mA / cm 2 , about 1mA / cm 2~about 50mA / cm 2 , about 5mA / cm 2 ~about 45mA / cm 2 , about 10mA / cm 2 ~about 40mA / cm 2 , about 15mA / cm 2 ~Approx. 35mA / cm 2 , about 20mA / cm 2 ~about 30mA / cm 2 , or about 50 mA / cm 2 The current density may include, but is not limited to, at least about 50 mA / cm 2 , about 50mA / cm 2 ~about 50A / cm 2 , about 5A / cm 2 ~about 45A / cm 2 , about 10A / cm 2 ~about 40A / cm 2 , about 15A / cm 2 ~About 35A / cm 2 , about 20A / cm 2 ~About 30A / cm 2 , or about 50 A / cm 2 The current density may include, but is not limited to, at least about 50 A / m 2 , about 50A / m 2 ~Approx. 7.0kA / m 2 , about 0.5kA / m 2 ~about 6.5kA / m 2 , about 1kA / m 2 ~about 6.0kA / m 2 , about 1.5kA / m 2 ~about 5.5kA / m 2 , about 2.0kA / m 2 ~Approx. 5.0kA / m 2 , about 2.5kA / m 2 ~about 4.5kA / m 2 , about 3.0kA / m 2 ~about 4.0kA / m 2 , or about 7.0 kA / m 2The electrochemical deposition apparatus and method can operate over a wide range of pH values, including, but not limited to, at least pH 0, pH 0 to about pH 10, about pH 1 to about pH 9, about pH 2 to about pH 8, about pH 3 to about pH 7, about pH 4 to about pH 6, or about pH 10.

[0167] The electrochemical deposition apparatus and method can operate at a wide range of pressure values, including, but not limited to, at least about 1 atm, about 1 atm to about 50 atm, about 5 atm to about 40 atm, about 10 atm to about 30 atm, or about 50 atm. The electrochemical deposition apparatus and method can operate at a differential pressure, including, but not limited to, at least about 0.1 psi, about 0.1 psi to about 60 psi, about 1 psi to about 55 psi, about 5 psi to about 50 psi, about 10 psi to about 45 psi, about 15 psi to about 40 psi, about 20 psi to about 35 psi, about 25 psi to about 30 psi, or about 60 psi.

[0168] The electrochemical deposition apparatus and methods are capable of selectively recovering metal from the feed, which may include, but is not limited to, at least about 30%, between about 30% and about 99%, between about 50% and about 97%, between about 70% and about 95%, between about 75% and about 90%, between about 80% and about 85%, or about 99%.

[0169] The electrochemical deposition apparatus and method can produce purified metals, which may have a purity of at least about 20%, between about 20% and about 99.9%, between about 25% and about 99%, between about 30% and about 97%, between about 35% and about 95%, between about 40% and about 90%, between about 45% and about 85%, between about 50% and about 80%, between about 55% and about 75%, between about 60% and about 70%, or about 99.9%.

[0170] The electrochemical deposition apparatus and method can operate with a fluid flow. The fluid flow can be laminar and / or turbulent. The fluid flow can be present as a flow rate. The flow rate can include, but is not limited to, at least about 0.5 mL / min, about 0.5 mL / min to about 10.0 mL / min, about 1.0 mL / min to about 9.5 mL / min, about 1.5 mL / min to about 9.0 mL / min, about 2.0 mL / min to about 8.5 mL / min, about 2.5 mL / min to about 8.0 mL / min, about 3.0 mL / min to about 7.5 mL / min, about 3.5 mL / min to about 7.0 mL / min, about 4.0 mL / min to about 6.5 mL / min, about 4.5 mL / min to about 6.0 mL / min, or about 10.0 mL / min. Flow rates may include, but are not limited to, at least about 10 mL / min, about 10 mL / min to about 100 mL / min, about 20 mL / min to about 90 mL / min, about 30 mL / min to about 80 mL / min, about 40 mL / min to about 70 mL / min, about 50 mL / min to about 60 mL / min, or about 100 mL / min. Flow rates may include, but are not limited to, at least about 100 mL / min, at least about 100 mL / min to about 1000 mL / min, about 200 mL / min to about 900 mL / min, about 300 mL / min to about 800 mL / min, about 400 mL / min to about 700 mL / min, about 500 mL / min to about 600 mL / min, or about 1000 mL / min. Flow rates can include, but are not limited to, at least about 1 L / min, at least about 1 L / min to 10 L / min, about 2 L / min to about 9 L / min, about 3 L / min to about 8 L / min, about 4 L / min to about 6 L / min, or about 10 L / min. Flow rates can include, but are not limited to, at least about 10 L / min, at least about 10 L / min to about 100 L / min, about 20 L / min to about 90 L / min, about 30 L / min to about 80 L / min, about 40 L / min to about 60 L / min, or about 100 L / min.

[0171] The electrochemical deposition apparatus may include a cross-flow membrane system and / or a dead-end flow system. The electrochemical deposition apparatus may include a modular membrane-like configuration, such as a plate-and-frame membrane configuration, a spiral wound configuration, a tubular configuration, or a hollow fiber configuration. There may be multiple electrochemical deposition apparatuses. The multiple electrochemical deposition apparatuses may be operated in parallel. By operating multiple electrochemical deposition apparatuses in parallel, more metals can be deposited on the porous cathode material compared to operating a single electrochemical deposition apparatus. The multiple electrochemical deposition apparatuses may be operated in series. By operating multiple electrochemical deposition apparatuses in series, one type of metal can be deposited on each of the porous cathode materials in series, and more types of metals can be simultaneously deposited compared to operating a single electrochemical deposition apparatus. By operating multiple electrochemical deposition apparatuses in series, a continuous redox process can be facilitated.

[0172] A feed flows through the electrochemical deposition apparatus. The feed may be synthetic or may originate from an industrial or commercial process. The feed may include a single metal or may include multiple metals. The feed may include, but is not limited to, metal feed, black mass, metal particulate, metal compounds, metal ions, or combinations thereof. The single metal or multiple metals may have a concentration including, but not limited to, at least about 1 mM, about 1 mM to about 30 mM, about 5 mM to about 25 mM, about 10 mM to about 20 mM, about 30 to 50 mM, about 40 mM to 100 mM, about 60 mM to 400 mM, about 200 mM to 1000 mM, or about 500 mM to 5000 mM. The feed may include an electrolyte. The electrolyte may comprise a concentration including, but not limited to, at least about 1 mM, about 1 mM to about 30 mM, about 5 mM to about 25 mM, about 10 mM to about 20 mM, about 30 to 50 mM, about 40 mM to 100 mM, about 60 mM to 400 mM, about 200 mM to 1000 mM, or about 500 mM to 5000 mM. The feed may comprise numerous types of materials including, but not limited to, synthetic magnets, recycled magnets, black mass, electrical waste, battery waste, recycled batteries, recycled metal scrap, ores, ore tailings, or combinations thereof. The ores may include, but are not limited to, RE, Ti, and / or Fe. The ores may be ilmenite ores. The battery waste may include Li-ion battery waste. The battery waste may include battery cathode waste. The battery cathode waste may include, but are not limited to, Ni, Mn, and Co. The feed components may be pre-treated. Pretreatment may include any number of processes including, but not limited to, demagnetization, ball milling, filtration, acid leaching, or combinations thereof.

[0173] The apparatus and methods may utilize an acid, which may include any number of acids including, but not limited to, phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, hydrogen peroxide, carbonic acid, acetic acid, hydrogen cyanic acid, formic acid, oxalic acid, sulfurous acid, nitrous acid, or combinations thereof.

[0174] The apparatus and methods may include an oxidizer, which may include any number of oxidizers including, but not limited to, chlorine, bromine, oxygen, carbon dioxide, ozone, iodine, or combinations thereof.

[0175] The apparatus and method may include a solvent extractant, which may include chemicals including, but not limited to, Alamine 336 (tri / octyl-decylamine), meta-xylene, Cyanex 272 (bis-(2,4,4-trimethylpentyl)phosphinic acid), hydroxyoxime, di(2-ethyl-hexyl)phosphate, hexane, tributyl phosphate, hydrocarbon diluents, dialkyl sulfides, alkylamines, sodium hydroxide, TPEN (N,N,N',N',-tetrakis(2-pyridylmethyl)ethylenediamine, D2EHPA, or combinations thereof.

[0176] Pretreatment of the feed components may include, but is not limited to, filtering, crushing, grinding, mixing, homogenizing, leaching, pH adjustment, precipitation, or combinations thereof. The feed may include, but is not limited to, coal fly ash. The coal fly ash may be pretreated. The coal fly ash may be pretreated by reheating in a gas (e.g., an inert gas) to produce metal-rich carbon vapor and impinging the metal-rich carbon vapor on a glass fiber filter and collecting it. The metal-rich carbon vapor may be collected and leached (e.g., acid leached).

[0177] The apparatus and method may include a buffer. A buffer may be used to maintain the solution at a pH above / below the pH achieved by the electrochemical process. Maintaining the pH may be useful for separation and / or deposition of metals. For example, at pH 2.5, Al 3+ and Cu 2+ Both Al and Al are completely dissolved. 3+ was completely precipitated at pH 4.2, and Cu 2+only begins to precipitate below a pH of about 4.2. To complete the rapid separation of the two during cathodic formation of hydroxide in the porous cathode material, a buffer can be used to limit the pH increase to 4.2, causing Al to precipitate and Cu to remain in solution.

[0178] The apparatus and method may include a reagent for influencing the precipitation of a metal. For example, sulfate (M 2+ SO 4 2- Co, Ni, and Mn as carbonates (M 2+ CO 3 2- Co, Ni, and Mn as hydroxides or oxides are practically insoluble in water. Co, Ni, and Mn as hydroxides or oxides have a range of solubility that depends on the oxidation state. Thus, when Co, Ni, and Mn sulfates are added to water, they may completely dissolve even at concentrations above 1M. The precipitated material composition can then be manipulated using certain reagents. Carbon dioxide and / or bicarbonate can be used as reagents to react with the cathode-produced hydroxides to form carbonates. The carbonates can then react with the Co-Ni-Mn sulfate solution, making all the metals insoluble and precipitating together by forming a Co-Ni-Mn mixed precipitate.

[0179] Water may be used as the cathodic reagent and chloride as the anodic reagent. For selective precipitation, reactive chloride species generated at the anode can first react specifically with, for example, Mn, increasing its oxidation state from 2+ to 4+. Then, Mn 4+ reacted with the cathode hydroxide to produce MnO 2 selectively precipitates MnO 2 can be separated from the dissolved Co and Ni. The reactive chloride species selectively oxidizes Co from 2+ to 3+, forming Co(OH) which can be separated from the dissolved Ni. 3 This can result in the selective precipitation of

[0180] The buffers and / or reagents may be used at a pH including, but not limited to, at least about 0, about pH 0 to about pH 13, about pH 1 to about pH 12, about pH 2 to about pH 11, about pH 4 to about pH 10, about pH 5 to about pH 9, about pH 6 to about pH 8, or about pH 13. The buffers and / or reagents may be at a concentration including, but not limited to, at least about 0.01M, about 0.01M to about 2M, about 0.02M to about 1.8M, about 0.05M to about 1.5M, about 0.1M to about 1.2M, about 0.2M to about 1.0M, or about 2M.

[0181] The apparatus and methods of the present invention may include the selection of cathodic and / or anodic reagents to selectively precipitate individual metals from a mixture or to simultaneously precipitate all metals from a mixture. The list of ions and / or reagents includes, but is not limited to, potassium tetraoxalate dihydrate (KH 3 C 4 O 8 2H 2 O); Potassium hydrogen tartrate (KHC 4 H 4 O 6 ); Potassium dihydrogen citrate (KH 2 C 6 H 5 O 7 );Citric acid;Citric acid monohydrate;Citric acid trisodium salt;Sodium citrate tribasic dihydrate;Potassium hydrogen phthalate (KHC 8 H 4 O 4 ); Trisodium phosphate 3 PO 4 ; Disodium hydrogen phosphate (Na 2 HPO 4 );Sodium phosphate dibasic dehydrate;Sodium phosphate dibasic tetrahydrate;Dipotassium hydrogen phosphate (K 2 HPO 4 ); Potassium dihydrogen phosphate (KH 2 PO 4 ); Sodium dihydrogen phosphate (KH 2 PO 4 );Sodium pyrophosphate dibasic;Sodium pyrophosphate tetrabasic decahydrate;Disodium tetraborate decahydrate(Na 2 B4 O 7 10H 2 O; Sodium tetraborate decahydrate; Carbon dioxide; Sodium bicarbonate or sodium hydrogen carbonate (NaHCO 3 ); Sodium carbonate (Na 2 CO 3 );Calcium hydroxide Ca(OH) 2;Sodium hydrogen diglycolate;Phosphoric acid;Acetic acid;Sodium acetate;Sodium acetate trihydrate;Piperazine phosphate;Tris hydrochloride;Tris;Potassium hydrochloride (KCl);Hydrochloric acid (HCl);Sodium hydroxide (NaOH);Tris(hydroxymethyl)aminomethane;Borax;Ammonium acetate;Trifluoroacetic acid;Ammonium trifluoroacetate;MES 2-(N-morpholino)ethanesulfonic acid;MES hemi-sodium salt;MES hydrate;MES monohydrate;MES potassium salt;MES sodium salt;BIS TRIS bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane;BIS TRIS HCl;ADA N-(2-Acetamido)-2-iminodiacetic acid;ADA disodium salt;ACES 2-[(2-amino-2-oxoethyl)amino]ethanesulfonic acid;PIPES piperazine-N,N´-bis(2-ethanesulfonic acid);PIPES dipotassium salt;PIPES disodium salt;PIPES sesquisodium salt;PIPES sodium salt;MOPSO 3-(N-morpholino)-2-hydroxypropanesulfonic acid;MOPSO sodium salt;BIS TRISPROPANE 1,3-bis[tris(hydroxymethyl)methylamino]propane;BES N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid;BES sodium salt;MOPS 3-(N-morpholino)propanesulfonic acid;MOPS hemisodium salt;MOPS sodium salt;TES N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid;TES hemisodium salt;TES sodium salt;HEPES N-(2-hydroxyethyl)piperazine-N´-(2-ethanesulfonic acid);HEPES hemisodium salt;HEPES potassium salt;HEPES sodium salt;DIPSO 3-[N,N-bis(2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid;MOBS 4-(N-morpholino)butanesulfonic acid;TAPSO 3-[N-tris(hydroxymethyl)methylamino]-2-hydroxypropanesulfonic acid;TRIZMA Tris(hydroxymethyl)methylamine;HEPPSO N-(2-hydroxyethyl)piperazine-N´-(2-hydroxypropanesulfonic acid);POPSO piperazine-N,N´-bis(2-hydroxypropanesulfonic acid);POPSO hydrate;TEA Tris(2-hydroxyethyl)amine;EPPS 4-(2-hydroxyethyl)-1-piperazinepropanesulfonic acid;Tricaine N-tris(hydroxymethyl)methylglycine;Gly-Gly N-glycylglycine;Bicine N,N-bis(2-hydroxyethyl)glycine;HEPBS N-(2-hydroxyethyl)piperazine-N´-(4-butanesulfonic acid);TAPS N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid;TAPS sodium salt;AMPD 2-amino-2-methyl-1,3-propanediol;TABS N-Tris(hydroxymethyl)methyl-4-aminobutanesulfonic acid;AMPSO3-[(1,1-dimethyl-2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid;CHES2-(N-cyclohexylamino)ethanesulfonic acid;CAPSO3-(cyclohexylamino)-2-hydroxy-1-propanesulfonic acid;CAPSO sodium salt;AMP2-Amino-2-methyl-1-propanol;CAPS3-(cyclohexylamino)-1-propanesulfonic acid;CABS4-(cyclohexylamino)-1-butanesulfonic acid;AMPSO;AMPSO sodium salt;TRIZMA acetate;TRIZMA base;TRIZMA HCl;TRIZMA MALEATE;TRIZMA MONOPHOSPHATE;BICINE;CACODYLIC ACID;SODIUM CACODYLATE TRIHYDRATE;SODIUM BITARTRATE MONOHYDRATE;SODIUM TARTRATE DIHYDRATE;CALCIUM ACETATE HYDRATE;CALCIUM CARBONATE;LIME;DICALCIUM PHOSPHATE;ETHANOLAMINE HYDROCHLORIDE;IMIDAZOLE;GLYCOLIC ACID;IMIDAZOLE HCl;GLYOXALINE;PERIODIC ACID;POTASSIUM ACETATE;POTASSIUM BICARBONATE;POTASSIUM CARBONATE;POTASSIUM CITRATE TRIBASIC MONOHYDRATE;POTASSIUM HYDROGEN PHTHALATE;DICALCIUM PHOSPHATE Potassium;Potassium phosphate dibasic trihydrate;Potassium phosphate monobasic;Potassium phosphate tribasic;Histidine;Lactic acid;Sodium lactate;Potassium lactate;Gluconic acid;Sodium gluconate;Potassium gluconate;Calcium gluconate;Aspartic acid;Sodium aspartate;Potassium aspartate;Calcium aspartate;Glutamic acid;Sodium glutamate;Potassium glutamate;Calcium glutamate;Succinic acid;Sodium succinate;Potassium succinate;Calcium succinate;Maleic acid;Sodium maleate;Potassium maleate;Calcium maleate;Fumaric acid;Sodium fumarate;Potassium fumarate;Calcium fumarate;Ketoglutaric acid;Glutarate salts;Oxalic acid;Oxalates;Malic acid;Malonic acid esters;EDTA formic acid;Formates;Carboxylic acids and their derivatives;Propionic acid;Propionates;Butyric acid;Butyrate salts;Benzoic acid, benzoates and their derivatives;Toluic acid;Eluents;Nitrobenzoic acid;Nitrobenzoates;Chlorobenzoic acid;Chlorobenzoates;Phenol, phenolates and their derivatives;Nitrophenols;Nitrophenolates;Halophenols ;Halophenolates;Alkylphenols;Alkylphenolates;Ammonia;Ammonium;Alkylamines and their derivatives;Aminoalcohols and their derivatives;Phosphates and their derivatives;Hydrogen fluoride and fluoride salts;Hydrogen iodide and iodide salts;Selenic acid and selenite;Iodic acid;Iodates;Hydrogen bromate;Bromates;Hydrogen sulfide;Hydrogen sulfide salts;Sulfide salts;Sulfur dioxide;;Sulfurous acid;Sulfite salts;Selenium dioxide;Selenious acid;Selenite salts;Selenic acid;Hydrogen selenate salts;Selenate salts;Silicon dioxide;Silicate;Silicate salts;Hydrogen chromate salts;Chromate salts;Hydrogen molybdate;Molybdate salts;Arsenic acid;Arsenates; may include perchloric acid; perchlorates; hydrogen cyanide; cyanide salts; hydrogen thiocyanate; thiocyanate salts; or combinations thereof.

[0182] The feed may include, but is not limited to, a solution, an aqueous solution, a non-aqueous solution, an organic solvent, an ionic liquid, a eutectic solvent, a gas, a homogeneous mixture, a heterogeneous mixture, a slurry, a non-Newtonian fluid, a vapor, or a combination thereof. The solution may include a metal stream. The feed flows via and / or through the porous cathode material of the electrochemical deposition apparatus. Multiple feeds may flow through the electrochemical deposition apparatus.

[0183] The electrochemical deposition apparatus and method may include a catalyst. The choice of catalyst may depend on the target porous cathode material and the anode reaction. For example, a hydrogen evolution reaction (HER) catalyst may be used in a reaction at the porous cathode material to reduce water and produce hydroxides (raising the pH). The specific HER catalyst may depend on cost, performance, and other parameters. The porous cathode material may be used for other processes other than water reduction, including, but not limited to, direct metal reduction precipitation; oxidant generation, including, but not limited to, reduction of oxygen to hydrogen peroxide; reductant generation, including, but not limited to, reduction of carbon dioxide to carbon dioxide radicals; and / or reduction of the required overall cell potential using oxygen rather than water as the sacrificial electron acceptor. The anode may be used for other processes, including, but not limited to, direct metal oxidation precipitation; oxidant generation, such as the oxidation of chloride to dichloride radicals; and / or reduction of the required overall cell potential using a sacrificial electron donor. Selective catalyst selection may have a significant impact on the electroextraction process, and catalyst selection may allow control of the desired metal precipitation process.

[0184] HER catalysts for porous cathode materials include, but are not limited to, metals, including Pt, Pt / C, Tl, In, Cd, Pb, Ga, Zn, Sn, Bi, Ag, Cu, Fe, Co, Ni, Au, Rh, Ir, Re, W, Mo, Nb, Ti, Ta, Al, Pd, Hg, V, Hf, or combinations thereof; Ni-Ti, Mo-Ni, Mo-Co, Mo-Pt, Ni-Zr, Mo-S, Ni-Co, Ni-Fe, Ni-Mo-Cd, Ni-Mo-Fe, La 5 Alloys, including but not limited to Ni alloys, or combinations thereof; carbon-based materials, including but not limited to graphene, graphene doped (with B, N, S, P), CNTs, CNTs doped (with B, N, DP), black carbon, activated carbon, or combinations thereof; IrO 2 -RuO 2 , Sr x NbO 3-δ or combinations thereof; MoS 2 , FeS 2 , FeNiS, TaS 2 , NbS 2 , Mo 2 C, MoSe 2 , CoMoS 2 , W.S. 2( MoS doped with Fe, Co, Ni, Cu, and Pt 2 , doped MoS 3 , or combinations thereof; 2D nanomaterials, including but not limited to Co-porphyrins, Rh-porphyrins, Fe-porphyrins, Ni-porphyrins, Cu-corroles, bisorganometallic diporphyrins, Ni-diphosphines, or combinations thereof; hydrogenases and hydrogenase mimetics; CoP, MoP 2 , or combinations thereof; carbides, including but not limited to WC; MoS 2 , NiS 2 Sulfides, including but not limited to, ZnS, CdS, or combinations thereof; R-SiW 12 O 4 0 4- , H 3 PMo 12 O 40 or combinations thereof.

[0185] An oxygen evolution catalyst (OEC) can be used at the anode, with TiO 2 , ZnO, WO 3 , IrO 2 , MnO 2 , Mn 2 O 3 , CoO, Co 2 O 3 , CoO 2 , Co 3 O 4 , Fe 2 O 3 , CuO, NiO, Ni2 O 3 , CoOOH, RuO 2 , PtO, FeOOH, PbO 2 , PtO 2 , Fe 3 O 4 , NiO x , SnO 2 , Ta 2 O 5 , ZrO 2 , WO 3 or a combination thereof; CoSe 2 , NiSe, Co 3 S 4 , MoS 2 , TaS 2 or combinations thereof; metal chalcogenides, including but not limited to SrTiO 2 , BiVO 4 , InSnO 2 , Co 3 V 2 O 8 , ZnCo 2 O 4 , CaMn 4 O 5 , CaMn 3 O 4 , CoNiO x , NiCuO x , CoMoO x , FeMoO x , CuCoO x , IrO 2- Ta 2 O 3 , NiCo 2 O 4 or combinations thereof; bimetallic oxides, including but not limited to NiFeS, NiCo 2 Se 4 or combinations thereof; 4 , BiCu 2 VO 6 , CoNiFe hydroxide, CoCrFeO x or combinations thereof; multi-metal oxides, including but not limited to N-TiO 2 , Ni-IrO 2 , Ni-RuO2 or combinations thereof; doped metal oxides including, but not limited to, La:NaTaO 3 , LaSrCrO 3 , B.A. 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 -δ , LaNiO 3 , SrCoO 3 , B.A. 2 NdIrO 6 , SrIrO 2 , LaNiO 3 , LaMnO 3 , LaCuO 3 , LaCrO 3 , LaCoO 3 , SrFeO 3 , NiLa 2 O 4 or combinations thereof, including but not limited to perovskites; polyoxymetallates; Ni(OH) 2 -CNT, layered double hydroxides, including but not limited to Ni-Ti, Ni-Fe, Co-Fe, Co-Mn, Ni-V, Fe-Ni-Co, or combinations thereof; CoO x , NiO x , FeO x , NiyCo1-yOx, NiFeO x , MoS 2 2D nanomaterials, including but not limited to, NiFe, NiCo, or combinations thereof; Metal Organic Frameworks (MOFs), including but not limited to, NiFe, NiCo, or combinations thereof; Ni 3 N.C. 3 N 4 or combinations thereof; 3 C 2borates; phosphides; graphene, including but not limited to N-doped or S-doped graphene, or combinations thereof; molecules / porphyrins / corroles, including but not limited to Mn-corroles, Co-porphyrins, Ni-porphyrins, Mn-porphyrins, Ru-polypyridines, Ru-amines, Ir-complexes, or combinations thereof; or combinations thereof.

[0186] The catalyst can also be used in oxygen reduction reactions, 2 +2e - +2H + →H 2 O 2 The production of two electrons by is preferred. Catalysts used to achieve the preferred oxygen reduction can include, but are not limited to, metals, including but not limited to Pt; carbon-based materials, including but not limited to graphene, graphene doped with (B, N, S, P), CNT, CNT doped with (B, N, DP), black carbon, activated carbon; or combinations thereof; porphyrins / corroles, including but not limited to cytochrome C(4e-), cytochrome C oxidase, Fe-porphyrin, Co-porphyrin, Mn-porphyrin, Cr-porphyrin, Cu-porphyrin; or combinations thereof; or combinations thereof.

[0187] The catalyst may include a general oxidation catalyst, such as RuO 2 , IrO 2 , SnO 2 , PbO 2 or combinations thereof; Sb-Sn-RuO 2 , Ru 0.3 Ti 0.7 O 2 , Ru 0.3 Sn 0.7 O 2 , IrO 2 / SnO 2 , SnO 2 -Sb 2O 5 , Bi 2 O 5- PbO 2 , Ti-Ru-SnO x or combinations thereof; mixed metal oxides including, but not limited to, SnO2 doped (with B, Bi, F, Cl, P, Sb), PbO doped (with Fe, Co, Bi, F, etc.) 2 , or combinations thereof; metals, including but not limited to Pt; carbon, including but not limited to boron doped diamond, graphite, carbon pellets, carbon felt, carbon black slurry, carbon fiber, glassy carbon, graphite particles, or combinations thereof; or combinations thereof.

[0188] The catalyst may include a general reduction catalyst, such as α-PMo 12 O 40 3- , P 2 W 18 O 62 6- , P 2 W 17 O 61 Fe(III)(H 2 O) 8- SiW 11 O 39 Fe(II)(H 2 O) 6- , P.W. 11 O 39 Ru(III)(H 2 O) 4- , K 17 [Ln(As 2 W 17 O 61 ) 2 ]a x H 2 O, Nd(SiMo 7 W 4 O 39 ) 2 13- , a-SiMo 12 O 40 4-or combinations thereof; carbon-based materials (coated and uncoated), including but not limited to CNT, carbon felt, carbon foam, carbon mesh, carbon nanofiber, or combinations thereof; metal-based materials (coated and uncoated), including but not limited to foam, felt, mesh from Ni, Cu, Al, or Ti, or combinations thereof; or combinations thereof.

[0189] A voltage can be applied to the porous cathode material. A feed may flow through the porous cathode material of the electrochemical deposition apparatus while the voltage is applied to the porous cathode material. The voltage can include, but is not limited to, at least about 0.25V, about 0.25V to about 5.0V, about 0.5V to about 4.75V, about 0.75V to about 4.5V, about 1.0V to about 4.25V, about 1.25V to about 4.0V, about 1.5V to about 3.75V, about 1.75V to about 3.5V, about 2.0V to about 3.25V, about 2.25V to about 3.0V, or about 5.0V.

[0190] Metals may be electroprecipitated, i.e., deposited, on the surface of the cathode material. Deposited metals include, but are not limited to, neodymium ("Nd"), praseodymium ("Pr"), dysprosium ("Dy"), copper ("Cu"), lithium ("Li"), sodium ("Na"), magnesium ("Mg"), potassium ("K"), calcium ("Ca"), titanium ("Ti"), vanadium ("V"), chromium ("Cr"), manganese ("Mn"), iron, and the like. ("Fe"), Cobalt ("Co"), Nickel ("Ni"), Cadmium ("Cd"), Zinc ("Zn"), Aluminum ("Al"), Silicon ("Si"), Silver ("Ag"), Tin ("Sn"), Platinum ("Pt"), Gold ("Au"), Bismuth ("Bi"), Lanthanum ("La"), Europium ("Eu"), Gallium ("Ga"), Scandium ("Sc"), and Strontium ("Sr"). Sr, Yttrium ("Y"), Zirconium ("Zr"), Niobium ("Nb"), Molybdenum ("Mo"), Ruthenium ("Ru"), Rhodium ("Rh"), Palladium ("Pd"), Indium ("In"), Hafnium ("Hf"), Tantalum ("Ta"), Tungsten ("W"), Rhenium ("Re"), Osmium ("Os"), Iridium (" The deposited metal may include Cr, Hg, Ir, Hg, Pb, Po, Cerium, Ce, Samarium, Erbium, Ytterbium, Thorium, Uranium, U, Plutonium, Terbium, Tb, Promethium, Tellurium, Te, or combinations thereof. n+ (OH) n , or (M n+ ) m O (n×m) / 2 The deposited metal may be, but is not limited to, a metal carbonate. The metal may be deposited in a non-ionic form. The deposited non-ionic metal may be, but is not limited to, a metal carbonate. The deposited metal may be, but is not limited to, a metal carbonate. 0The metals may be deposited according to a particular stoichiometry. For example, if the first metal is M1, the second metal is M2, and the third metal is M3, the metals may be deposited in a stoichiometric ratio of M1:M2:M3. The metals may be deposited in any stoichiometric ratio, including but not limited to 1:1:1, 1:2:1, 1:1:2, or 2:1:1 stoichiometric ratios. The stoichiometrically deposited metals can be extracted, for example, from Co-containing materials. The stoichiometrically deposited metals may be deposited as metal hydroxides. The stoichiometrically deposited metals may be used as cathode materials. For example, stoichiometrically deposited Ni-Mn-Co hydroxides can be used to fabricate cathodes for Li-ion batteries.

[0191] The electrochemical deposition apparatus and method can change the oxidation state of one or more metals. Alkali metals, including but not limited to H, Li, Na, K, Rb, Cs, or combinations thereof, can only exist in aqueous solution as +1 oxidation. Native metals in the zero oxidation state are the only other common form, and this oxidation state reacts violently with water to produce hydrogen and the metal oxide. Alkali metal ions can have high water solubility and tend not to precipitate during electroextraction.

[0192] Alkali metals, including but not limited to Be, Mg, Ca, Sr, Ba, or combinations thereof, can only exist in aqueous solution as +2 oxidation. Naturally occurring metals in the zero oxidation state are the only other common form and react violently with water to produce hydrogen and the metal oxide. These metal ions have high water solubility and tend not to precipitate during electroextraction. [Table 1]

[0193] Metal hydroxides with higher transition metal oxidation states may have a more thermodynamically favorable metal cation-hydroxide anion bond and may be more prone to precipitate as metal hydroxides. For example, metal ions with an oxidation state of ≥ +4 may be more likely to precipitate at pH < 2 (or [HO-] < 10-12 Metal ions with an oxidation state of +3 tend to precipitate at 1 to 6 (or 10 M). -13 <[HO-]<10 -8 ) in the pH range of 6 to 10 (or 10). -8 <[HO-]<10 -4 ) pH range. Metal ions with an oxidation state of +1 precipitate at pH > 10 (or 10 -4 <[HO-]). Native metals precipitate naturally in water.

[0194] By oxidizing one metal to a higher oxidation state so that it precipitates at a lower pH, selective precipitation of a single metal ion may be possible. For example, the four primary metals in black mass may be nickel, manganese, cobalt, and lithium. Ni 2+ , Mn 2+ , and Co 2+ The standard reduction (reverse oxidation) potentials of Li are listed in Table 2. + cannot be further oxidized, so Li + The oxidation potential of Mn is not listed. Mn has a lower oxidation potential than Co or Ni, 2+ Selectively oxidize Mn to manganese dioxide (MnO 2 There may be several electroextraction strategies that can be used to precipitate as . [Table 2]

[0195] First, a low pH mixed Ni / Mn / Co feed may be passed through the porous cathode material where reduction of water may produce hydroxides and raise the pH. The solution is then diluted with Co 2+ Instead, oxidized Mn 2+ The oxidized Mn can then be passed through the anode at a sufficient anode potential to 4+ MnO 2 The resulting precipitate may be collected by filtration. An exemplary embodiment of this process is shown in FIG.

[0196] First, a mixed Ni / Mn / Co feed at moderate pH was added to the Co 2+ Instead of Mn 2+ The oxidized Mn may then be passed through the anode at an anodic potential sufficient to oxidize Mn. 2 The Ni / Co solution is precipitated as NiCo hydroxide and filtered by a separate filter placed either on the porous anode or between the anode and the porous cathode material. The remaining Ni / Co solution can then be passed through the porous cathode material where water reduction produces hydroxides, thereby raising the pH and precipitating the mixed NiCo hydroxide product. The mixed NiCo hydroxide product can then be collected by filtration. An exemplary embodiment of this process is shown in FIG.

[0197] A mixed Ni / Mn / Co feed at a moderate pH may flow through the anode first, and a NaCl electrolyte feed may flow between the anode and the porous cathode material. The NaCl electrolyte feed may flow through both the anode and the porous cathode material separately. As NaCl flows through the anode, chloride may be oxidized to chlorine, which is then oxidized to Mn in the anode flow. 2+ It reacts selectively with MnO as a precipitate. 2 Then, MnO 2 may be filtered out and the remaining Ni / Co solution may then flow through the porous cathode material. As the NaCl solution flows through the porous cathode material, water reduction occurs to produce hydroxides, which react with the Ni / Co in the solution to produce NiCo mixed metal hydroxides (MHP products). An exemplary embodiment of this process is shown in FIG.

[0198] A low pH mixed Ni / Mn / Co feed may flow in from the outside through the anode, and the electrolyte feed flows in from the outside through the porous cathode material, with both reaction solutions mixing between the electrodes. 2+ Instead of Mn 2+ When the anode is passed at a potential sufficient to oxidize Mn, Mn is selectively oxidized to Mn4+ Then, MnO 2 As the electrolyte passes through the porous cathode material, water is reduced to hydrogen and hydroxides, which mix in the center chamber and raise the pH to form MnO. 2 The precipitation of MnO can then be promoted. 2 can be collected by filtration. An exemplary embodiment of this process is shown in FIG.

[0199] If it is desired to separate all three metals individually, various electrochemical deposition chambers can be used in series to separate the multiple metals individually. For example, the anode potential for the second metal separation process is Co 3+ ToCo 2+ The temperature may be higher than in the first process so that oxidation is achieved. Then, Co 3+ reacts with the hydroxide produced by the porous cathode material to form Co(OH) 3 or CoOOH, which can be collected by filtration. The remaining Ni solution then flows through the porous cathode material to further increase the pH and form Ni(OH). 2 An exemplary embodiment of this process is shown in FIG.

[0200] Another flow regime for separating two or more individual metals can be to flow a mixed Ni / Mn / Co solution of moderate pH through an anode with an anodic potential sufficient to oxidize the electrolyte chloride to chlorine as it flows past the anode. The chlorine produced is then oxidized to Mn 2+ Oxidize to Mn 4+ This is MnO 2 Then, MnO 2 The remaining Ni / Co solution is then flowed through another anode at a potential sufficient to oxidize chloride to dichloride radical anions as the remaining Ni / Co solution flows through the anode. The resulting dichloride radical anions then convert Co 2+ Co3+ The Ni solution is oxidized to NiOOH, which precipitates and is collected by filtration. The remaining Ni solution flows through the porous cathode material, where it is reduced by the water flowing through the porous cathode material to produce hydroxide. The hydroxide reacts with Ni to form Ni(OH). 2 The resulting solution may be precipitated as a phosphate buffer, which can then be collected by filtration. An exemplary embodiment of this process is shown in FIG.

[0201] To precipitate the three metals Ni, Mn, and Co at once, a weakly acidic mixture of dissolved Ni / Mi / Co ("NMC") solution is flowed through the porous cathode material while an electrolyte solution is flowed between the anode and the porous cathode material. As the electrolyte flows through the porous cathode material, water is reduced to produce hydrogen and hydroxide anions, which are reacted with the dissolved Ni flowing therethrough. 2+ / Mn 2+ / Co 2+ to produce a mixed NMC hydroxide precipitate. If bicarbonate rather than sulfate is used as the electrolyte, the bicarbonate may react with the hydroxide to produce carbonate, which precipitates NMC to produce a mixed NMC carbonate precipitate. Similar strategies may be used to produce other NMC salts. The electrolyte flowing through the anode may undergo hydroxide to produce oxygen and protons / acid, which may then be recycled to the first leaching step. An exemplary embodiment of this process is shown in FIG. 30.

[0202] The flow scheme may be used for other metal mixtures, including but not limited to Fe, Cu, Ni, Co, PGMs, or combinations thereof, present in, for example, sulfide ores. In Table 1, the numbers under the elements are the common, e.g., typically observed, oxidation states. The multiple oxidation states indicate that the oxidation state may be manipulated by electrochemical redox processes. This process may take place directly at the anode or porous cathode material, or indirectly through the generation of reactive reducing agents, including but not limited to oxidizing agents such as carbon dioxide radicals or chlorine. For example, Cu 1+Cu 0 may occur in the porous cathode material, or Mn 2+ Mn 4+ Oxidation to may occur directly at the anode or indirectly via chlorine formation.

[0203] According to Table 2, when multiple metals with multiple oxidation states (e.g., the black mass extract initially has Ni, Co, and Mn all in the 2+ state, but the individual metals have multiple oxidation states Ni(2+), Co(2+, 3+), Mn(2+, 4+, 7+)), the applied electrochemical potential can then be rationally manipulated to selectively oxidize only one of the metals. For example, in the case of black mass, Mn can first be oxidized by applying an anodic potential of 1.25 to 1.85 V (or the appropriate range according to the Nernst equation for the particular Mn concentration). 2+ Mn 4+ to MnO for subsequent removal by filtration. 2 Co can then be selectively precipitated by applying a potential above 1.9 V (or the appropriate range according to the Nernst equation for the particular Co concentration). 2+ to selectively oxidize Co(OH) for subsequent removal by filtration. 3 Finally, by increasing the hydroxide concentration of the solution, the NiOOH that does not oxidize further can be precipitated. 2+ Ni(OH) 2 It may also be precipitated as such.

[0204] Metals, e.g. Ni, in the ore / concentrate (e.g. chalcopyrite) can be leached. The leached concentrate can be leached to remove e.g. Fe 2+ , Cu 1+ / 2+ , and Ni 2+ The solution first flows through a flow regime where dissolved Cu is first reduced to metallic copper at the porous cathode material. Dissolved Fe is then 2+ At the anode, Fe 3+ It can be oxidized to Fe 3+ precipitates to form Fe(OH) 3 or Fe2 O 3 The remaining Ni 2+ The solution is Ni 2+ flows through the porous cathode material to form Ni(OH) 2 The nitrate can be passed through another flow regime where it can be collected by filtration, producing hydroxides that precipitate as nitrate. An exemplary embodiment of this process is shown in Figure 31.

[0205] Low electroextraction reactivity metals, e.g. Li + can be collected as the product. + Li may be concentrated in a transportable brine, possibly as a carbonate, or precipitated after concentration. Electroextraction techniques may be hybridized, and electrodialysis techniques may be used to extract Li. + During electrodialysis, a bipolar electrode system can be used in combination with an anion exchange membrane placed near the anode and a cation exchange membrane placed near the porous cathode material, with the membrane being placed between the two electrodes. Electrodialysis can then separate the anions and cations in the electrolyte by using the electric field generated by the electrodes and the ions (cathode anionic hydroxides and anode cationic protons) generated during the splitting of water. For example, when a lithium sulfate solution flows between the ion exchange membranes, the positive lithium ions electromigrate through the cation exchange membrane toward the porous cathode material, and the negative sulfate ions electromigrate through the anion exchange membrane toward the anode. The ion exchange membrane can allow only ions to pass and prevent the passage of water. Thus, the ions that electromigrate through the membrane can be concentrated in the membrane permeate. If cationic contaminants are present in the lithium sulfate solution, Li + These can be eliminated by using a Li-ion specific cation exchange membrane that allows only Li to pass through. Finally, if a Li precipitate rather than a Li concentrate is the end product, carbonate ions can be cathodically generated using sodium bicarbonate electrolyte. 2CO 3 ) has a significantly lower STP solubility than lithium hydroxide (LiOH) at 130 g / L (5.4 M) compared to 13 g / L (0.18 M), respectively. The hybrid electroextraction-electrodialysis system can be further integrated to use the generated acid and / or base in alternative leaching and precipitation processes, respectively. The anodic / cathodic reactions can be used for oxidation / reduction of metals, and the increase / decrease in charge of the metals can drive an electromigration process similar to the proton / hydroxide during the splitting of water. An exemplary embodiment of this process is shown in FIG. 32.

[0206] The metal may be deposited as a metal hydroxide. The deposited metal hydroxide may be n+ (OH) n The porous cathode material may be in the form of an electrocatalyst for the reduction of water. The electrocatalytic reduction of water is carried out according to the chemical reaction 2H 2 O+2e - →H 2 +2HO - Hydroxide anions from the reduced water can react with metal ions to produce metal hydroxides. The hydroxide concentration near the cathode material can be high compared to other locations in the feed. The high relative hydroxide concentration near the cathode material promotes uniform metal or metal oxide precipitation and deposition on the porous cathode material. Metal hydroxides can be formed according to the following chemical formula: 2e - +2H 2 O→H 2 +2OH - M n+ +(OH) n →M(OH) n(s) M n+ +2e - +2H 2 O→H 2 +M(OH) n(s) . For example, cobalt hydroxide can be formed according to the following equation where the hydroxide ions are in stoichiometric excess compared to Co: 2e - +2H2 O→H 2 +2OH - Co 2+ +2OH - →Co(OH) 2(s) Co 2+ +2e - +2H 2 O→H 2 +Co(OH) 2(s) .

[0207] A single metal can be deposited on the surface of the porous cathode material. A single metal can be deposited on the surface of multiple porous cathode materials. Depositing a single metal on the surface of multiple porous cathode materials may include, for example, sequentially reducing the amount of metal in the feed by passing the feed through a first porous cathode material and depositing, for example, 90% of the metal in the feed on the first porous cathode material to form a depleted solution, and passing the depleted solution through a second porous cathode material to deposit, for example, 90% of the metal in the depleted solution on the second porous cathode material. The porous cathode material may have a long service life. The lifetime of the porous cathode material can include, but is not limited to, at least about 50 hours, about 50 hours to about 1000 hours, about 100 hours to about 900 hours, about 200 hours to about 800 hours, about 300 hours to about 700 hours, about 400 hours to about 600 hours, about 500 hours to about 1200 hours, about 1200 hours to about 2000 hours, about 1500 hours to about 3000 hours, about 2200 hours to about 4000 hours, or about 5000 hours.

[0208] A plurality of metals may be deposited on the surface of a plurality of porous cathode materials. For example, a first metal, such as Nd, may be deposited on a first porous cathode material, and a second metal, such as Pr, may be deposited on a second porous cathode material. In another example, Cu may be deposited on a first porous cathode material at 1.5V, and then Ni or Co may be deposited on a second porous cathode material at 3.0V.

[0209] Metals may be deposited on the porous cathode material to remove impurities from the feed and allow the metal of interest, e.g., Li, to pass through the electrochemical deposition apparatus for collection. Metal deposition on the porous cathode material results in a permeate. The permeate may be metal-free or metal-depleted. The metal-depleted permeate may be recycled as feed to the electrochemical deposition apparatus. Metal deposition on the porous cathode material may result in multiple permeates.

[0210] The deposited metal can be removed from the porous cathode material to form a concentrate and / or extract containing the metal. The concentrate and / or extract can be recycled as a feed to the electrochemical deposition apparatus. The deposited metal removed from the porous cathode material can form multiple concentrates and / or extracts.

[0211] The deposited metal is removed from the porous cathode material. The deposited metal can be removed from the porous cathode material by increasing the cross-flow over the surface of the porous cathode material and / or by air washing. The deposited metal can also be removed from the porous cathode material by passing a countercurrent through an electrochemical deposition device. The deposited metal can be removed from the porous cathode material by a pulsed current that repels the deposited metal from the porous cathode material. The deposited metal can also be removed from the porous cathode material by increasing the cross-flow over the surface of the porous cathode material in combination with a pulsed current. Additionally, the deposited metal can be removed from the porous cathode material by passing a countercurrent through an electrochemical deposition device in combination with a pulsed current.

[0212] The electrochemical deposition method may include a solvent extractant. The solvent extractant may be non-covalently bound to the cathode material. The solvent extractant may include, but is not limited to, tributyl phosphate, trioctylamine, tridecylamine, di(2-ethyl-hexyl)phosphate, dialkyl sulfides, hydroxyoximes, or combinations thereof. The solvent extractant may be dissolved in the feed solution, which may be aqueous or non-aqueous. The solvent extractant may facilitate an in situ reversible electrochemical metal solid-phase extraction process. The electrochemical deposition apparatus may include multiple solvent extractants.

[0213] The electrochemical deposition apparatus may have a center flow design. The center flow design may include an area for receiving the feed; an area for receiving the feed electrolyte; a first outlet; a porous cathode material; and an anode. The porous cathode material may be in communication with the area for receiving the feed. Hydroxide ions may migrate across the porous cathode material, originate at the surface of the porous cathode material, and / or originate within the porous cathode material and enter the area for receiving the feed. Metal ions may be deposited on the porous cathode material and may be converted to metal hydroxides. The converted metal hydroxides may form a metal hydroxide concentrate in the area for receiving the feed. The metal hydroxide concentrate may exit the electrochemical deposition apparatus through the first outlet. Water may be electrolyzed at the anode to form hydrogen ions and oxygen. Water may be electrolyzed at the porous cathode material to form hydrogen and hydroxide ions. The electrochemical deposition apparatus may further include a second outlet. The feed electrolyte may exit the electrochemical deposition apparatus through the second outlet. The feed electrolyte may be recycled to the leach solution (e.g., acidic leach solution). The electrochemical deposition apparatus may also include an anode permeate region, a feed region, and an electrolyte feed region. Optionally, there may be cross-flow between the anode permeate region, the feed region, and the electrolyte feed region. The electrochemical deposition apparatus may include a surface to prevent outflow from the electrolyte feed region. The surface may be, for example, a rigid wall, a valve, a flexible membrane, or a combination thereof. The electrochemical deposition apparatus may also include a third outlet. The first, second, and third outlets may be positioned in the electrochemical deposition apparatus to allow outflow from the anode permeate region, the feed region, and the electrolyte feed region.

[0214] The center-flow design can create a positive pressure perpendicular to and moving away from the porous cathode material and the anode. Metal hydroxides produced at or near the porous cathode material may be resuspended and / or collected by the cross-flow through the center-flow design.

[0215] The method of the present invention may include contacting or passing a feed containing metal ions through an electrochemical deposition apparatus, contacting the feed with a porous cathode material, depositing metal on the surface of the porous cathode material, and converting the metal ions to metal hydroxides to form a metal hydroxide concentrate. The method may further include recovering the metal hydroxides from the metal hydroxide concentrate. Recovering the metal hydroxides from the metal hydroxide concentrate may include passing the metal hydroxide concentrate through an apparatus including, but not limited to, a filter, a filtration apparatus, a sedimentation process, a centrifuge, a press, or combinations thereof. The method may further include electrolyzing water to form hydrogen gas and hydroxide ions. The method may further include electrolyzing water to form oxygen gas and hydrogen ions. The water may be electrolyzed at the porous cathode material and / or the anode. The method may further include contacting an electrolyte feed across the porous cathode material and / or the anode. The electrolyte feed may include HCl, HNO 3 , or other salts. The electrolyte feed may include, but is not limited to, electrolytic protons and electrolytic hydroxides. The electrolyte feed stream may transport electrolytic protons across the anode and electrolytic hydroxides across the porous cathode material. The method may also include recycling the electrolyte to the leach solution (e.g., acidic leach solution). Output from the feed region and / or the anode permeate region may also be recycled.

[0216] The invention may further comprise a filtration device. The filtration device may receive the metal hydroxide concentrate. The filtration device may comprise an inlet, an outlet, a housing, and a filter. The inlet may receive the metal hydroxide concentrate. The metal hydroxide depleted solution may exit the filtration device via the outlet. The filter may comprise a pore, a membrane, an exchange column, or a combination thereof. The filter may be capable of capturing the metal hydroxide. The invention may further comprise a vessel for containing the feed flowing into the electrochemical deposition apparatus. The invention may also include a user interface. The user interface may comprise a screen. The screen may be a touch screen. The user interface may comprise an automatic control system. The automatic control system may be used for cleaning, in situ cleaning, or cleaning cycles using a feedback loop.

[0217] The electrochemical deposition apparatus can generate gases. The gases include oxygen, hydrogen, chlorine, NO x (wherein X is an integer from 1 to 4), or a combination thereof. The electrochemical deposition apparatus may also include a gas release valve. The gas release valve can release gas generated by the electrochemical deposition apparatus. The gas release valve can include a vent, a manual valve, or a combination thereof.

[0218] The electrochemical deposition apparatus may include a filter press. The filter press may include a filter plate, a filter press cylinder, a porous cathode material, an anode, an inlet, and an outlet. The filter press may also include a mesh, a gasket, a current collector, a color gasket, or a combination thereof. A pair of meshes, gaskets, current collectors, and color gaskets may be at least partially disposed on either side of the filter plate. The mesh may be at least partially disposed within the filter plate. The current collector may include an elongated current collector. The elongated current collector may include a perforated metal sheet. The elongated current collector may include, but is not limited to, Ti, stainless steel, or other metals. The filter plate may be at least partially disposed between two gaskets. The porous cathode material may be at least partially disposed between the first current collector and the first collar. The anode may be at least partially disposed between the second current collector and the second collar. The collar may be at least partially disposed between the current collector and the color gasket. The electrolyte solution may flow through and / or across the filter plate. The porous cathode material may separate the feed and the electrolyte feed, for example, by preventing the feed and the electrolyte feed from mixing.

[0219] The electrochemical deposition apparatus may include a filter press and may include a plurality of plates arranged in parallel. The parallel arranged plates may form at least two channels. Each plate of the plurality of plates may receive the electrolyte. An electrode and an anode may be arranged at least partially around the plates. At least one channel formed by the parallel arranged plates may contact two porous cathode materials. A feed may be received by at least one channel in contact with the two porous cathode materials. At least one channel formed by the parallel arranged plates may contact two anodes. An anode permeate may be received by at least one channel in contact with the two anodes.

[0220] The electrochemical deposition apparatus, including the filter press, is configured to generate a flow rate of at least about 50 mL / min per plate, between about 50 mL / min per plate and about 10 L / min per plate, between about 100 mL / min per plate and about 9 L / min per plate, between about 200 mL / min per plate and about 8 L / min per plate, between about 300 mL / min per plate and about 7 L / min per plate, between about 400 mL / min per plate and about 500 mL / min per plate, between about 500 mL / min per plate and about 10 L / min per plate, between about 100 mL / min per plate and about 9 L / min per plate, between about 200 mL / min per plate and about 8 L / min per plate, between about 300 mL / min per plate and about 7 L / min per plate, between about 400 mL / min per plate and about 500 mL / min per plate, The feed flow rate and / or electrolyte feed flow rate may include, but are not limited to, at least about 6 L / min, about 500 mL / min per plate to about 5 L / min per plate, about 600 mL / min per plate to about 4 L / min per plate, about 700 mL / min per plate to about 3 L / min per plate, about 800 mL / min per plate to about 2 L / min per plate, about 900 mL / min per plate to about 1 L / min per plate, or about 10 L / min per plate. The total feed flow rate and / or electrolyte feed flow rate may include, but are not limited to, at least about 500 L / min, about 500 L / min to about 1500 L / min, about 600 L / min to about 1400 L / min, about 700 L / min to about 1300 L / min, about 800 L / min to about 1200 L / min, about 900 L / min to about 1100 L / min, or about 1500 L / min. The anode permeate flow rate may include, but is not limited to, at least about 18 L / min, about 18 L / min to about 99 L / min, about 27 L / min to about 90 L / min, about 36 L / min to about 81 L / min, about 45 L / min to about 72 L / min, about 54 L / min to about 63 L / min, or about 99 L / min. The anode permeate may include, but is not limited to, at least about 10%, about 10% to about 50%, about 20% to about 40%, or about 50% of the electrolyte feed. The anode permeate flow rate per plate may include, but is not limited to, at least about 1 L / min, about 1 L / min to about 36 L / min, about 9 L / min to about 27 L / min, or about 36 L / min.

[0221] The electrochemical deposition apparatus may be equipped with a computer control system that can evaluate the performance of the electrochemical deposition apparatus to design extractants with improved cathode material binding and / or metal selectivity. The computer control system can also evaluate the performance of the electrochemical deposition apparatus for real-time optimization of operating conditions.

[0222] The electrochemical deposition process may further include leaching. The leaching is performed by applying a current density (A / m 2 ) The current density should be at least 1 A / m 2 , about 1A / m 2 ~about 7000A / m 2 , about 10A / m 2 ~about 6500A / m 2 , about 50A / m 2 ~about 6000A / m 2 , about 100A / m 2 ~About 5000A / m 2 , about 200A / m 2 ~About 4500A / m 2 , about 300A / m 2 ~about 4000A / m 2 , about 400A / m 2 ~About 3500A / m 2 , about 500A / m 2 ~About 3000A / m 2 , about 600A / m 2 ~about 2500A / m 2 , about 700A / m 2 ~About 2000A / m 2 , about 800A / m 2 ~about 1500A / m 2 , or about 7000 A / m 2 may include, but is not limited to:

[0223] Leaching may generate acids and / or reagents. The generation rate is a function of the current density (A / m 2 ), electrode area (m 2 ), and the current efficiency of the reaction (η; the fraction of electrons flowing that results in the desired reaction). In the case of acid generation from water, the reaction is a function of the anodic water oxidation (2H2 O→4H + +4e-+O 2 ) for each electron transferred. + For example, 7000 A / m 2 at maximum current density of 1m 2 With an area of ​​1000 nm, the current at a single electrode is 7000 A or (7000 C / s) / (Faraday's constant; 96845 C / mol e-), which indicates that protons can be produced at a maximum rate of +d[H+] / dt=0.072 moles / sec, e.g., 1 mole of protons can be produced in 13.8 seconds. The overall production rate may be increased by multiple parallel electrodes.

[0224] Single electrode (1m 2 The range of acid production rates for the process may depend on both the steady-state current density and the current efficiency of the process. The steady-state current density can be reduced by decreasing the feed input rate. The current efficiency can be reduced by manipulating the simultaneous anodic oxidation reaction, which can reduce the proportion of the total current going to the water oxidation reaction. For example, 3 L of 4 M sulfuric acid per kg of black mass can be used for black mass leaching. Sulfuric acid has a pKa of -2.8 and 2, and a concentration of 4 M sulfuric acid can result in a pH between -1 and 0. This pH range indicates that in an aqueous solution of this concentration, all sulfuric acid molecules dissociate to produce protons and bisulfate. Thus, 12 moles of H are required for every kg of black mass to be leached. + can be used. 1000A / m 2 At a current density of 0.01 moles / sec and +d[H+] / dt=0.01 moles / sec, 12 moles of H are needed to leach 1 kg of black mass. + It takes 1200 seconds or 20 minutes to generate the required H. + The production time can be reduced.

[0225] The time scale of leaching can range from seconds to minutes, hours to days. The time scale of leaching can depend on the rate of acid production and / or the rate of particle dissolution. Particle dissolution can be a surface limited process, and the surface area to volume ratio of the particles can affect the overall dissolution or leaching rate. The size of the leached particles can range from tens to hundreds of microns for ore concentrates and tailings, to millimeters for crushed ore particles. The leached particles can have diameters including, but not limited to, at least 100 microns, about 100 microns to about 50 mm, about 300 microns to about 25 mm, about 500 microns to about 10 mm, about 1 mm to about 5 mm, or about 50 mm. Nanoparticle catalysts can also be used to accelerate the time scale of leaching. Larger particles can be subjected to further processing, such as, for example, grinding, milling, crushing, sonication, or a combination thereof, to achieve a smaller particle size distribution and increase the leaching rate. The leached particles may be agglomerated prior to leaching. The amount of material that needs to be dissolved can also affect the time scale of leaching with larger masses requiring longer leaching times. Particle sorting, including but not limited to magnetic separation, flotation, density separation, or combinations thereof, can be used to reduce the total mass and increase the leaching rate.

[0226] The type and oxidation state of the metal particles can also affect the timescale of leaching. Metal oxides and hydroxides react with acids (M n+ O (n / 2)(S) +nH + (aq) →M n+ (aq) +(n / 2)H 2 O), which may be leached directly to a high initial oxidation state (n +The higher the pH, the slower the dissolution and the lower the leaching rate. Oxides and / or hydroxides can be reduced by the addition of reducing agents (e.g. hydrogen peroxide, bisulfite, etc.) to decrease the oxidation state and increase the leaching rate. For example, a reducing acid (hydrogen peroxide + sulfuric acid) leach can be used for black mass. If the material to be dissolved is a metal or metal sulfide, an oxidizing acid leach may be required. Aqueous soluble metal ions of the metal (e.g. Pt 0 +Cl 2 →Pt 2+ +2Cl - ) or the initial oxidation of sulfides to higher oxidation states (S 2- +2O 2 →SO 4 2- ) may be required. This additional step can limit the overall rate of leaching.

[0227] Leaching efficiencies may include, but are not limited to, at least about 0.5%, about 0.5% to about 99%, about 1% to about 97%, about 5% to about 95%, about 10% to about 90%, about 20% to about 80%, about 30% to about 70%, about 40% to about 60%, or about 99%. A low leaching efficiency may be preferred when traces of high value materials or traces of hazardous materials are present during leaching. A high leaching efficiency may be preferred when most of the metals in the leached material are valuable. An intermediate leaching efficiency is preferred when only the target metal or hazardous metal is dissolved.

[0228] Acids may be used as oxidizing agents. Acids may include, but are not limited to, sulfuric acid, nitric acid, other acids, or combinations thereof. Acids may include, but are not limited to, mineral acids (or inorganic acids) derived from one or more inorganic compounds (compounds that are not carbon-based). Inorganic acids may include, but are not limited to, hydrofluoric acid; hydrochloric acid; hydrobromic acid; sulfuric acid, sulfurous acid; nitric acid; perchloric acid; perbromic acid; phosphorous acid; pyrophosphoric acid; sulfamic acid; fluorosilicic acid; selenic acid; phosphoric acid; hypophosphorous acid; phosphomolybdic acid; polyphosphoric acid; periodic acid; iodic acid; boric acid; molybdic acid; tungstosilicic acid; phosphotungstic acid; chlorosulfonic acid; chloroplatinic acid; metaphosphoric acid; hexafluorophosphoric acid; tetrafluoroboric acid; nitrosylsulfuric acid; hydroxylamine-O-sulfonic acid; hydrogen cyanide; hydrogen azide; chromic acid; water; hydrogen sulfide; carbonic acid; hydrogen peroxide; ammonium; arsenous acid; arsenic acid; or combinations thereof.

[0229] The acid may include organic acids. Organic acids are organic compounds with acidic properties (organic compounds are generally any chemical compound that contains a carbon-hydrogen bond). Organic acids include formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, benzenesulfonic acid, bromoacetic acid, dibromoacetic acid, tribromoacetic acid, glycolic acid, trifluoromethanesulfonic acid, peracetic acid, ethylenediaminetetraacetic acid, maleic acid, phthalic acid, succinic acid, aminomethanesulfonic acid, bromochloroacetic acid, salicylic acid, thioacetic acid, sulfanilic acid, oxalic acid, thioglycolic acid, malonic acid, chlorodifluoroacetic acid, propionic acid, anthranilic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, formic acid, lactic acid, tartaric acid, gallic acid, The carboxylic acids may include, but are not limited to, barbituric acids, fatty acids, tannic acids, malic acids, fumaric acids, benzoic acids, amino acids, fatty acids, sulfosalicylic acids, citric acids, toluenesulfonic acids, sorbic acids, nitrilotriacetic acids, pyruvic acids, iodoacetic acids, dehydroquinic acids, phenols and substituted phenols, thiophenols and substituted thiophenols, aminophenols and substituted aminophenols, anilines, picric acids, pyridines and substituted pyridines, methylammonium and other alkylammoniums, any carboxylic acid, or combinations thereof. Carboxylic acids are organic acids that contain a carboxyl group (C(=O)OH) attached to the R group. The general formula for carboxylic acids is R-COOH or R-CO 2 H, and R refers to an alkyl, alkenyl, aryl or other group.

[0230] Leaching may be carried out over a range of pH values, including, but not limited to, at least about -3.0, from about -3.0 to about 5.0, from about -2.5 to about 2.5, from about -2.0 to about 2.0, from about -1.5 to about 1.5, from about -1.0 to about 1.0, or about 5.0. Leaching may also be carried out under basic conditions.

[0231] Various types of materials can be leached. Materials that can be leached include, but are not limited to, black mass; agglomerated particles; concentrates, slurries, mixtures of metals, plastics, glass, fibers, polymers, or combinations thereof; battery materials, including but not limited to Li-ion batteries and / or NiMH batteries; catalyst scrap, including but not limited to catalytic converters, magnets, petroleum refining catalysts, or combinations thereof; manufacturing scrap; plating industry scrap and solutions; metal filter cakes; non-ferrous scrap; alloy scrap, including but not limited to Ni-Co alloy scrap; shredded and / or fragmented mixed non-ferrous scrap; Ni scrap; electric motors; precious metal solutions and / or sweeps; electronic waste, including but not limited to circuit boards; wiring; tailings; metal-containing thin films and / or coatings; crushed and / or pulverized metal materials; metal-containing particulates captured in filters; or combinations thereof.

[0232] Leaching may include an oxidizing agent. An oxidizing agent, also known as an oxidant or oxidizer, is a material that has the ability to oxidize other materials. An oxidizing agent may be used in combination with an acid for metal dissolution when metal particulates are present in metallic or sulfide state. In metallic state, the oxidizing agent may change from metallic state to cationic state to allow dissolution of metal ions. In metal sulfides, an oxidizing agent may be used to convert sulfur to a higher oxidation state with a lower binding energy with the metal ion that allows its release and dissolution from the solid. When an oxidizing agent is used with metal sulfides, the in situ generation of sulfuric acid from sulfide oxidation may be used as the leaching acid. Oxidants include fluorine, chlorine, bromine, iodine, hydroxyl radical, hydrogen peroxide, superoxide, hydroperoxide radical, oxygen, hypochlorous acid, hypofluorite, hypobromite, hypoiodite, dichloride radical, dibromide radical, diiodide radical, ozone, O-atom, carbonate radical, azide radical, amino radical, nitrogen dioxide radical, nitrogen trioxide radical, phosphite radical, sulfite radical, sulfate radical, peroxomonosulfate radical, selenite radical, dithiocyanate radical, chlorine dioxide, permanganate, ferrate, bromine dioxide, perborate, lead dioxide, aqua regia (3HCl + HNO 3 ), concentrated nitric acid, HNO 3 +H 2 SO 4 , persulfuric acid, Caro's acid, perchloric acid, chromic acid, chromium trioxide, nitrous oxide, nitrogen dioxide, or combinations thereof.

[0233] Leaching may involve a reducing agent. A reducing agent (also known as a reductant, reducer, or electron donor) is an element or compound that loses electrons in a redox chemical reaction or "donates" electrons to an electron acceptor (known as an oxidizing agent, oxidant, or oxidizer). A reducing agent can be used if the metal to be leached is present in a high oxidation state (>2+) that resists dissolution. A reducing agent reacts with a higher valence metal ion to produce a lower valence metal ion that is more easily dissolved (e.g., Fe 3+ +e-→Fe 2+ Reducing agents may include, but are not limited to, aqueous electrons, H atoms, carbon dioxide radicals, phosphorous radicals, sulfur dioxide radicals, sulfites, hydrogen peroxide, hydrazine, hydrogen, sodium borohydride, sodium aluminum hydride, ferrous ions, stannous ions, sulfur dioxide, dithionates, thiosulfates, ascorbic acid, reducing sugars, phosphites, dithiothreitol, carbon monoxide, cyanide, reduced carbon, hydroquinone, or combinations thereof.

[0234] Various types of metals, minerals, and / or ore concentrates can be leached. An ore concentrate is an ore material that has been crushed, ground, and / or milled to a small particle size and then concentrated with respect to the desired metals by a separation process such as magnetic separation, density separation, flotation, size separation, etc. The ore concentrates can include, but are not limited to, copper concentrates; nickel concentrates; cobalt concentrates; titanium concentrates; base metal concentrates; gold concentrates; silver concentrates; RE concentrates; precious metal concentrates; mixed concentrates including, but not limited to, Ni-Cu, Ni-Co, Co-Cu, Ni-Co-Cu, Ni-Co-Cu with platinum group metals (PGMs). Minerals that may be leached include, but are not limited to, ilmenite; coal or coal by-products such as fly ash, bauxite, acanthite, baryte, beryl, bornite, cassitate, chromite, cinnabar, columbit-tantalite, galena, molybdenite, pentlandite, scheelite, sperillite, sphalerite, uraninite, wolframite, taconite, pyrolusite, brunites, psilomelane, and rhodochrosite, or combinations thereof; Li in spomdenite, pegmatite, petalite, lepidolite, hectorite clays, and other clays; and Li in argon, malachite, azurite, cuprite, tetrahedrite, digenite, malachite, azurite, cuprite, tetrahedrite, tetrahedrite, digenite, malachite, azurite, cuprite, tetrahedrite, tetrahedrite, digenite, tetrahedrite ... Cu ores including tephra, chrysocolla, tennantite, dioptase, and enagite; Fe ores including but not limited to magnetite, hematite, goethite, limonite, siderite, and taconite; co-ores including but not limited to cobaltates; Ni in millerite, nickel line, pentandite, kamasite, theenite, laterite, nickel-bearing limonite, and garnierite; Zn in sphalerite, smithsonite, hemimorphite, wurtzite, and hydrozinsite; Nb in coulombe, pyrochlore, euxenite, and carbonatite; Mo in wulfenite, powderite, and molybdenite; Ru in pentlandite and pyroxenite; Rh as free metal; Pd in ​​cooperite, polarite, and free metal;Ag in acanthite, argentite, free metals, chlorazilite, pnictides, and chalcogenides; Sn in cassiterite, stannite, cylindrite, frankite, camphordite, and thearite; Ta in tantalite, microlite, wodginite, euxenite, polyclase, samarsite, and fergusonite; W in wolframite, scheelite, ferberite, and wolframite; Molybdenite, sulfides, te PGM metals as tellurides, antimonides and arsenides and Re in alloys with nickel and copper; Pt as free metal, alloys, sulphides, tellurides, antimonides, arsenides, spectrilite and cooperite; free / native metal, alloys with Ag, Hg, Te etc., electromagnets, vein deposits, nuggets, calaverite, crenelite, nagiite, petzite, sylvanite, muldonite, aurostivite, auricipite, argill ... Au as lydo, novodneprite, and weissianite; Pb in galena, bolangerite, anglaisite, and cerussite; Bi as bismuthite and bismuthate; xenotime, monazite, gadolinite, samarckite, euxenite, yttrotantalite, yttrotungstite, yttrofluorite, salenite, yttrialite, eudialyte, bastansite, allanite, loparite, ansilite. rare earth elements (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb) in tungsten, pallasite, lanthanite, kebukinites, celite, stillwellite, bryolite, fluorescelite, cerianite, carbonatite, pegmatite; U in carnotite, autunite, uranophane, trubernite, coffinite, lignite, monazite; or combinations thereof.

[0235] The leaching may include counterions. If the reagent and / or buffer is anionic, the cationic counterion may be H + , Na + , K + , Rb + , Cs + , N.H. 4+ , B.E. 2+ , Mg 2+ , Ca 2+ , Sr2+ , B.A. 2+ , Al 3+ , Bi 2+ , tetraphenylphosphonium, tetraalkylammonium, 1-ethyl-3-methylimidazolium and derivatives, ionic liquid cations, or combinations thereof. When the recited reagent / buffer is cationic, the anionic counterion may be F - , Cl - , Br - , I - , borate, nitrate, sulfate, phosphate, bromate, chlorate, iodate, acetate, formate, tetrafluoroborate, hexafluorophosphate, tetraphenylborate, tetrakis(pentafluorophenyl)borate, ionic liquid anions, or combinations thereof. [Industrial Applicability]

[0236] The invention is further illustrated by the following non-limiting examples. Example 1

[0237] Cobalt filter cake or "black mass" was obtained from a vendor. The black mass was produced by first isolating an end-of-life Li-ion battery mixture, inert shredding this mixture, and then mechanically separating the bulk plastic and metal (current collector) from the active anode (graphite) and porous cathode material (metals, i.e., Ni, Mn, Co) powders. The latter was the black mass. The primary metal weight of the black mass was calculated. The remaining mass was oxide oxygen, anode graphite, and polymer binder. A general procedure was developed to leach metals from the black mass following reported literature on low pH reductive Co dissolution methods.

[0238] Metal leaching was completed in a 2L Erlenmeyer flask by adding 500mL of 4M sulfuric acid, 200mL of 30% hydrogen peroxide, and 120g of black mass. Black mass was added in smaller aliquots of 10-20g with vigorous stirring to prevent the formation of graphite-stabilized foam from oxygen gas formation. Upon black mass addition, the reaction solution was heated. Once the black mass solution was stabilized, it was heated to 60-80C for 2-3 hours under magnetic stirring. The solution was then diluted to 1L with DI water and filtered through a 0.3 micron nylon membrane to remove undissolved material. The pinkish tan filtrate was then measured for pH (typically 1-2) and UV-vis metal content (typically 100-150mM Co / Ni). The procedure was determined to leach >90% of the metals in the black mass as received and was successful on the first attempt.

[0239] The pH of the acidic metal leach solution was then raised to 4-5 by the addition of small aliquots of 2M NaOH. Once this pH was reached, a tan precipitate began to form in the solution (bottom left center of Scheme 1). The pH adjusted solution was then filtered through a 0.3 micron membrane to remove the precipitated material. At this point, the black mass extract had a Ni:Mn:Co:Li metal ion ratio of 3:2:4:1. Trace metals such as Fe, Cu, and Al were mostly removed by the pH adjustment and filtration steps. The NMC BME was ready for the electrochemical deposition apparatus to reuse the active porous cathode material as metal hydroxides.

[0240] The above examples can be repeated with equal success by substituting the generally or specifically described components and / or operating conditions of embodiments of the invention for those used in the above examples.

[0241] Although particular metals, reagents, acids, pretreatments, material types, and operating parameters have been described with reference to particular embodiments, other metals, reagents, acids, pretreatments, material types, and operating parameters may be used in accordance with the present invention, particularly since each material or metal being recycled or processed requires customized reagents, processes, and operating parameters. Variations and modifications of the present invention for such customization will be apparent to those skilled in the art, and it is intended to cover all such customizations.

[0242] It is to be noted that, in the specification and claims, "about" or "approximately" means within twenty percent (20%) of a given amount or value.

[0243] Although the present invention has been described in detail with particular reference to the disclosed embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be apparent to those skilled in the art, and it is intended to cover all such modifications and equivalents. The entire disclosures of all references, applications, patents, and publications cited above and / or in the appended documents, and of the corresponding applications, are incorporated herein by reference. Unless specifically stated above as "essential," none of the various components or their interrelationships are essential to the operation of the present invention. Rather, the various components can be substituted and / or their relationships rearranged with respect to one another to achieve desired results.

Claims

1. A metal electrodeposition system, wherein the metal comprises a metal compound, elemental metal, metal ions, or a combination thereof, and the metal electrodeposition system comprises at least one porous cathode material, at least one anode, and is provided with the at least one porous cathode material and the at least one anode form an interelectrode region, the interelectrode region existing between the opposing surfaces of the at least one anode and the at least one porous cathode material, and the interelectrode region does not include a physical separation layer, the electrochemical deposition system further comprises a housing disposed around the at least one porous cathode material and the at least one anode, at least one gas release channel, at least one inlet, at least one outlet, A metal electrodeposition system comprising.

2. The metal electrodeposition system according to claim 1, comprising a plurality of metal electrodeposition systems, wherein the plurality of electrodeposition systems are arranged such that an electrolyte flows in series between the plurality of electrodeposition systems.

3. The metal electrodeposition system according to claim 1, comprising a plurality of metal electrodeposition systems, wherein the plurality of electrodeposition systems are arranged such that an electrolyte flows in parallel between the plurality of electrodeposition systems.

4. The metal electrodeposition system according to claim 1, further comprising a filter.

5. The metal electrodeposition system according to claim 1, further comprising a current collector.

6. The metal electrodeposition system according to claim 1, further comprising a computer control system.

7. The metal electrodeposition system according to claim 1, wherein the at least one porous cathode material contains carbon.

8. The metal electrodeposition system according to claim 1, wherein the at least one porous cathode material contains metal.

9. The metal electrodeposition system according to claim 1, wherein the at least one porous cathode material contains metal.

10. The at least one porous cathode material includes an electroactive region of at least about 25 cm ２ of the electrodeposition system of a metal according to claim 1.

11. The metal electrodeposition system according to claim 1, comprising a dead-end flow system configuration.

12. The metal electrodeposition system according to claim 1, including a plate and frame membrane configuration.

13. The metal electrodeposition system according to claim 1, including a spiral wound configuration.

14. The metal electrodeposition system according to claim 1, including a tubular configuration.

15. The electrodeposition system of the metal according to Claim 1, including a hollow fiber structure.

16. The electrodeposition system of the metal according to Claim 1, further including an acid.

17. The electrodeposition system of the metal according to Claim 1, further including an oxidizing agent.

18. The electrodeposition system of the metal according to Claim 1, further including a solvent extractant.

19. The electrodeposition system of the metal according to Claim 1, further including a buffer.

20. The electrodeposition system of the metal according to Claim 1, wherein at least one electrode includes a catalyst.

21. The electrodeposition system of the metal according to Claim 1, further including an electrode reagent.

22. The electrodeposition system of the metal according to Claim 1, further including a filter press.

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