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WO2025076384A1 - Synthèse électrochimique de composés métalliques et dérivés de métaux à réduction directe - Google Patents

Synthèse électrochimique de composés métalliques et dérivés de métaux à réduction directe Download PDF

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Publication number
WO2025076384A1
WO2025076384A1 PCT/US2024/050004 US2024050004W WO2025076384A1 WO 2025076384 A1 WO2025076384 A1 WO 2025076384A1 US 2024050004 W US2024050004 W US 2024050004W WO 2025076384 A1 WO2025076384 A1 WO 2025076384A1
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WO
WIPO (PCT)
Prior art keywords
metal
iron
electrodeposition
docket
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/050004
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English (en)
Inventor
Lance KAVALSKY
Venkatasubramanian Viswanathan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Michigan System
University of Michigan Ann Arbor
Original Assignee
University of Michigan System
University of Michigan Ann Arbor
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Michigan System, University of Michigan Ann Arbor filed Critical University of Michigan System
Publication of WO2025076384A1 publication Critical patent/WO2025076384A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt 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
    • 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
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • 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
    • C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
    • 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
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • 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
    • C25C7/02—Electrodes; Connections thereof

Definitions

  • Figure 7 Surface phases for adsorbates at coverages 1/6 ML, 1/3 ML as well as mixed OH + H phases.
  • Figure 8 Free energy diagram for sequential electrodeposition of iron atoms on an Fe110 terrace. Light grey atoms in the atomic images highlight the iron atoms deposited so far. The supercells have been repeated to visualize the overarching patterns.
  • Figure 9 Free energy diagram for sequential electrodeposition of iron atoms at an Fe210 step. Light grey atoms in the atomic images highlight the iron atoms deposited so far. The supercells have been repeated to visualize the overarching patterns.
  • Figure 10 Schematics of the absorption structures with hydrogen placed a) at terrace surface hollow site (top and side views), b) below terrace short bridge site (top and side views), c) hollow site near step edge, d) hollow site adjacent to step, e) below short bridge site near step edge.
  • Outermost surface iron atoms are darkest grey, subsurface iron Docket No. Docket No.30275/59668 UM 2024-153-02 atoms are grey, and hydrogen atoms have a thick outline.
  • FIG. 11 Free energy diagrams for HER on the terrace sites (1/4 ML and 1 ML coverage), beside the step, near the step edge, and on a hydrogenated step.
  • DETAILED DESCRIPTION [0019] An electrowinning process for reduction of metal from a metal-containing ore in accordance with the disclosure can be performed in an electrochemical cell comprising oppositely disposed electrodes immersed in a water-in-salt electrolyte.
  • the process (Fig.1) includes dissolving the metal-containing ore in the water-in-salt electrolyte under acidic conditions to form a solution comprising one or more metal cations from the metal-containing ore.
  • Methods of the disclosure can provide for extraction of pure metal from a metal- containing ore in a room temperature aqueous acidic electrowinning process, thereby avoiding the problem of prior known processes in requiring high temperature and coke resulting in CO 2 formation.
  • HER water-in-salt electrolyte suppressed hydrogen evolution reaction
  • the metal to be extracted from the ore can be any one or more of iron, tin, nickel, cobalt, cadmium, chromium, zinc, manganese, and titanium.
  • the potential can be selected from the Pourbaix diagram of the metal by a region where a pure metal phase exists within the acidic pH (i.e., pH ⁇ 7) where HER is suppressed, as indicated by the HER line in the Pourbaix diagram.
  • the potential can be applied in a range of -0.1 V vs standard hydrogen electrode (SHE) to -1.0 V vs SHE.
  • SHE standard hydrogen electrode
  • Such potential can be useful when the metal is iron, for example.
  • the potential can be -1.4 V vs SHE to -2.3 V vs SHE and pH can be in the range - Docket No.
  • the former has a rectangular pattern on the surface whereas the latter forms a hexagonal pattern, as shown in Fig.2A H* shows a slight preference towards the hexagonal configuration at 1/2 ML coverage, in agreement with previous work.
  • OH* and O* also show a slight preference towards the hexagonal phase at this coverage. However, on a per-atom basis, this preference is at most a difference of 30 meV for the three adsorbates.
  • H* shows a preference towards the orthogonal configuration at both 1/6 ML and 1/3 ML coverage, but by only ⁇ 5 meV/surface atom.
  • the differing behavior of H* may be rationalized by decreased steric effects, as Docket No. Docket No.30275/59668 UM 2024-153-02 evidenced by the vertical OH* orientations on the surface. Both OH* and O* prefer the pattern formed via the non-orthogonal cell at these coverages.
  • mixed OH* + H* phases were also considered, as they can be formed via the chemical dissociation of water.
  • the water layer structure on metallic interfaces is an area of extensive study.
  • OH has been Docket No. Docket No.30275/59668 UM 2024-153-02 observed to incorporate itself into the water layer network on Pt which can stabilize it on the surface.
  • solvation has a negligible effect on atomic O adsorbates.
  • the most stable phase of pure OH is the 1/4 ML OH phase, where the most stable mixed phase involving OH is the 1/4 ML OH + 1/4 ML H phase.
  • the difference between the formation energy of these phases and the 1 ML H phase as a function of pH and applied potential was calculated.
  • pH 0, the OH molecules would need to be stabilized by 10.51 eV for the entire 1 ML H region to be replaced by 1/4 OH.
  • the difference at this pH is slightly smaller for the mixed 1/4 ML OH + 1/4 ML H phase, 8.32 eV, but remains substantial.
  • Fig.5 represents phases the surface will be driven towards. While not shown in the diagram (Fig.5), intermediate coverages or combinations of these surface phases may coexist on the surface.
  • Theoretical overpotentials for iron electrodeposition [0066] To understand the most relevant region of the surface Pourbaix for iron electrodeposition (the reverse reaction of Eq.5), the theoretical limiting potentials and overpotentials associated with plating were calculated. The theoretical limiting potential UL is the least negative applied potential for which all steps are downhill in a free energy landscape for a given reaction mechanism. Taking the difference between this limiting potential and the equilibrium potential yields the theoretical overpotential. [0067] For iron electrowinning, the reaction of interest is electrodeposition. The energetics of this process govern the efficiency of the growth of pure iron plates.
  • the most uphill step in this growth mechanism is placement of the first iron atom with a value of 0.50 eV.
  • the limiting potential is calculated by referenced to SHE. Since the theoretical overpotential is the difference between the standard reduction potential and limiting potential, it is calculated by . Therefore, this initial island nucleation step is the potential determining step, yielding a limiting potential UL of -0.70 V vs SHE. Propagating this quantity to obtain the theoretical overpotential, this value was calculated to be 0.25 V for deposition on a terrace. [0069] Further investigating the terrace growth mechanism, it was found that for placing the second iron atom on the surface there are two symmetrically unique configurations.
  • the size restricted model herein focuses on the overall growth energetics without considering the grow of island clusters as intermediate growth stage.
  • Previous epitaxial growth investigations have observed island formation followed by coalescence with increasing coverage. Specifically for electrodeposition, layer-by-layer growth with relatively flat deposits after island formation has also been reported using this method.
  • the calculated limiting potentials of both terrace and step site mechanisms both lie within the 1 ML H region of the surface Pourbaix diagram (Fig.5). This observation implies that potentials required to electroplate the iron cations from solution will also thermodynamically drive hydrogen adsorbate formation. In other words, iron deposition may proceed on Fe110 in the presence of hydrogen adsorbates thereby introducing the possibility for more complicated interactions and growth mechanisms.
  • the hydrogen will first adsorb onto the surface at the hollow site via a Volmer process (Fig.10a).
  • Fig.10a a Volmer process
  • the number of layers in the model was increased from 4 to 5 with the top 3 layers free to move.
  • the terrace Docket No. Docket No.30275/59668 UM 2024-153-02 supercell model is kept at 2 ⁇ 2.
  • the hydrogen was relaxed on the surface at the hollow site, and the calculated adsorption enthalpy was -0.91 eV.
  • the hydrogen was relaxed in the subsurface underneath the top site, hollow site, long bridge, and short bridge.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

Un procédé d'extraction électrolytique pour la réduction de métal à partir d'un minerai contenant du métal dans une cellule électrochimique comprenant des électrodes disposées en regard immergées dans un électrolyte eau-dans-sel peut comprendre la dissolution du minerai contenant du métal dans l'électrolyte eau-dans-sel dans des conditions acides pour former une solution comprenant un ou plusieurs cations métalliques à partir du minerai contenant du métal; et l'application d'un potentiel pour déposer sélectivement un ou plusieurs des cations métalliques présents dans la solution sur l'une des électrodes, ce qui permet de faire croître une plaque métallique de haute pureté sur l'électrode.
PCT/US2024/050004 2023-10-06 2024-10-04 Synthèse électrochimique de composés métalliques et dérivés de métaux à réduction directe Pending WO2025076384A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363543011P 2023-10-06 2023-10-06
US63/543,011 2023-10-06

Publications (1)

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WO2025076384A1 true WO2025076384A1 (fr) 2025-04-10

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668370A (en) * 1984-11-07 1987-05-26 Oronzio De Nora Implanti Elettrochimici S.P.A. Electrode for electrochemical processes and use thereof in electrolysis cells
US20020175083A1 (en) * 2001-04-17 2002-11-28 Milbourne Joseph Charles Process to remove ferric iron impurities from an acidic aqueous solution used in the electro-winning of copper
US20080006538A1 (en) * 2006-07-04 2008-01-10 Canales Miranda Luis A Process and device to obtain metal in powder, sheet or cathode from any metal containing material
US20100044243A1 (en) * 2006-09-21 2010-02-25 Qit-Fer & Titane Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes
US20210002742A1 (en) * 2014-09-09 2021-01-07 MetOx PTE.LTD System, apparatus, and process for leaching metal and storing thermal energy during metal extraction
US20220380919A1 (en) * 2021-03-24 2022-12-01 Electrasteel, Inc. 2-step iron conversion system
US20220389601A1 (en) * 2021-06-01 2022-12-08 Nth Cycle, Inc. Electrochemical metal deposition system and method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668370A (en) * 1984-11-07 1987-05-26 Oronzio De Nora Implanti Elettrochimici S.P.A. Electrode for electrochemical processes and use thereof in electrolysis cells
US20020175083A1 (en) * 2001-04-17 2002-11-28 Milbourne Joseph Charles Process to remove ferric iron impurities from an acidic aqueous solution used in the electro-winning of copper
US20080006538A1 (en) * 2006-07-04 2008-01-10 Canales Miranda Luis A Process and device to obtain metal in powder, sheet or cathode from any metal containing material
US20100044243A1 (en) * 2006-09-21 2010-02-25 Qit-Fer & Titane Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes
US20210002742A1 (en) * 2014-09-09 2021-01-07 MetOx PTE.LTD System, apparatus, and process for leaching metal and storing thermal energy during metal extraction
US20220380919A1 (en) * 2021-03-24 2022-12-01 Electrasteel, Inc. 2-step iron conversion system
US20220389601A1 (en) * 2021-06-01 2022-12-08 Nth Cycle, Inc. Electrochemical metal deposition system and method

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