WO2023209544A1 - Systèmes et procédés de production électrolytique continue de métaux - Google Patents

Systèmes et procédés de production électrolytique continue de métaux Download PDF

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Publication number
WO2023209544A1
WO2023209544A1 PCT/IB2023/054198 IB2023054198W WO2023209544A1 WO 2023209544 A1 WO2023209544 A1 WO 2023209544A1 IB 2023054198 W IB2023054198 W IB 2023054198W WO 2023209544 A1 WO2023209544 A1 WO 2023209544A1
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Prior art keywords
metal
cathode
mixture
electrochemical cell
harvester
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PCT/IB2023/054198
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English (en)
Inventor
Akmal Irfan MAJID
Yali Tang
Giulia FINOTELLO
John Van Der Schaaf
Niels DEEN
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Technische Universiteit Eindhoven
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Publication of WO2023209544A1 publication Critical patent/WO2023209544A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode

Definitions

  • the present invention relates to continuous electrolytic production of metals, particularly methods for converting metal salts and/or metal oxides to metals, and electrochemical cells, methods, and systems associated with same.
  • the present disclosure relates to the continuous production of metal powder via electrodeposition using an electrochemical cell.
  • the embodiments of the present disclosure are advantageous for converting metal salts and metal oxides by electrochemical deposition (electrodeposition) of metals that generate dendritic metal structures.
  • electrochemical deposition electrochemical deposition
  • a continuous (electrolytic) metal powder production can be achieved. This allows shortening of production time and more effective production processes.
  • metal recovery from incinerator bottom ash may contain metal salts and/or metal oxides.
  • metal salts and/or metal oxides can be also reduced to metallic form by using wet processing methods i.e. electrochemical methods, such as disclosed in embodiments of the present disclosure. This can also give future benefit in terms of production effectiveness and circularity of metal wastes.
  • an electrochemical cell for converting metal salt or metal oxide to metal comprises: a) a mixture comprising an electrolyte and metal salt or metal oxide; b) an anode submerged in the mixture; c) a cathode partially submerged in the mixture and moveable along a closed loop path; and d) a harvester disposed at an exposed portion of the cathode outside of the mixture; wherein an electrical charge supplied to the electrochemical cell reduces the metal salt or metal oxide to metal at and disposed onto the cathode, and wherein the harvester removes the metal from the exposed portion of the cathode.
  • the metal salt or metal oxide is selected from one or more of FeCh, FeSO 4 , Fe2(SO 4 ) 3 , ZnSO 4 , Zn 2 (SO 4 ) 3 , ZnCl 2 , CoC12, CuSO4, Fe 2 O 3 , Fe 3 O 4 , FeO, ZnO, CuO, MgO, Co 3 O 4 , and MnO.
  • the metal is selected from one or more of Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • the metal forms a plurality of dendritic structures disposed onto the cathode.
  • the cathode may comprises a disc.
  • the cathode comprises a connected looping structure.
  • the harvester comprises a mechanical harvester, a magnetic harvester, or combinations thereof.
  • the electrochemical cell further comprises: i) a rinsing unit configured to spray cleaning fluid onto the metal; and ii) a cartridge to retain the metal removed from the cathode by the harvester.
  • the metal salt or metal oxide is iron oxide; the electrolyte is alkaline electrolyte; and the metal is iron.
  • a method for converting metal salt or metal oxide into metal comprises: a) providing a metal salt or oxide in an electrolyte in an electrochemical cell to form a mixture, wherein the electrochemical cell includes an anode submerged in the mixture and a cathode partially submerged in the mixture and moveable along a closed loop path; b) supplying an electrical charge in the electrochemical cell, and reducing the metal salt or metal oxide in the mixture to form the metal at and disposed onto the cathode; c) moving the cathode having the metal disposed thereon from the mixture to provide an exposed portion of the cathode outside of the mixture; and d) harvesting the metal from the exposed portion of the cathode.
  • the method is a continuous process, wherein the abovementioned steps a) to d), and, optionally, further steps mentioned below, may be repeated in a cyclical manner.
  • the method further comprises: e) rinsing the metal; and f) collecting the metal.
  • the method is a continuous process comprising repeating the steps a) to d) or a) to f).
  • the metal salt or metal oxide is selected from one or more of FeCL, FeSCU, Fe2(SO4)s, ZnSC , Z SOf ZnCL, CoC12, CuSO4, Fe2C>3, FesC , FeO, ZnO, CuO, MgO, CO3O4, and MnO.
  • the metal is selected from one or more of Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • the metal forms a plurality of dendritic structures disposed onto the cathode.
  • the cathode is a cathode assembly comprising a plurality of moveable cathodes.
  • the harvester is a harvester assembly comprising a plurality of harvester units positioned for harvesting metal from the plurality of movable cathodes.
  • the metal salt or metal oxide is iron oxide; the electrolyte is alkaline electrolyte; and the metal is iron.
  • the method further comprises heating the mixture and generating current in the electrochemical cell concurrently with heating the mixture. In some embodiments, the mixture is heated to a temperature between about 80°C to about 115°C.
  • the method further comprises stirring the mixture for a period of time to form a stirred suspension.
  • the mixture is stirred for a period of time ranging from about 10 minutes to 20 minutes or more.
  • the mixture comprises aqueous sodium hydroxide at a concentration of at least about 5 M; or wherein the metallic iron comprises a purity greater than about 90%; or wherein a mass fraction of iron oxide in the suspension is between about 5% to about 33%.
  • the method includes the electrochemical cell comprising a faradaic efficiency greater than about 85%. In some embodiments, the electrochemical cell has an electrical energy consumption of less than 6 kWh/kg iron.
  • a continuous system for converting metal salt or metal oxide into metal comprises: an inlet to receive a mixture comprising a metal salt or metal oxide, an electrolyte, or a combination thereof, where the inlet feeds the mixture to an electrochemical cell; the electrochemical cell including the mixture, an anode submerged in the mixture, and a cathode partially submerged in the mixture and moveable along a closed loop path, wherein an electrical charge supplied to the electrochemical cell reduces the metal salt or metal oxide to the metal at and disposed onto the cathode; optionally a rinsing unit to spray cleaning fluid onto the metal disposed onto the cathode; optionally a drying unit to remove moisture from the metal; a harvester disposed at an exposed portion of the cathode outside of the mixture to remove the metal from the exposed portion of the cathode; and an outlet to discharge suspension or mixture from the system.
  • the metal salt or metal oxide is selected from one or more of FeCk, FeSCU, Fe2(SO4)s, ZnSCU, Zni SOfh, ZnCk, CoC12, CuSO4, Fe2C>3, FesCU, FeO, ZnO, CuO, MgO, CO3O4, and MnO.
  • the metal is selected from one or more of Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • the metal forms a plurality of dendritic structures disposed onto the cathode.
  • the cathode comprises a disc.
  • the cathode comprises a connected looping structure.
  • the harvester comprises a mechanical harvester, a magnetic harvester, or combinations thereof.
  • the metal salt or metal oxide is iron oxide; the electrolyte is alkaline electrolyte; and the metal is iron.
  • the system further comprises maintaining the mixture at a concentration of at least about 5M.
  • FIG. 1 shows a schematic diagram of an exemplary embodiment of the continuous and integrated systems of electrolytic metal production.
  • FIGs. 2A-2B schematically illustrate electrochemical cells according to embodiments herein.
  • FIG. 2A is a front view of an exemplary electrochemical cell having a rotating cathode configured to move along a closed loop path by rotating in and out of the electrolyte, a harvester for removing metal from the cathode, and a cartridge for collecting the metal.
  • FIG. 2B shows a top view of the electrochemical cell as in FIG. 2 A illustrating an electrical motor for rotating the cathode, where the cathode is shown as a disc.
  • FIG. 3 illustrates a front view of another exemplary electrochemical cell showing a cathode as a moveable belt that is moveable along a closed loop path.
  • FIG. 4 illustrates yet another exemplary electrochemical cell showing the cathode including a plurality of rotating discs.
  • FIG. 5B is an image showing the microstructure of the metallic iron from a selected dendritic iron structure (according to FIG. 5A).
  • FIG. 5C is an image showing the microstructure of the metallic iron collected from crushed dendritic iron structures (according to FIG. 5 A).
  • FIG. 6A shows a side view of the cathode;
  • FIG. 6B shows a front view of the cathode; and
  • FIG. 6C shows a front view of the cathode and the dendritic iron after rinsing with distilled water.
  • FIG. 7A is an image showing the microstructure of dendritic structures of the metallic iron deposited on the cathode as shown in FIGs. 6A-6C.
  • FIG. 7B is an image showing the morphology of crushed metallic iron taken from the dendritic structures of the metallic iron deposited on the cathode as shown in FIGs. 6A-6C.
  • FIG. 8 shows a schematic diagram of a continuous feedstock supply (continuous system) for converting a metal salt, such as an iron oxide, to metal (here, metallic iron) according to embodiments herein.
  • a metal salt such as an iron oxide
  • metal here, metallic iron
  • the present disclosure relates to systems and methods of continuous electrolytic production of metals using an electrochemical cell. Exemplary embodiments of the present disclosure provide for such continuous processes, wherein process steps may be repeated in a cyclical manner.
  • a mixture of metal salt and/or metal oxide in electrolyte is reduced to elemental metal.
  • the elemental metal is formed as rough and brittle dendrites on a surface or edge of the cathode.
  • the dendritic metal is brittle, which advantageously is easily removed from the cathode with a harvester using mechanical force (e.g., a knife or a scraper) or using magnetic force (e.g., a magnet to attract those metals).
  • Metals that form metal dendritic structures or dendrites under the appropriate conditions include non-limiting examples Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • Example references are provided in Table I, the disclosures of which are incorporated by reference herein, which describe exemplary processes and conditions used for forming metal dendritic structures with various metals.
  • metal dendrites may be understood to refer to a characteristic three dimensional tree-like agglomerate or structure, consisting of individual metallic crystals, the crystals having the dimensions in the range of about 10 nanometers to about 100 micrometers, growing on the electrode surface, e.g., cathode surface.
  • Such structures typically have the total length on the order of at least about 0.1 mm up to about 10 cm or more.
  • the cathode is configured such that it or a portion thereof may move in and out of the electrolyte along a closed loop path.
  • FIG. 1 shows a schematic diagram of continuous systems of electrolytic metal production according to exemplary embodiments herein and outlines an exemplary method 100 for the continuous production of metal.
  • a salt is defined as a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge.
  • Metallic oxides are made of metal and oxygen.
  • an oxide is defined as a chemical compound that contains at least one oxygen atom and one other element.
  • Non-limiting examples of metal salts suitable in the present disclosure include FeCh, FeSC , Fe2(SO4)s, ZnSC , Zni SOfh, ZnCh, C0CI2, Q1SO4, or combinations thereof.
  • Non-limiting examples of metal oxides suitable in the present disclosure include Fe20s, FesCU, FeO, ZnO, CuO, MgO, CO3O4, MnO, or combinations thereof.
  • a metal salt or metal oxide (as in FIG. 1, iron oxide) 110 is added to an electrolyte (as in FIG. 1, aqueous alkaline electrolyte) 120 in an electrochemical cell as in 150.
  • electrolyte as in FIG. 1, aqueous alkaline electrolyte
  • the choice of electrolyte may include acidic or alkaline group(s).
  • the metal salt or metal oxide (e.g., the iron oxide) and an electrolyte (e.g., aqueous alkaline electrolyte) form a mixture or suspension that is pre-mixed 130 and heated 140.
  • the stirring at 130 is stopped and a current is applied to the electrochemical cell at 150 to facilitate the reduction of the metal salt or metal oxide, e.g., iron oxide, to its metal (e.g., metallic iron). More generally, an electrical charge may be supplied, which may result in a voltage or current generated in the electrochemical cell 150.
  • the conversion of the metal salt or metal oxide (e.g., iron oxide) to metallic form results in metal (e.g., metallic iron) 160 deposited on the cathode in the form of dendritic structures 170.
  • Heating 165 can include current being applied to facilitate the reduction of metal salt or metal oxide (e.g., iron oxide) to metal (e.g., metallic iron).
  • the cathode or a portion thereof is rotatable, moveable, or otherwise repositionable, so that at least a portion of the cathode is removed from the electrolyte for rinsing and/or drying 175.
  • the metal e.g., metallic iron
  • the metal is then mechanically or magnetically removed or harvested from the cathode (e.g., by a mechanical force such as scraping) 180 to form metal 185 (e.g., metallic iron powder).
  • the metal e.g., metallic iron powder
  • Exemplary methods can be advantageously implemented as continuous processes, wherein some or all of the steps may be repeated in a cyclical manner.
  • methods described herein e.g., for reducing iron oxide, use low temperature (e.g., 90°C ⁇ 5°C to 110°C ⁇ 5°C) electrolytic conversion to obtain a suitable form of (e.g., brittle, non-regular, and/or non-uniform) deposition of metallic iron that can be harvested as taught in the present disclosure.
  • a suitable form of (e.g., brittle, non-regular, and/or non-uniform) deposition of metallic iron that can be harvested as taught in the present disclosure Non-regular/non-uniform structure promotes deposits containing dendritic iron, especially on the side/edge/corner. This feature simplifies and facilitates harvesting the metallic deposits, thus allowing for ease of conversion and collection of metallic powder.
  • Dendritic structures can be more easily harvested than deposits that are regular and/or uniform and/or compact in structure.
  • Heating 140 the mixture and/or heating 165 for iron electrodeposition preferably occurs at temperatures at 90°C ⁇ 5°C to 110°C ⁇ 5°C. While dendrites were already observed forming at 80°C ⁇ 5°C to 90°C ⁇ 5°C, higher temperatures may be preferred, such as below the boiling point of NaOH 50 wt% (at about 120°C, e.g., 100°C ⁇ 5°C to 110°C ⁇ 5°C). Alternatively or additionally, the production and removal of metallic iron from the cathode may be performed in a continuous manner. Exemplary methods for producing other metals may include other mixture compositions, electrolytes, process steps, and temperature conditions.
  • Metallic iron produced using the methods described herein can achieve a purity of about 90% by weight or greater and comprises an average particle size between about 20 microns to 150 microns.
  • the metallic iron produced can be a powder or “iron powder”.
  • the iron powder comprises greater than 90% by weight iron, where % by weight is based upon total weight of the powder.
  • the iron powder may comprise greater than 95% by weight iron, greater than 97% by weight iron, or greater than 99% by weight iron.
  • the average particle size of the resultant metallic iron may vary.
  • the resultant particle size can depend on the harvesting process and/or the operating conditions that produce the dendrites prior to harvesting.
  • the iron powder may have an average particle size ranging from 20 microns to 150 microns, e.g., from 20 pm to 150 pm, from 25 pm to 125 pm, or from 30 pm to 100 pm. In terms of lower limits, the average particle size of the iron powder may be greater than 20 pm, e.g., greater than 25 pm, or greater than 30 pm. In terms of upper limits, the average particle size of the iron powder may be less than 150 pm, e.g., less than 125 pm, or less than 100 pm.
  • FIG. 2A illustrates a front view of electrochemical cell 200 having a cathode 210 configured to move along a closed loop path by rotating in and out of a mixture or suspension S.
  • cathode 210 is a plate-like disc that rotates in a clockwise direction D, as shown.
  • the direction of rotation is non-limiting, e.g., the cathode can move in reverse or a counter-clockwise direction as desired.
  • Cathode 210 may be made of, but not limited to, stainless steel or other cathodic materials, such as graphite, nickel, and/or copper.
  • the cathode 210 is rotatable so that the disc is partially submerged in a mixture or suspension S comprising an electrolyte (e.g., alkaline electrolyte) and a metal salt or metal oxide (e.g., iron oxide).
  • Anode 220 is fully submerged in mixture or suspension S and is arranged to be adjacent to, and preferably parallel with, the portion of cathode 210 that is also submerged in mixture or suspension S.
  • the anode may be made of, for example, nickel mesh/gauze plate, platinum, or other inert anodic materials.
  • An electrical charge may be supplied between the anode 220 and the cathode 210, which may result in a voltage or current generated in the cell 200.
  • current C is generated in cell 200 to reduce the metal salt or metal oxide in mixture or suspension S to form the metal.
  • Cathode 210 is then rotated to provide an exposed portion 212 of cathode 210 to have the metal harvested, e.g., removed from the cathode.
  • Exposed portion 212 of cathode 210 having been rotated out of the mixture or suspension S to another position, is no longer submerged in mixture or suspension S.
  • Rinsing unit 270 uses a cleaning fluid, such as distilled water, to clean away excess mixture or suspension S on the exposed portion of cathode 210 leaving the deposited metal that can then be dried using dryer 275.
  • Harvester 280 is disposed at the cathode 210 and is positioned for mechanical removal of metal from the cathode 210.
  • a suitable mechanical harvester includes a scraper.
  • the harvester can be positioned for magnetic removal of metallic iron from the cathode.
  • Cartridge (or collector) 290 collects the harvested metal upon removal of the metal from cathode 210 of electrochemical cell 200.
  • FIG. 2B illustrates a top view of electrochemical cell 200 as in FIG. 2A.
  • Electrical motor M provides for moving (here, rotating) cathode 210 in direction D so that the cathode disc is moved into the mixture or suspension S, through the mixture or suspension S, and then out of the mixture or suspension S for harvesting converted metal, which can be performed in a cyclical manner.
  • FIG. 3 illustrates an alternative electrochemical cell 300, which is similar to cell 200 except that the cathode 310 of cell 300 is a connected looping structure, such as a belt, a strap, connected plates or a combination thereof.
  • the connected looping structure of the cathode 310 can include discrete parts, e.g., one or more plates, so long as they are connected in such a way that the structure has a periphery capable of moving along a closed loop path for continuous electrodeposition and harvesting of metal as taught in the present disclosure.
  • Cathode 310 is moveable along a closed loop path P that here is defined by the belt.
  • Motor M facilitates the cathode 310 circulating using a plurality of rollers, e.g., Rl, R2, R3, R4, etc.
  • a current is generated (and, optionally, heat) so that the metal salt or metal oxide in the mixture or suspension S is converted to the metal.
  • an electrical charge may be supplied, which may result in a voltage or current generated in the cell 300.
  • the anode 320 is preferably located underneath the cathode 310, but can also be located above the cathode 310. While FIG.
  • FIG. 3 illustrates a horizontally oriented anode 320, it may have any suitable orientation, such as a vertical or tilted orientation.
  • cleaning fluid such as water or distilled water
  • rinsing unit 370 optionally dried using dryer not shown
  • the harvester 380 may be positioned in any suitable location, such as above or below the cathode 310, or both.
  • FIG. 4 illustrates yet another exemplary electrochemical cell 400 configuration.
  • Cell 400 includes cathode assembly 410 comprising a plurality of cathodes, illustrated here as rotating discs DI - D5.
  • the plurality of cathodes are configured to move along a plurality of closed loop paths by rotating in and out of a mixture or suspension S (not shown) and may have any construction described in connection with other embodiments of the present disclosure.
  • five cathodes are illustrated, any suitable number of cathodes is within the scope of the present disclosure. In the embodiment depicted in FIG.
  • discs D1-D5 rotate about axis A in a clockwise direction in the mixture or suspension (not shown) for removal of the metal from the cathodes by harvester assembly 480.
  • the direction of rotation is non-limiting, e.g., the cathode can move in reverse or a counter-clockwise direction as desired.
  • Anode assembly 420 includes one or more anode portions (not shown) submerged in the mixture or suspension S.
  • One or more anode portions are arranged to be adjacent to, and preferably parallel with, the appropriate portions of cathode assembly 410 (such as portions of the cathodes D1-D5) that are also submerged in the mixture or suspension S.
  • An electrical charge is supplied, which may result in a voltage or current generated in cell 400 to reduce a metal salt or metal oxide in the mixture or suspension S to form its metal.
  • Cathode assembly 410 is rotated to provide exposed portions 412 of cathode discs D1-D5 to have the metal harvested, e.g., removed from the cathode discs, preferably in a continuous, cyclical process.
  • Harvester assembly 480 is disposed at the cathode assembly 410 and is positioned for removal of the metal from the cathode assembly 410.
  • the harvester assembly 480 includes a plurality of harvester units 481-485.
  • Harvester units 481-485 are preferably positioned for harvesting the metal from the exposed portions 412 of cathode discs D1-D5.
  • the harvester units 481-485 can include mechanical and/or magnetic metal removal devices.
  • Cartridge (or collector) 490 collects the harvested metal upon removal of the metallic iron from cathode 410 of electrochemical cell 400.
  • FIGs. 5A-5C, 6A-6C, and 7A-B show the microstructure and the morphology of the metallic iron (iron powder) that is collected from the dendritic structures.
  • the microstructure and the particle size of the final metallic iron depend on the electrochemical and process conditions.
  • the particle size of the metallic iron is easily varied or controlled by the duration of operation of the electrochemical cell or the rotation speed of the cathode.
  • FIG. 5A is a photo demonstrating iron dendrite formation on a rectangular cathode.
  • FIG. 5B shows an image of the microstructure of the metallic iron from a selected dendritic iron structure (as in FIG. 5A).
  • FIG. 5C shows an image of the microstructure of the metallic iron collected from crushed dendritic iron structures (according to FIG. 5 A) as evidence of electrolytic iron powder as a final product.
  • FIG. 6A shows a side view of the cathode;
  • FIG. 6B shows a front view of the cathode; and
  • FIG. 6C shows a front view of the cathode and the dendritic iron after rinsing with water.
  • FIG. 7A is an image showing the microstructure of dendritic structures of the metallic iron deposited on the cathode as shown in FIGs. 6A-6C.
  • FIG. 7B is an image showing the morphology of crushed metallic iron taken from the dendritic structures of the metallic iron deposited on the cathode as shown in FIGs. 6A-6C.
  • the present disclosure provides for low electrical energy consumption, less than about 6 kWh/kg iron. Additionally, certain systems and methods herein may use renewable energy to power up the electrolytic conversion process. The electrolytic reduction process may be conducted using electrical energy directly converted from renewable energy, thus preventing CO2 emission.
  • the electrochemical cell of the present disclosure may include an electrolyte with a mixture or suspension of metal salt or metal oxide powder, an anode, and one or more rotating disc or belt cathodes controlled by an electric motor.
  • the system comprises a plurality of moveable cathodes to improve the system’s productivity.
  • the cathode and anode are for example connected to a power supply with a constant current.
  • the electrochemical process is for example conducted at an elevated temperature of about 110°C ⁇ 5 °C.
  • the electrochemical cell may be further equipped with a rinsing unit that cleans the metal disposed onto the cathode with a cleaning fluid, such as distilled water.
  • the rinsing unit is used to remove electrolyte and metal salt or metal oxide that may still be present in the metal.
  • the metal may be rinsed before being mechanically or magnetically removed (e.g., scraped off) the cathode, after being harvested from the cathode, or after the metal has been collected in a cartridge.
  • the electrochemical cell may also further comprise a cartridge to collect the metal after removing, e.g., scraping from the cathode.
  • the exemplary electrolyte mixture comprises aqueous sodium hydroxide (NaOH) 50 wt%, about 18 M or pH of about 15.3 (at 25°C) or at least about 5 M, and micronsized iron oxide powder with a mass fraction between about 5% to about 33% over the total mixture.
  • the alkaline electrolyte comprises aqueous potassium hydroxide.
  • the powders are fed into the solution and are pre-mixed for about 10-20 minutes to ensure the homogeneity of the suspension.
  • Alternative and/or additional additive to the alkaline electrolyte include non-limiting examples ammonium and/or potassium sulphate, which can be provided in electrolyte to increase the conductivity and reduce adhesion of the converted metallic iron as fine powder.
  • the electrochemical process may be conducted without any agitation/stirring.
  • metallic iron with rough dendritic structures is deposited on the cathode, particularly at sides, corners, and edges, as shown in FIG. 5 A and FIGs. 6A-6C.
  • These dendrites have a rough, solid, and brittle nature.
  • the growth of the dendrites is a relatively slow, but stable process depending on the duration of the process.
  • the metallic iron produced by this method has a high purity (90% and greater), and the electrolytic conversion has a high-faradaic efficiency (greater than 85% or greater than 90%).
  • the combination of the anode and cathode arrangement, along with the current density settings of the electrochemical cell specifically lead to formation of dendritic, brittle, iron deposition onto the cathode of the cell.
  • the cathode moveable along a closed loop path allows for direct and continuous harvesting of metal powder in a cyclical manner, whereby some or all steps of the exemplary processes can be repeated.
  • a harvester is coupled to the rotating disc cathode to facilitate the removal of the deposited metal from the cathode, which is collected into a cartridge.
  • the harvester may be a knife or a scraper, and the harvester collects metal from the cathode.
  • the harvester may include a mechanical and/or a magnetic component to facilitate collecting.
  • the harvester comprises a knife, a scraper, a magnet, or combinations thereof.
  • An exemplary rotating disc cathode is for example partially submerged in the electrolyte and the rest of the rotating disc cathode is under contact with the knife/harvester.
  • the cathode may be rotated at a low speed or the deposited surface and the harvesting surface may be alternated to allow for the continuous production and collection of the metal.
  • the production cycles may be continuous or performed as multiple cycles.
  • Harvesters can be positioned alongside or perpendicular (or any angle there between) to any of the moveable cathodes according to embodiments herein.
  • Mechanical harvesters work by mechanically contacting the deposit in order to remove the metal.
  • the deposited iron on the cathode can be removed by using a (mechanical) scraper.
  • harvesters as in any of the embodiments herein can be magnetic for removal of the metal from the cathode.
  • a magnetic scraper works by utilizing a magnetic field, for example, using a magnet, to attract the metal that has been deposited on the cathode. The magnetic field can be alternated (on/off system) to attract and remove the metal deposit from the magnet and place it at a desired location.
  • the deposited iron on the cathode can be harvested by applying a magnetic field to capture the iron powder.
  • a system as disclosed herein may include continuous feeding of the electrolyte and discharge system of the electrolyte.
  • the continuous system 1000 is illustrated in FIG. 8.
  • the electrochemical cell 500 is shown schematically but can be any as described herein, e.g., cell 200, cell 300, or cell 400 having cathodes 210, 310, or 410 respectively.
  • the system 1000 continuously converts metal salt or metal oxide (e.g., iron oxide) to metal (e.g., metallic iron) by including an inlet I for receiving a metal salt or metal oxide, an electrolyte (e.g., alkaline electrolyte), or combinations thereof to form and maintain a mixture or suspension at a desired concentration.
  • metal salt or metal oxide e.g., iron oxide
  • metal e.g., metallic iron
  • the inlet feeds the mixture or suspension to the electrochemical cell 500 and may be connected to pump P for providing the mixture or suspension from another container 550, which is supplied with a metal salt or metal oxide, an electrolyte, or combinations thereof as needed to maintain desired concentration.
  • Pump P may include a stirrer to mix the mixture or suspension prior to supplying to cell 500 via inlet I.
  • Electrochemical cell 500 includes the mixture or suspension S, an anode (included in cell 500) submerged in the mixture or suspension S, and the cathode partially submerged in the mixture or suspension and moveable along a closed loop path.
  • a current C is applied to the electrochemical cell to reduce the metal salt or metal oxide (of the mixture or suspension S) to metal at and disposed onto the cathode in the manner as previously described for any of cell 200, cell 300, or cell 400.
  • System 100 optionally includes a rinsing unit to spray cleaning fluid, such as distilled water, onto the metal disposed onto the cathode to remove at least some residual suspension from the metal as previously described as is optionally a drying unit to remove at least some moisture content from the metal is included in system 1000.
  • Drying of metal can be performed, preferably before, but also after, harvesting it from the cathode of cell 500.
  • system 1000 comprises a drying system (within cell 500) to remove moisture from the metal prior to the metal, e.g., dendritic structures, being removed.
  • a drying system (within cell 500) can remove moisture postharvesting, e.g. dried in the cartridge after the metal is harvested and removed from cell 500.
  • the drying system may comprise hot air spray, e.g., using a heater, or other drying means.
  • a harvester is disposed at an exposed portion of the cathode outside of the mixture suspension S and is configured to remove the metal from the exposed portion of the cathode and to deposit it in cartridge 590 for collection. This may be performed mechanically or magnetically.
  • System 1000 also includes an outlet O for discharging the mixture or suspension S from the system back to container 550 or away from system 1000. Outlet O helps remove the unused mixture or suspension, which can be electrolyte depleted from metal salt or metal oxide.
  • electrochemical cell 500 includes heating as previously described and/or container 550 is heated by heater H.
  • An electrochemical cell for converting metal salt or metal oxide to metal comprising: a) a mixture comprising an electrolyte and metal salt or metal oxide; b) an anode submerged in the mixture; c) a cathode partially submerged in the mixture and moveable along a closed loop path; and d) a harvester disposed at an exposed portion of the cathode outside of the mixture; wherein an electrical charge supplied to the electrochemical cell reduces the metal salt or metal oxide to metal at and disposed onto the cathode, and wherein the harvester removes the metal from the exposed portion of the cathode.
  • Clause 2 The electrochemical cell of clause 1, wherein the metal salt or metal oxide is selected from one or more of FeCh, FeSO 4 , Fe2(SO4)3, ZnSO 4 , Zn2(SO 4 ) 3 , ZnCL, CoC12, CuSO4, Fe 2 O 3 , Fe 3 O 4 , FeO, ZnO, CuO, MgO, Co 3 O 4 , and MnO.
  • the metal salt or metal oxide is selected from one or more of FeCh, FeSO 4 , Fe2(SO4)3, ZnSO 4 , Zn2(SO 4 ) 3 , ZnCL, CoC12, CuSO4, Fe 2 O 3 , Fe 3 O 4 , FeO, ZnO, CuO, MgO, Co 3 O 4 , and MnO.
  • Clause 3 The electrochemical cell of either clause 1 or 2, wherein the metal is selected from one or more of Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • Clause 4 The electrochemical cell of any of clauses 1-3, wherein the metal forms a plurality of dendritic structures disposed onto the cathode.
  • Clause 7 The electrochemical cell of any of clauses 1-6, wherein the harvester is a mechanical harvester.
  • Clause 8 The electrochemical cell of any of clauses 1-7, wherein the harvester is a magnetic harvester.
  • Clause 9 The electrochemical cell of any of clauses 1-8, further comprising: i) a rinsing unit configured to spray cleaning fluid onto the metal; and ii) a cartridge to retain the metal removed from the cathode by the harvester.
  • Clause 10 The electrochemical cell of any of clauses 1-9, wherein: the metal salt or metal oxide is iron oxide; the electrolyte is alkaline electrolyte; and the metal is iron.
  • a method for converting metal salt or metal oxide into metal comprising: a) providing a metal salt or oxide in an electrolyte in an electrochemical cell to form a mixture, wherein the electrochemical cell includes an anode submerged in the mixture and a cathode partially submerged in the mixture and moveable along a closed loop path; b) supplying an electrical charge in the electrochemical cell, and reducing the metal salt or metal oxide in the mixture to form the metal at and disposed onto the cathode; c) moving the cathode having the metal disposed thereon from the mixture to provide an exposed portion of the cathode outside of the mixture; and d) harvesting the metal from the exposed portion of the cathode.
  • Clause 12 The method of clause 11, further comprising: e) rinsing the metal; and f) collecting the metal.
  • Clause 13 The method of either clause 11 or 12, wherein the method is a continuous process comprising repeating the steps a) to d) or a) to f).
  • Clause 14 The method of any of clauses 11-13, wherein the metal salt or metal oxide is selected from one or more of FeCh, FeSO 4 , Fe2(SO4)3, ZnSO 4 , Zn2(SO 4 ) 3 , ZnCL, CoC12, CuSO4, Fe 2 O 3 , Fe 3 O 4 , FeO, ZnO, CuO, MgO, Co 3 O 4 , and MnO.
  • Clause 15 The method of any of clauses 11-14, wherein the metal is selected from one or more of Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • Clause 16 The method of any of clauses 11-15, wherein the metal forms a plurality of dendritic structures disposed onto the cathode.
  • Clause 17 The electrochemical cell of any of clauses 1-9 or the method of any of claims 11-15, wherein the cathode is a cathode assembly comprising a plurality of moveable cathodes.
  • Clause 18 The electrochemical cell of any of clauses 1-9 or the method of any of claims 11-15, wherein the cathode is a cathode assembly comprising a plurality of moveable cathodes and the harvester is a harvester assembly comprising a plurality of harvester units positioned for harvesting metal from the plurality of movable cathodes.
  • Clause 19 The method of any of clauses 11-18, wherein: the metal salt or metal oxide is iron oxide; the electrolyte is alkaline electrolyte; and the metal is iron.
  • Clause 20 The method of any of clauses 11-19, further comprising heating the mixture and generating current in the electrochemical cell concurrently with heating the mixture.
  • Clause 21 The method of clause 20, wherein the mixture is heated to a temperature between about 80°C to about 115°C.
  • Clause 22 The method of any of clauses 11-21, further comprising stirring the mixture for a period of time to form a stirred suspension.
  • Clause 23 The method of clause 22, wherein the mixture is stirred for a period of time ranging from about 10 minutes to 20 minutes.
  • Clause 24 The electrochemical cell of clause 10 or the method of claim 19, wherein the mixture comprises aqueous sodium hydroxide at a concentration of at least about 5 M; or wherein the metallic iron comprises a purity greater than about 90%; or wherein a mass fraction of iron oxide in the suspension is between about 5% to about 33%.
  • Clause 25 The electrochemical cell of clause 10 or the method of claim 19, the electrochemical cell comprising a faradaic efficiency greater than about 85%.
  • Clause 26 The electrochemical cell of clause 10 or the method of claim 19, wherein the electrochemical cell has an electrical energy consumption of less than 6 kWh/kg iron.
  • a continuous system for converting metal salt or metal oxide into metal comprising: an inlet to receive a mixture comprising a metal salt or metal oxide, an electrolyte, or a combination thereof, where the inlet feeds the mixture to an electrochemical cell; the electrochemical cell including the mixture, an anode submerged in the mixture, and a cathode partially submerged in the mixture and moveable along a closed loop path, wherein an electrical charge supplied to the electrochemical cell reduces the metal salt or metal oxide to the metal at and disposed onto the cathode; optionally a rinsing unit to spray cleaning fluid onto the metal disposed onto the cathode; optionally a drying unit to remove moisture from the metal; a harvester disposed at an exposed portion of the cathode outside of the mixture to remove the metal from the exposed portion of the cathode; and an outlet to discharge suspension or mixture from the system.
  • Clause 28 The system of clause 27, wherein the metal salt or metal oxide is selected from one or more of FeCk, FeSCU, Fe2(SO4)3, ZnSCU, Zni SOfh, ZnCk, CoC12, CuSO4, Fe2C>3, FesCU, FeO, ZnO, CuO, MgO, CO3O4, and MnO.
  • Clause 29 The system of either clause 27 or claim 28, wherein the metal is selected from one or more of Fe, Cu, Ni, Zn, Co, Mn, Ag, Pt, Pd, Au, Ag, Mg, Li, and Pb.
  • Clause 30 The system of any of clauses 27-29, wherein the metal forms a plurality of dendritic structures disposed onto the cathode.
  • Clause 31 The system of any of clauses 27-30, wherein the cathode comprises a disc.
  • Clause 32 The system of any of clauses 27-31, wherein the cathode comprises a connected looping structure.
  • Clause 33 The system of any of clauses 27-32, wherein the harvester comprises a mechanical harvester, a magnetic harvester, or combinations thereof.
  • Clause 34 The system of any of clauses 27-33, wherein: the metal salt or metal oxide is iron oxide; the electrolyte is alkaline electrolyte; and the metal is iron.
  • Clause 35 The system of clause 34, further comprising maintaining the mixture at a concentration of at least about 5M.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

Cellule électrochimique pour convertir un sel métallique ou un oxyde métallique en métal comprenant : a) un mélange comprenant un électrolyte et un sel métallique ou un oxyde métallique ; b) une anode immergée dans le mélange ; c) une cathode partiellement immergée dans le mélange et mobile le long d'un trajet en boucle fermée ; et d) une moissonneuse disposée au niveau d'une partie exposée de la cathode à l'extérieur du mélange, une charge électrique fournie à la cellule électrochimique réduisant le sel métallique ou l'oxyde métallique en métal au niveau de la cathode et disposée sur celle-ci, et la moissonneuse retirant le métal de la partie exposée de la cathode. Des procédés et des systèmes de conversion de sel métallique ou d'oxyde métallique en métal, sont également divulgués, comprenant des procédés et des systèmes continus.
PCT/IB2023/054198 2022-04-26 2023-04-24 Systèmes et procédés de production électrolytique continue de métaux WO2023209544A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU377211A1 (ru) * 1971-05-03 1973-04-17 Новочеркасский научно исследовательский институт посто нных магнитов Устройство для непрерывного удаления осадка ферромагнитного порошка
US3860509A (en) * 1973-02-20 1975-01-14 Envirotech Corp Continuous electrowinning cell
SU956628A1 (ru) * 1981-02-19 1982-09-07 Шосткинский Филиал Всесоюзного Государственного Научно-Исследовательского И Проектного Института Химико-Фотографической Промышленности Устройство дл непрерывного удалени осадка ферромагнитного порошка из электролитической ванны
WO2016081030A1 (fr) * 2014-11-18 2016-05-26 Aqua Metals Inc. Dispositifs et procédé améliorés pour le recyclage sans fonderie d'accumulateurs au plomb
WO2017191605A1 (fr) * 2016-05-05 2017-11-09 University Of Pretoria Production de métaux

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU377211A1 (ru) * 1971-05-03 1973-04-17 Новочеркасский научно исследовательский институт посто нных магнитов Устройство для непрерывного удаления осадка ферромагнитного порошка
US3860509A (en) * 1973-02-20 1975-01-14 Envirotech Corp Continuous electrowinning cell
SU956628A1 (ru) * 1981-02-19 1982-09-07 Шосткинский Филиал Всесоюзного Государственного Научно-Исследовательского И Проектного Института Химико-Фотографической Промышленности Устройство дл непрерывного удалени осадка ферромагнитного порошка из электролитической ванны
WO2016081030A1 (fr) * 2014-11-18 2016-05-26 Aqua Metals Inc. Dispositifs et procédé améliorés pour le recyclage sans fonderie d'accumulateurs au plomb
WO2017191605A1 (fr) * 2016-05-05 2017-11-09 University Of Pretoria Production de métaux

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