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WO2024250052A1 - Réacteur à flux électrochimique - Google Patents

Réacteur à flux électrochimique Download PDF

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Publication number
WO2024250052A1
WO2024250052A1 PCT/AU2023/050499 AU2023050499W WO2024250052A1 WO 2024250052 A1 WO2024250052 A1 WO 2024250052A1 AU 2023050499 W AU2023050499 W AU 2023050499W WO 2024250052 A1 WO2024250052 A1 WO 2024250052A1
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WO
WIPO (PCT)
Prior art keywords
catholyte
iron
flow reactor
inlet
conduit
Prior art date
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Pending
Application number
PCT/AU2023/050499
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English (en)
Inventor
Bartlomiej Piotr KOLODZIEJCZYK
Bjorn Winther-Jensen
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Fortescue Future Industries Pty Ltd
Original Assignee
Fortescue Future Industries Pty Ltd
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Priority to PCT/AU2023/050499 priority Critical patent/WO2024250052A1/fr
Publication of WO2024250052A1 publication Critical patent/WO2024250052A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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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
    • 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
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • 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
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • 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
    • C25C7/04—Diaphragms; Spacing elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells

Definitions

  • the present disclosure relates to an electrochemical flow reactor, in particular an electrochemical flow reactor for continuous production of an iron-bearing product from iron ore particles.
  • metallic iron on a stationary, rotating or colloidal cathode from an alkaline or acidic solution.
  • the metallic iron may be recovered by removing the cathode from the electrolytic cell and scraping the metallic iron from the surface of the cathode.
  • the recovery of the metallic iron requires either disassembly of the electrochemical cell or at least removal of the cathode to recover the iron that is deposited thereon.
  • Such processes can only enable batch mode processing and are not suitable for a continuous production of metallic iron from large volumes of iron ore.
  • the present disclosure provides an electrochemical flow reactor, in particular an electrochemical flow reactor for continuous production of an iron-bearing product from iron ore particles.
  • an electrochemical flow reactor for continuous production of an iron-bearing product from iron ore particles comprising: an electrochemical cell comprising a cathodic compartment and an anodic compartment separated by a separator; the cathodic compartment containing a catholyte comprising a suspension of iron ore particles in a first alkaline solution, and a cathode at least partially in contact with the catholyte and arranged to facilitate reduction of the iron ore particles to the iron-bearing product, the cathodic compartment having an inlet for ingress of the catholyte and an outlet for egress of a spent catholyte containing the iron-bearing product, wherein the outlet is in fluid communication with the inlet via a first conduit in an arrangement whereby spent catholyte may be recirculated from the outlet of the cathodic compartment to the inlet thereof; the anodic compartment containing an anolyte comprising a second alkaline solution and
  • the electrochemical cell comprises an arrangement of alternating cathodic compartments and anodic compartments, wherein adjacent cathodic and anodic compartments are separated by respective separators.
  • an electrochemical flow reactor for continuous production of an iron-bearing product from iron ore particles comprising: an electrochemical cell assembly comprising an arrangement of alternating cathodic compartments and anodic compartments, wherein adjacent cathodic and anodic compartments are separated by respective separators; each cathodic compartment containing a catholyte comprising a suspension of iron ore particles in a first alkaline solution, and a cathode at least partially in contact with the catholyte and arranged to facilitate reduction of the iron ore particles to the iron-bearing product, the cathodic compartment having an inlet for ingress of the catholyte and an outlet for egress of a spent catholyte containing the iron-bearing product, wherein the outlet is in fluid communication with the inlet via a first conduit in an arrangement whereby spent catholyte may be recirculated from the outlet of the cathodic compartment to the inlet thereof; each ano
  • the second conduit may be provided with a respective inlet for ingress of the second alkaline solution to replenish the spent anolyte prior to recirculation to the inlet of the anodic compartment.
  • the electrochemical flow reactor further comprises a first pump associated with the first conduit to circulate the catholyte through the cathodic compartment, and a second pump associated with the second conduit to circulate the anolyte through the anodic compartment.
  • the first and second pumps may circulate the catholyte and anolyte in co-current flow with respect to one another.
  • the first and second pumps may circulate the catholyte and anolyte in counter-current flow with respect to one another.
  • the first conduit may be provided with respective inlets for separate ingress of iron ore particles and the first alkaline solution. It will be appreciated that the iron ore particles may be introduced as a slurry through one inlet or if present more than one inlet.
  • the first conduit may be provided with a catholyte chamber configured to receive and mix the iron ore particles and the first alkaline solution.
  • the first pump may be operated in a manner to maintain the iron ore particles in suspension in the first alkaline solution.
  • the electrochemical flow reactor may further comprise a particle suspending means capable of maintaining the iron ore particles in suspension in the first alkaline solution.
  • said particle suspending means may include, but is not limited to, an agitator or a sonication means.
  • Said particle suspending means may be disposed in, or associated with the catholyte chamber.
  • said particle suspending means may be disposed in-line in the first conduit.
  • the separation means may comprise a magnetic separator to separate the iron-bearing product from the spent catholyte.
  • the separation means may comprise a filter, centrifugal separator or a cyclonic separator.
  • the separation means may be disposed in-line in the first conduit downstream from the outlet of the cathodic compartment.
  • one or more magnets may be arranged in-line in the first conduit in an arrangement whereby the one or more magnets may be removed from the first conduit without disrupting or ceasing operation of the electrochemical flow reactor.
  • the separation means may be disposed in fluid communication with the first conduit and externally to a circuit defined by the first conduit extending between the outlet and the inlet of the cathodic compartment.
  • a feed line may be provided from the first conduit at an upstream point of said circuit to direct spent catholyte to the separation means in an arrangement whereby depleted catholyte is subsequently redirected by a return line to the first conduit at a downstream point of said circuit.
  • the separation means may be disposed upstream of the catholyte chamber so that the iron-bearing product may be separated from the spent catholyte before the depleted catholyte is replenished with iron ore particles and/or the first alkaline solution.
  • the electrochemical flow reactor further comprises a means to maintain the catholyte at a predetermined temperature.
  • the first conduit may be arranged to circulate the catholyte and/or replenished catholyte through a heat exchanger.
  • the first and second alkaline solutions may be the same or different.
  • the first and second alkaline solution may independently comprise sodium hydroxide, potassium hydroxide, lithium hydroxide, caesium hydroxide, magnesium hydroxide, calcium hydroxide or a mixture of one or more thereof, optionally in combination with a neutral salt of an alkali metal such as lithium chloride.
  • the first and second alkaline solution may comprise 20-80 wt% sodium hydroxide or potassium hydroxide solution, or 30-60 wt% sodium hydroxide or potassium hydroxide solution.
  • the first alkaline solution may be carbon-free.
  • the cathode may comprise a rotating or a non-rotating electrode assembly.
  • the cathode may be formed from a material including, but not limited to, glassy carbon, carbon fibre, graphite, steel, stainless steel or other grades of steel, iron or iron alloys or composite materials.
  • the anode may comprise a rotating or a non-rotating electrode assembly.
  • the anode may be formed from any suitable non-sacrificial material including, but not limited to, a plate, mesh, net, foam, fibres, sintered particles or other forms of electrode construction from nickel, nickel-iron alloys or blends, or other metals or conductive materials including composite materials that are suitable for use as oxygen evolution electrodes in alkaline media.
  • the cathode and anode are arranged in parallel alignment with one another.
  • the separator may comprise any semi-permeable ion conducting membrane suitable for alkaline electrolysis.
  • a semi-permeable ion conducting membrane includes the ZirfonTM (Agfa) separator membrane.
  • the iron ore particles may comprise a powder having a P80 less than or equal to 20 pm, a P80 less than or equal to 10 pm, or a P80 less than or equal to 2 pm.
  • FIG. 1 is a schematic representation of one embodiment of an electrochemical flow reactor as described herein comprising a single electrochemical cell arranged for co-current flow of the catholyte and anolyte;
  • Figure 2 is a schematic representation of the embodiment shown in Figure 1 with cocurrent flow of the catholyte and anolyte in the opposite direction;
  • FIG. 3 is schematic representation of an alternative embodiment of the electrochemical flow reactor comprising a single electrochemical cell arranged for countercurrent flow of the catholyte and anolyte;
  • Figure 4 is a schematic representation of the embodiment shown in Figure 3 with counter-current flow of the catholyte and anolyte in the opposite direction;
  • FIG. 5 is a schematic representation of another embodiment of the electrochemical flow reactor as described herein comprising a single electrochemical cell arranged for cocurrent flow of the catholyte and anolyte, wherein a separation means for separating the iron- bearing product is depicted outside the electrochemical flow reactor circuit;
  • FIG. 6 is a schematic representation of a further embodiment of the electrochemical flow reactor as described herein comprising a dual electrochemical cell assembly arranged for co-current flow of the catholyte and anolyte;
  • Figure 7 is a schematic representation of the embodiment shown in Figure 6 but arranged for counter-current-current flow of the catholyte and anolyte;
  • FIG. 8 is a schematic representation of another embodiment of the electrochemical flow reactor as described herein comprising a dual electrochemical cell assembly arranged for co-current flow of the catholyte and anolyte, wherein a separation means for separating the iron-bearing product is depicted outside the electrochemical flow reactor circuit;
  • Figure 9 is a schematic representation of another embodiment of the electrochemical flow reactor as described herein comprising a triple electrochemical cell assembly arranged for co-current flow of the catholyte and anolyte;
  • Figure 10 is a schematic representation of another embodiment of the electrochemical flow reactor as described herein comprising a triple electrochemical cell assembly arranged for counter-current flow of the catholyte and anolyte;
  • FIG. 11 is a schematic representation of another embodiment of the electrochemical flow reactor as described herein comprising a triple electrochemical cell assembly arranged for co-current flow of the catholyte and anolyte, wherein a separation means for separating the iron-bearing product is depicted outside the electrochemical flow reactor circuit.
  • the present disclosure relates to an electrochemical flow reactor, in particular an electrochemical flow reactor for continuous production of an iron-bearing product from iron ore particles.
  • first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
  • Spatially relative terms such as “inner,” “outer,” “beneath”, “below”, “lower”, “above”, “upper” and the like, may be used herein for ease of description to describe one element or feature’s relationship to another element(s) or feature(s) as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
  • the term “about” as used herein means within 5%, and more preferably within 1%, of a given value or range. For example, “about 3.7%” means from 3.5 to 3.9%, preferably from 3.66 to 3.74%.
  • “about” is associated with a range of values, e.g., “about X% to Y%”, the term “about” is intended to modify both the lower (X) and upper (Y) values of the recited range. For example, “about 20% to 40%” is equivalent to “about 20% to about 40%”.
  • iron ore refers to iron-bearing minerals including, but not limited to haematite, goethite, magnetite, limonite, taconite, iron aluminosilicate minerals or any other ore types that contain iron oxide.
  • iron-bearing product refers to metallic iron particles or metallic iron particles containing one or more phases of iron oxide including but not limited to haematite (FesOg), goethite (FeO(OH)), limonite, taconite and magnetite (FegO ⁇ .
  • the iron- bearing product may be produced by reducing the iron ore particles in the electrochemical flow reactor via one or more electrochemical reduction steps.
  • anolyte refers to an aqueous salt solution capable of allowing electrons to flow from a positively-charged anode.
  • catholyte refers to an aqueous salt solution capable of allowing electrons to flow to a negatively-charged cathode.
  • the catholyte comprises a suspension of iron ore particles in a first alkaline solution, whereby the first alkaline solution allows the electrons to flow to the negatively-charged cathode and the iron ore particles undergo reduction to the iron-bearing product via one or more electrochemical reduction steps in the cathodic compartment.
  • a reference to the term ‘spent catholyte’, as used herein, refers to said suspension of iron ore particles, wherein the iron ore particles have at least partially undergone one or more reduction reactions.
  • the spent catholyte may refer to a suspension of iron-bearing product in the first alkaline solution and/or the first alkaline solution at least partially depleted in iron ore particles. It will be appreciated by those skilled in the art that the spent catholyte may contain iron-bearing product and unreduced iron ore particles suspended in the first alkaline solution.
  • depleted catholyte refers to the spent catholyte from which the iron bearing product has been at least partially separated therefrom.
  • saturated anolyte refers to the second alkaline solution that has undergone one or more oxidation reactions in the anodic compartment of the electrochemical cell.
  • Px is defined in the art as a size distribution for which x% of the particles are smaller than the specified value. Accordingly, a P80 of 2 pm means size distribution for which 80% of the particles are smaller than 2 pm.
  • the term ‘at least partially in contact with’ refers to a portion of an electrochemical surface area of the cathode or the anode being available for liquid-solid interface interactions respectively between the catholyte and cathode electrode or the anolyte and the anode electrode.
  • the portion of the electrochemical surface area of the cathode or the anode being available for said interactions may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,
  • Figures 1 - 11 show various embodiments of an electrochemical flow reactor 10 arranged for continuous production of an iron-bearing product from iron ore particles.
  • the electrochemical flow reactor 10 includes an electrochemical cell 12 including a cathodic compartment 14 and an anodic compartment 16 separated by a separator 18.
  • the cathodic compartment 14 contains a catholyte 20 comprising a suspension of iron ore particles in a first alkaline solution, and a cathode 22 at least partially in contact with the catholyte 20 and arranged to facilitate reduction of the iron ore particles to the iron-bearing product via one or more reduction reactions.
  • the anodic compartment 16 contains an anolyte 24 comprising a second alkaline solution, and an anode 26 at least partially in contact with the anolyte 24.
  • the iron ore particles may comprise a powder having a P80 less than or equal to 20 pm, a P80 less than or equal to 10 pm, or a P80 less than or equal to 2 pm.
  • the solids density of the catholyte may be 1 -25 wt%.
  • the first and second alkaline solutions may independently comprise sodium hydroxide, potassium hydroxide, lithium hydroxide, caesium hydroxide, magnesium hydroxide, calcium hydroxide or a mixture of one or more thereof, optionally in combination with a neutral salt of an alkali metal such as lithium chloride.
  • the first and second alkaline solutions may comprise 20-80 wt% sodium hydroxide or potassium hydroxide solution, or 30-60 wt% sodium hydroxide or potassium hydroxide solution.
  • the catholyte may be carbon free.
  • the electrochemical flow reactor 10 as will be described below is configured and operated to deter deposition and/or adhesion of the iron-bearing product on the cathode 22 so that it may be readily separated from the catholyte 20. In this way, the electrochemical flow reactor 1 may be operated continuously without the need to cease production and disassemble the electrochemical cell 1 to recover electrodeposited iron-bearing product from the cathode 22.
  • the cathodic and anodic compartments 14, 16 may be fabricated from any suitable solid material that is chemically inert under the operating conditions of the electrochemical cell 12.
  • suitable solid materials include, but are not limited to, glass, metals, alloys or solid plastic materials.
  • the separator 18 separates the cathodic and anodic compartments 14, 16 to prevent physical contact between the cathode 22 and the anode 26 while allowing transport of ionic charge carriers between the cathodic and anodic compartments 14, 16.
  • the separator 18 may be any semi-permeable membrane suitable for alkaline electrolysis that allows water, cations and/or anions to pass therethrough.
  • a semi-permeable ion conducting membrane includes the ZirfonTM (Agfa) separator membrane.
  • hydrogen gas may be produced in the cathodic compartment 14 at the cathode 22 as a product of a competing side reaction (i.e.
  • the cathode 22 and the anode 26 may be fabricated from respective electrically conductive materials that are inert or insoluble under the alkaline electrolysis conditions maintained in the electrochemical cell 12.
  • the cathode 22 may be fabricated from an electrically conductive material having poor catalytic properties for the hydrogen evolution reaction, leading to high overvoltage for hydrogen evolution and surface properties that deter deposition and/or adhesion of the iron-bearing product thereon.
  • Suitable examples of electrically conductive materials from which the cathode 22 may be fabricated include, but are not limited to, glassy carbon, carbon fibre, graphite, steel, stainless steel or other grades of steel, iron, iron alloys or composite materials.
  • the anode 26 may be fabricated from an electrically conductive material having acceptable catalytic properties towards the oxygen evolution reaction leading to acceptable overvoltage for oxygen evolution and minimum side reactions.
  • electrically conductive materials from which the anode 26 may be fabricated include, but are not limited to, a plate, mesh, net, foam, fibers, sintered particles or other forms of electrode construction fabricated from nickel, iron, steel, stainless steel, nickel-iron alloys, composites or blends, or other metals or conductive materials including composite materials that is suitable for use as oxygen evolution electrodes in alkaline media..
  • the cathode 22 and the anode 26 may be a rotating electrode assembly.
  • the cathode 22 and the anode 26 may be a non-rotating electrode assembly.
  • the cathode 22 and the anode 26 may comprise respective stationary plates in parallel alignment with one another, as shown in the Figures.
  • the anode 26 may have a larger electrochemically active surface area than the cathode 22.
  • a suitable power supply may be configured in electrical communication with the cathode 22 and the anode 26 to supply a cell potential of greater than 1 .4 V to the electrochemical cell 12 to maintain a current density of at least greater than or equal to 0.05 A/cm2.
  • the power supply may supply a cell potential of about 1 .5 V to 2.5 V, more particularly about 1 .5 V to 1.9 V.
  • the cathode 22 and the anode 26 will be provided with a respective current collector configured to electrically connect the cathode 22 and the anode 26 to the power supply.
  • the cathodic compartment 14 is provided with an inlet 28 for ingress of the catholyte and an outlet 30 for egress of a spent catholyte containing the iron-bearing product.
  • the outlet 30 is in fluid communication with the inlet 28 via a first conduit 32 in an arrangement whereby spent catholyte may be recirculated from the outlet 30 of the cathodic compartment to the inlet 28 thereof.
  • a first pump 34 may be associated with the first conduit 32 to facilitate flow of catholyte, spent catholyte and/or depleted catholyte through the cathodic compartment 14.
  • the first pump 34 may be any suitable pump including, but not limited to, a peristaltic pump, diaphragm pump, rotary vane pump, centrifugal pump, gear pump, progressive cavity pump or scroll pump.
  • the anodic compartment 16 is provided with an inlet 36 for ingress of the anolyte and an outlet 38 for egress of spent anolyte.
  • the outlet 38 is in fluid communication with the inlet 36 via a second conduit 40 in an arrangement whereby spent anolyte may be recirculated from the outlet 38 of the anodic compartment to the inlet 36 thereof.
  • a second pump 42 may be associated with the second conduit 40 to facilitate flow of anolyte and/or spent anolyte through the anodic compartment 16.
  • the second pump 42 may be any suitable pump including, but not limited to, a peristaltic pump, diaphragm pump, rotary vane pump, centrifugal pump, gear pump, progressive cavity pump or scroll pump.
  • the first and second pumps 34, 42 may circulate the catholyte and anolyte in cocurrent flow with respect to one another, as shown in Figures 1 , 2, 5, 6, 8, 9 and 11. Alternatively, the first and second pumps 34, 42 may circulate the catholyte and anolyte in counter-current flow with respect to one another, as shown in Figures 3, 4, 7 and 10.
  • the first conduit 32 is provided with a catholyte chamber 44 having an inlet 46 for ingress of iron ore particles and an inlet 48 for ingress of the first alkaline solution to replenish said depleted catholyte prior to recirculation to the inlet 28 of the cathodic compartment 14.
  • the catholyte chamber 44 may be configured to receive and mix the iron ore particles and the first alkaline solution. It will be appreciated, however, that in alternative arrangements, the catholyte chamber 44 may be provided with a single inlet to receive a ready-mixed catholyte of iron ore particles suspended in the first alkaline solution.
  • the first pump 34 may be operated in a manner to maintain the iron ore particles in suspension in the first alkaline solution.
  • the electrochemical flow reactor 10 may include a particle suspending means capable of maintaining the iron ore particles in suspension in the first alkaline solution (not shown).
  • said particle suspending means may include, but is not limited to, an agitator or a sonication means or a combination of means such as an agitator and a sonicator.
  • Said particle suspending means may be disposed in, or associated with the catholyte chamber 44.
  • said particle suspending means may be disposed inline in the first conduit 32.
  • the second conduit 40 is provided with an anolyte chamber 50 having an inlet 52 for ingress of the second alkaline solution to add anolyte to the anolyte chamber 50 or replenish the spent anolyte prior to recirculation to the inlet 36 of the anodic compartment 16.
  • the respective inlets 46, 48, 52 may be integral with the first and second conduits 32, 40.
  • a separation means 54 may be associated with the first conduit 32 to separate the iron-bearing product from the spent catholyte. The resulting depleted catholyte may then be recirculated to the inlet 28 of the cathodic compartment 14.
  • the separation means 54 may include a magnetic separator to separate the iron-bearing product from the spent catholyte. Alternatively, or additionally, the separation means 54 may comprise a filter, centrifugal separator or a cyclonic separator, or a combination of separation means.
  • the separation means may separate the iron-bearing product from the spent catholyte in a batch or continuous (in-line) mode.
  • the separation means 54 may be disposed in-line in the first conduit 32 downstream from the outlet 30 of the cathodic compartment 14.
  • the separation means may be one or more magnets that may be arranged inline in the first conduit 32 in an arrangement whereby the one or more magnets may be removed from the first conduit 32 without disrupting or ceasing operation of the electrochemical flow reactor 10.
  • the separated iron-bearing product may then be collected from the one or more magnets by well-known conventional techniques.
  • the separation means 54 may be disposed in fluid communication with the first conduit 32 and externally to a circuit defined by the first conduit 32 extending between the outlet 30 and the inlet 28 of the cathodic compartment 14.
  • a feed line 56 may be provided from the first conduit 32 at an upstream point of said circuit to direct spent catholyte to the separation means 54 in an arrangement whereby depleted catholyte is subsequently redirected by a return line 58 to the first conduit at a downstream point of said circuit.
  • the separation means 54 may be disposed upstream of the catholyte chamber 44 so that the iron-bearing product may be separated from the spent catholyte before the resulting depleted catholyte is replenished with iron ore particles and/or the first alkaline solution.
  • the electrochemical flow reactor 10 may be configured to recirculate the catholyte, spent catholyte or depleted catholyte through a heat exchanger (not shown). In this way, the catholyte and anolyte may be maintained at a temperature of greater than or equal to 90 °C and preferably up to boiling point of the first and second alkaline solutions.
  • a heating means may be associated with the electrochemical cell 12, 12’, 12” to maintain the anolyte and the catholyte at a desired temperature.
  • Suitable heating means includes, but is not limited to, a heating jacket, heating mantle or heating plate configured in a suitable arrangement to heat the electrochemical cell.
  • FIG. 6-8 and Figures 9-11 there is shown an assembly of electrochemical cells 12’, 12” comprising a plurality of cathodic compartments 14 and anodic compartments 16 in alternating parallel alignment with one another.
  • the cathodic compartments 14 and the anodic compartments 16 may be arranged as described above.
  • iron ore particles and the first alkaline solution may be fed through inlets 46, 48 into the catholyte chamber 44 where they are mixed until the catholyte comprising the suspension of iron ore particles in the first alkaline solution is produced.
  • the catholyte is circulated by first pump 34 through the first conduit 32 to inlet 28 of the cathodic compartment 14 of the electrochemical cell 12.
  • the catholyte may be heated to a temperature greater than or equal to 90 °C before it is circulated to inlet 28 of the cathodic compartment 14.
  • the catholyte chamber 44 may be provided with a single inlet to receive a ready-mixed catholyte of iron ore particles suspended in the first alkaline solution.
  • the ready-mixed catholyte may be heated to a temperature greater than or equal to 90 °C.
  • a cell potential of greater than 1.4 V, in particular a cell potential of about 1.5 V to about 2.5 V per cell is supplied to the electrochemical cell(s) 12 by the power supply (not shown) to maintain a current density of at least greater than or equal to 0.05 A/cm 2 , whereupon at least some of the iron ore particles in the catholyte undergo one or more reduction reactions to produce an iron-bearing product.
  • the spent catholyte then leaves the cathodic compartment 14 via outlet 30.
  • Iron-bearing product may be separated from the spent catholyte by the separation means 54 disposed inline in first conduit 32, thereby producing a depleted catholyte.
  • the spent catholyte may be directed via feed line 56 to the separation means 54 which separates the iron-bearing product from the spent catholyte, whereupon the resulting depleted catholyte is re-directed to the first conduit 32 via return line 58.
  • the depleted catholyte may then be recirculated to the catholyte chamber 44 and replenished with incoming iron ore particles and/or the first alkaline solution via inlets 46, 48.
  • the second alkaline solution may be fed through inlet 52 into the anolyte chamber 50 and then circulated by second pump 42 via second conduit 40 to inlet 36 of the anodic compartment 16.
  • the anolyte may be heated to a temperature greater than or equal to 90 °C before it is circulated to inlet 36.
  • the anolyte undergoes an oxidation reaction at the anode 26 and the spent anolyte exits the anodic compartment 16 via outlet 38.
  • the spent anolyte may be recirculated to the anolyte chamber 50 where it may be replenished with the second alkaline solution.

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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 Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un réacteur à flux électrochimique pour la production continue d'un produit contenant du fer à partir de particules de minerai de fer. Le réacteur à flux électrochimique comprend une cellule électrochimique comprenant un compartiment cathodique et un compartiment anodique séparés par un séparateur. Le compartiment cathodique contient un catholyte comprenant une suspension de particules de minerai de fer dans une première solution alcaline, et une cathode au moins partiellement immergée dans le catholyte pour faciliter la réduction des particules de minerai de fer pour donner le produit contenant du fer. Le compartiment cathodique présente une entrée pour l'admission du catholyte et une sortie pour l'évacuation d'un catholyte usé contenant le produit contenant du fer, la sortie étant en communication fluidique avec l'entrée par l'intermédiaire d'un premier conduit dans un agencement par lequel le catholyte usé peut être remis en circulation de la sortie du compartiment cathodique jusqu'à son entrée. Le compartiment anodique contient un anolyte comprenant une seconde solution alcaline et une anode qui y est au moins partiellement immergée. Le compartiment anodique présente une entrée pour l'admission de l'anolyte et une sortie pour l'évacuation d'un anolyte usé, la sortie étant en communication fluidique avec l'entrée par l'intermédiaire d'un second conduit dans un agencement par lequel l'anolyte usé peut être remis en circulation de la sortie du compartiment anodique jusqu'à son entrée. Le réacteur à flux électrochimique comprend également un moyen de séparation associé au premier conduit pour séparer le produit contenant du fer du catholyte usé. Les premier et second conduits peuvent être pourvus de moyens respectifs qui permettent le réapprovisionnement du catholyte appauvri et de l'anolyte usé avant la recirculation vers les compartiments cathodique et anodique.
PCT/AU2023/050499 2023-06-07 2023-06-07 Réacteur à flux électrochimique Pending WO2024250052A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/AU2023/050499 WO2024250052A1 (fr) 2023-06-07 2023-06-07 Réacteur à flux électrochimique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/AU2023/050499 WO2024250052A1 (fr) 2023-06-07 2023-06-07 Réacteur à flux électrochimique

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WO2024250052A1 true WO2024250052A1 (fr) 2024-12-12

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140027301A1 (en) * 2012-07-26 2014-01-30 Ohio University Selective reductive electrowinning apparatus and method
AU2021215184A1 (en) * 2021-05-24 2022-12-08 Fortescue Future Industries Pty Ltd Apparatus and process for producing iron

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140027301A1 (en) * 2012-07-26 2014-01-30 Ohio University Selective reductive electrowinning apparatus and method
AU2021215184A1 (en) * 2021-05-24 2022-12-08 Fortescue Future Industries Pty Ltd Apparatus and process for producing iron

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NOBLE BERKLEY B, MOUTARLIER LOUKA J, KEMPLER PAUL A: "Electrochemical Chlor-Iron Process for Iron Production from Iron Oxide and Seawater", CHEMRXIV, 1 January 2023 (2023-01-01), XP093250527, Retrieved from the Internet <URL:https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/63f67ea732cd591f12549219/original/electrochemical-chlor-iron-process-for-iron-production-from-iron-oxide-and-seawater.pdf> *

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