US20050121333A1 - Electrolytic reduction of metal oxides - Google Patents

Electrolytic reduction of metal oxides Download PDF

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US20050121333A1
US20050121333A1 US10/474,745 US47474504A US2005121333A1 US 20050121333 A1 US20050121333 A1 US 20050121333A1 US 47474504 A US47474504 A US 47474504A US 2005121333 A1 US2005121333 A1 US 2005121333A1
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electrolyte
cell
metal
anode
molten
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Lazar Strezov
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BHP Billiton Innovation Pty Ltd
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BHP Billiton Innovation Pty Ltd
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

Definitions

  • the present invention relates to electrolytic reduction of metal oxides.
  • the present invention was made during the course of an on-going research project on the electrolytic reduction of titania (TiO 2 ) carried out by the applicant.
  • the CaCl 2 -based electrolyte was a commercially available source of CaCl 2 , namely calcium chloride dihydrate, that decomposed on heating and produced a very small amount of CaO.
  • the applicant operated the electrolytic cell at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the applicant also believes that the O ⁇ anions, once extracted from the titania, migrated to the anode and reacted with anode carbon and produced CO and released electrons that facilitated electrolytic reduction of titania to titanium in the cathode.
  • the applicant believes that carbon in the anode reacted with Ca ++ cations and produced a complex calcium carbide.
  • the experimental worked carried out by the applicant produced evidence of Ca metal in the electrolyte.
  • the applicant believes that the Ca metal was the result of electrodeposition of Ca ++ cations as Ca metal on electrically conductive sections of the cathode and that at least part of the Ca metal dissolved in the electrolyte and migrated to the vicinity of the titania in the cathode and participated in chemical reduction of oxides.
  • the applicant carried out experimental work to identify the mechanism for carbon transfer and to determine how to minimise carbon transfer and/or to minimise the adverse effects of carbon transfer.
  • the invention resides in replacing the carbon anode with a molten metal anode.
  • an electrolytic cell for electrolytic reduction of a metal oxide in a solid state which electrolytic cell includes (a) a molten electrolyte, (b) a cathode formed at least in part from the metal oxide in contact with the electrolyte, and (c) a molten metal anode in contact with the electrolye.
  • the metal of the molten metal anode has a relatively high saturation level for oxygen at the operating temperature of the cell.
  • the metal is chosen such that its melting point is within the operating temperature ranges of the electrolyte.
  • the melting point of the metal of the molten metal anode is higher than the melting point of the electrolyte and lower than the vaporisation and/or decomposition temperature of the electrolyte in order to prevent electrolyte consumption and removal through vaporisation.
  • the metal of the molten metal anode has a very low solubility in the molten electrolyte at the cell operating temperatures, as high solubility is detrimental because the anode metal will deplete and deposit on the cathode. The latter might not be a serious problem where there is low solubility and reactability of the metal with the cathode metal at the operating temperature.
  • the metal of the molten metal anode is silver or copper.
  • the solubility of oxygen in the Ag—O system at 1000° C. is around 0.32% by weight.
  • Ag has a melting point of 960° C., which is about 300 to 100° C. above the melting point of alkali and alkaline earth halides that provide suitable electrolytes.
  • the solubility of oxygen in the Cu—O system at 1100° C. is 0.39% by weight.
  • the melting point of copper is 1083° C., which is well below the boiling points of the above mentioned electrolytes.
  • the electrolytic cell further includes a means for removing oxygen that has diffused into the molten metal anode from the cell.
  • Such an “oxygen scavenging pump” means can have a number of different forms.
  • One option includes a duct that communicates with the molten metal anode and a device to create a partial pressure reduction between the molten metal anode and a head of molten metal within the duct.
  • An advantage of an “oxygen scavenging pump” means is that the amount of the molten metal anode required can be minimised, since the saturation wt % limits of oxygen within the molten anode metal are no longer the sole determining parameter of oxygen uptake by the anode.
  • a method of electrolytically reducing a metal oxide in a solid state in an electrolytic cell which electrolytic cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, and (c) a molten metal anode in contact with the electrolye, which method includes applying a cell potential across the anode and the cathode.
  • the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal anode.
  • the method includes maintaining the cell temperature below the vaporisation and/or decomposition temperatures of the electrolyte.
  • the method includes applying a cell potential above a decomposition potential of at least one constituent of the electrolyte so that there are cations of a metal other than that of the cathode metal oxide in the electrolyte.
  • the metal oxide is a titanium oxide.
  • the metal oxide be titania.
  • the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents.
  • the method includes maintaining the cell potential above the decomposition potential for CaO.
  • the method includes maintaining the cell potential below the decomposition potential for CaCl 2 .
  • the method includes maintaining the cell potential less than 3.0V.
  • the method includes maintaining the cell potential below 2.5V.
  • the method includes maintaining the cell potential below 2.0V.
  • the method includes maintaining the cell potential at least 1.5V.
  • the following example illustrates an application of the invention in the process of reducing titania into substantially pure titanium using an electrolytic cell constructed in accordance with the present invention and as illustrated schematically in FIG. 1 .
  • FIG. 1 is a schematic illustration of a electrolytic cell that can be scaled-up in application of the present invention.
  • the electrolytic cell 5 includes a graphite-free crucible 10 made of a suitable refractory material that is essentially inert as regards reaction with the electrolyte and electrode materials described below at cell operating temperatures of between 1000° C. and 1200° C.
  • the electrolytic cell further includes a pool 18 of molten CaCl 2 electrolyte within the crucible 10 .
  • the electrolytic cell 5 further includes a pool 14 of molten silver or copper (within the crucible 10 .
  • the molten Ag or Cu forms the anode 14 of the cell.
  • the molten metal anode 14 is below the molten electrolyte pool 18 .
  • the electrolytic cell 5 further includes a titania plate 12 positioned within a cage 12 b .
  • the cage 12 b (and therefore the plate 12 ) is suspended into the crucible 10 by means of a lead 12 a .
  • This assembly forms the cathode 20 of the cell.
  • the electrolytic cell 5 further includes a power source 16 and electrical connections between the power source 16 and the anode 14 and the cathode 20 .
  • the connections include electrical leads 17 and 12 a and a suitable high-temperature resistant plate member 15 , preferably of stainless steel, that provides electric connection between the interior of crucible 10 (and thus anode 14 ) and the lead 17 .
  • power source 16 provides for constant potential (voltage) settings thereby allowing the cell 5 to draw the amount of charge required during the electrolytic refining of the metal oxide body at a selectable potential.
  • the electrolytic cell 5 further includes type B thermocouples contained in heat-resistant, inert sheaths (not illustrated) for monitoring temperature in the molten metal anode 14 and the molten electrolyte 18 .
  • the electrolytic cell 5 further includes a refractory tube 20 that connects the interior of the crucible 10 , below the molten metal anode bath level (a), with a device for imparting a negative pressure differential between anode bath 14 and the head (b) of molten Ag suctioned into the tube 20 .
  • the pressure differential need only be slight to provide a driving force for diffusion and transport of oxygen that is dissolved into the metal anode bath 14 into the tube 20 which is preferably vented to atmosphere.
  • the above-described electrolytic cell 5 is positioned in a suitable furnace to maintain the electrolyte and the anode metal in their respective molten states.
  • the atmosphere around the crucible 10 is preferred to be an inert gas, such as argon, that does not react with the molten electrolyte.
  • a constant voltage of around 2.5-3 V is applied between the cell electrodes 12 and 14 , the cell potential being above the decomposition potential of CaO in the electrolyte but below the decomposition potential of CaCl 2 , whereby reduction of the titania in the cathode is carried out as described above.
  • the oxygen that passes into the electrolyte 18 is subsequently transported to the metal bath anode 14 where it dissolves.
  • the dissolved oxygen then diffuses through the molten anode bath 14 under the pressure differential imparted through duct 20 and is released as O 2 into the surrounding atmosphere.
  • this transport mechanism is effective for as long as oxygen in the molten metal anode is below the saturation level.

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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

An electrolytic cell and a method of electrolytically reducing a metal oxide, such as titania, in a solid state are disclosed. The electrolytic cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, and (c) a molten metal anode (such as silver or copper) in contact with the electrolyte.

Description

    1. FIELD OF THE INVENTION
  • The present invention relates to electrolytic reduction of metal oxides.
  • 2. BACKGROUND OF AND PRIOR ART TO THE INVENTION
  • The present invention was made during the course of an on-going research project on the electrolytic reduction of titania (TiO2) carried out by the applicant.
  • During the course of the research project the applicant carried out experimental work on an electrolytic cell that included a graphite crucible that formed an anode of the cell, a pool of molten CaCl2-based electrolyte in the crucible, and a cathode that included solid titania.
  • The CaCl2-based electrolyte was a commercially available source of CaCl2, namely calcium chloride dihydrate, that decomposed on heating and produced a very small amount of CaO.
  • The applicant operated the electrolytic cell at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl2.
  • The applicant found that the cell could electrolytically reduce titania to titanium with very low concentrations of oxygen.
  • The applicant does not have a clear understanding of the electrolytic cell mechanism at this stage. Nevertheless, whilst not wishing to be bound by the comments in this paragraph, the applicant offers the following comments by way of an outline of a possible cell mechanism. The applicant believes that operating the experimental electrolytic cell above a potential at which the CaCl2-based electrolyte partially decomposed had the result of producing Ca++ cations that migrated to the vicinity of the titania in the cathode and provided a driving force that facilitated extraction of O−− anions produced by electrolytic reduction of titania to titanium in the cathode. The applicant also believes that the O−− anions, once extracted from the titania, migrated to the anode and reacted with anode carbon and produced CO and released electrons that facilitated electrolytic reduction of titania to titanium in the cathode. In addition, the applicant believes that carbon in the anode reacted with Ca++ cations and produced a complex calcium carbide. The experimental worked carried out by the applicant produced evidence of Ca metal in the electrolyte. The applicant believes that the Ca metal was the result of electrodeposition of Ca++ cations as Ca metal on electrically conductive sections of the cathode and that at least part of the Ca metal dissolved in the electrolyte and migrated to the vicinity of the titania in the cathode and participated in chemical reduction of oxides.
  • However, notwithstanding that the cell could electrolytically reduce titania to titanium with very low concentrations of oxygen, the applicant also found that there were relatively significant amounts of carbon transferred from the anode to the electrolyte and to the titanium produced at the cathode under a wide range of cell operating conditions. Carbon in the titanium is an undesirable contaminant. In addition, carbon transfer was responsible for low energy efficiency of the cell. Both problems are significant barriers to commercialisation of electrolytic reduction technology.
  • The applicant carried out experimental work to identify the mechanism for carbon transfer and to determine how to minimise carbon transfer and/or to minimise the adverse effects of carbon transfer.
  • 3. SUMMARY OF INVENTION
  • Broadly, the invention resides in replacing the carbon anode with a molten metal anode.
  • According to the present invention there is provided an electrolytic cell for electrolytic reduction of a metal oxide in a solid state, which electrolytic cell includes (a) a molten electrolyte, (b) a cathode formed at least in part from the metal oxide in contact with the electrolyte, and (c) a molten metal anode in contact with the electrolye.
  • Preferably the metal of the molten metal anode has a relatively high saturation level for oxygen at the operating temperature of the cell.
  • Preferably the metal is chosen such that its melting point is within the operating temperature ranges of the electrolyte.
  • Preferably the melting point of the metal of the molten metal anode is higher than the melting point of the electrolyte and lower than the vaporisation and/or decomposition temperature of the electrolyte in order to prevent electrolyte consumption and removal through vaporisation.
  • Preferably the metal of the molten metal anode has a very low solubility in the molten electrolyte at the cell operating temperatures, as high solubility is detrimental because the anode metal will deplete and deposit on the cathode. The latter might not be a serious problem where there is low solubility and reactability of the metal with the cathode metal at the operating temperature.
  • Preferably the metal of the molten metal anode is silver or copper.
  • The solubility of oxygen in the Ag—O system at 1000° C. is around 0.32% by weight. Ag has a melting point of 960° C., which is about 300 to 100° C. above the melting point of alkali and alkaline earth halides that provide suitable electrolytes.
  • The solubility of oxygen in the Cu—O system at 1100° C. is 0.39% by weight. The melting point of copper is 1083° C., which is well below the boiling points of the above mentioned electrolytes.
  • Preferably the electrolytic cell further includes a means for removing oxygen that has diffused into the molten metal anode from the cell.
  • Such an “oxygen scavenging pump” means can have a number of different forms.
  • One option includes a duct that communicates with the molten metal anode and a device to create a partial pressure reduction between the molten metal anode and a head of molten metal within the duct.
  • An advantage of an “oxygen scavenging pump” means is that the amount of the molten metal anode required can be minimised, since the saturation wt % limits of oxygen within the molten anode metal are no longer the sole determining parameter of oxygen uptake by the anode.
  • For example, in order to reduce log of titania to pure titanium, 1 kg Ag would be required in the absence of an oxygen scavenging pump means to remove substantially all of the oxygen from the molten metal anode. Continuous removal of oxygen from the molten metal anode facilitated by the means allows the process to be performed continuously, as compared with batch processing.
  • According to the present invention there is also provided a method of electrolytically reducing a metal oxide in a solid state in an electrolytic cell, which electrolytic cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, and (c) a molten metal anode in contact with the electrolye, which method includes applying a cell potential across the anode and the cathode.
  • Preferably the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal anode.
  • Preferably the method includes maintaining the cell temperature below the vaporisation and/or decomposition temperatures of the electrolyte.
  • Preferably the method includes applying a cell potential above a decomposition potential of at least one constituent of the electrolyte so that there are cations of a metal other than that of the cathode metal oxide in the electrolyte.
  • Preferably the metal oxide is a titanium oxide.
  • It is preferred that the metal oxide be titania.
  • In a situation in which the metal oxide is titania it is preferred that the electrolyte be a CaCl2-based electrolyte that includes CaO as one of the constituents.
  • In such a situation it is preferred that the method includes maintaining the cell potential above the decomposition potential for CaO.
  • It is also preferred that the method includes maintaining the cell potential below the decomposition potential for CaCl2.
  • It is preferred that the method includes maintaining the cell potential less than 3.0V.
  • It is preferred particularly that the method includes maintaining the cell potential below 2.5V.
  • It is preferred more particularly that the method includes maintaining the cell potential below 2.0V.
  • It is preferred that the method includes maintaining the cell potential at least 1.5V.
  • The following example illustrates an application of the invention in the process of reducing titania into substantially pure titanium using an electrolytic cell constructed in accordance with the present invention and as illustrated schematically in FIG. 1.
  • 4. DESCRIPTION OF EXEMPLARY EMBODIMENT
  • FIG. 1 is a schematic illustration of a electrolytic cell that can be scaled-up in application of the present invention.
  • Whilst the example described below relates to the electrolytic reduction of titania, the basic principle is equally applicable to other metal oxides, in particular oxides of Si, Ge or alloys containing these metals.
  • With reference to the figure, the electrolytic cell 5 includes a graphite-free crucible 10 made of a suitable refractory material that is essentially inert as regards reaction with the electrolyte and electrode materials described below at cell operating temperatures of between 1000° C. and 1200° C.
  • The electrolytic cell further includes a pool 18 of molten CaCl2 electrolyte within the crucible 10.
  • The electrolytic cell 5 further includes a pool 14 of molten silver or copper (within the crucible 10. The molten Ag or Cu forms the anode 14 of the cell. In view of the different densities, the molten metal anode 14 is below the molten electrolyte pool 18.
  • The electrolytic cell 5 further includes a titania plate 12 positioned within a cage 12 b. The cage 12 b (and therefore the plate 12) is suspended into the crucible 10 by means of a lead 12 a. This assembly forms the cathode 20 of the cell.
  • The electrolytic cell 5 further includes a power source 16 and electrical connections between the power source 16 and the anode 14 and the cathode 20. The connections include electrical leads 17 and 12 a and a suitable high-temperature resistant plate member 15, preferably of stainless steel, that provides electric connection between the interior of crucible 10 (and thus anode 14) and the lead 17.
  • In use, power source 16 provides for constant potential (voltage) settings thereby allowing the cell 5 to draw the amount of charge required during the electrolytic refining of the metal oxide body at a selectable potential.
  • The electrolytic cell 5 further includes type B thermocouples contained in heat-resistant, inert sheaths (not illustrated) for monitoring temperature in the molten metal anode 14 and the molten electrolyte 18.
  • The electrolytic cell 5 further includes a refractory tube 20 that connects the interior of the crucible 10, below the molten metal anode bath level (a), with a device for imparting a negative pressure differential between anode bath 14 and the head (b) of molten Ag suctioned into the tube 20. The pressure differential need only be slight to provide a driving force for diffusion and transport of oxygen that is dissolved into the metal anode bath 14 into the tube 20 which is preferably vented to atmosphere.
  • In use, the above-described electrolytic cell 5 is positioned in a suitable furnace to maintain the electrolyte and the anode metal in their respective molten states. The atmosphere around the crucible 10 is preferred to be an inert gas, such as argon, that does not react with the molten electrolyte.
  • Once the cell reaches its operating temperature, about 1150 to 1200° C., depending on the anode metal employed, a constant voltage of around 2.5-3 V is applied between the cell electrodes 12 and 14, the cell potential being above the decomposition potential of CaO in the electrolyte but below the decomposition potential of CaCl2, whereby reduction of the titania in the cathode is carried out as described above.
  • The oxygen that passes into the electrolyte 18 is subsequently transported to the metal bath anode 14 where it dissolves. The dissolved oxygen then diffuses through the molten anode bath 14 under the pressure differential imparted through duct 20 and is released as O2 into the surrounding atmosphere.
  • As will be noted, this transport mechanism is effective for as long as oxygen in the molten metal anode is below the saturation level.
  • By way of example, it is noted that other shapes and configurations of the titania cathode 20 are equally employable, bearing in mind the need to ensure proper electric contact between the power source 16 and the titania to be reduced within the cell.

Claims (20)

1. An electrolytic cell for electrolytic reduction of a metal oxide in a solid state, which electrolytic cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, and (c) a molten metal anode in contact with the electrolyte.
2. The electrolytic cell defined in claim 1 wherein the metal of the molten metal anode has a relatively high saturation level for oxygen at the operating temperature of the cell.
3. The electrolytic cell defined in claim 1 wherein the metal of the molten metal anode is chosen such that its melting point is within the operating temperature ranges of the electrolyte.
4. The electrolytic cell defined in claim 1 wherein the melting point of the metal of the molten metal anode is higher than the melting point of the electrolyte and lower than the vaporisation and/or decomposition temperature of the electrolyte.
5. The electrolytic cell defined in claim 1 wherein the metal of the molten metal anode has a very low solubility in the molten electrolyte at the cell operating temperatures,
6. The electrolytic cell defined in claim 1 wherein the metal of the molten metal anode is silver or copper.
7. The electrolytic cell defined in claim 1 further including a means for removing oxygen that has diffused into the molten metal anode from the cell.
8. The electrolytic cell defined in claim 7 wherein the cell oxygen removal means includes a duct that communicates with the molten metal anode and a device to create a partial pressure reduction between the molten metal anode and a head of molten metal within the duct.
9. A method of electrolytically reducing a metal oxide in a solid state in an electrolytic cell, which electrolytic cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, and (c) a molten metal anode in contact with the electrolyte, which method includes applying a cell potential across the anode and the cathode.
10. The method defined in claim 9 including maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal anode.
11. The method defined in claim 9 including applying a cell potential above a decomposition potential of at least one constituent of the electrolyte so that there are cations of a metal other than that of the cathode metal oxide in the electrolyte.
12. The method defined in claim 9 wherein the metal oxide is a titanium oxide.
13. The method defined in claim 9 wherein the metal oxide is titania.
14. The method defined in claim 9 wherein the electrolyte is a CaCl2-based electrolyte that includes CaO as one of the constituents.
15. The method defined in claim 14 including maintaining the cell potential above the decomposition potential for CaO.
16. The method defined in claim 14 including maintaining the cell potential below the decomposition potential for CaCl2.
17. The method defined in claim 14 including maintaining the cell potential below 3.0V.
18. The method defined in claim 14 including maintaining the cell potential below 2.5V.
19. The method defined in claim 14 including maintaining the cell potential below 2.0V.
20. The method defined in including maintaining the cell potential at least 1.5V.
US10/474,745 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides Abandoned US20050121333A1 (en)

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AUPR4438 2001-04-10
AUPR4438A AUPR443801A0 (en) 2001-04-10 2001-04-10 Removal of oxygen from metal oxides and solid metal solutions
PCT/AU2002/000457 WO2002083993A1 (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides

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EP (1) EP1412558A4 (en)
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CA (1) CA2443960A1 (en)
WO (1) WO2002083993A1 (en)
ZA (1) ZA200307914B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090045070A1 (en) * 2006-02-06 2009-02-19 Becker Aaron J Cathode for electrolytic production of titanium and other metal powders
KR20150101457A (en) * 2012-12-24 2015-09-03 메탈리시스 리미티드 Method and apparatus for producing metal by elecrolytic reduction
WO2015198052A1 (en) * 2014-06-26 2015-12-30 Metalysis Limited Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal
KR101588123B1 (en) * 2014-06-03 2016-02-15 한국원자력연구원 Electrolytic reduction method for metal oxide using liquid anode and apparatus thereof
WO2016040278A1 (en) * 2014-09-10 2016-03-17 Alcoa Inc. Systems and methods of protecting electrolysis cell sidewalls
WO2019084045A1 (en) * 2017-10-23 2019-05-02 Arconic Inc. Electrolytic-based methods for recycling titanium particles
US10590553B2 (en) 2014-06-26 2020-03-17 Metalysis Limited Method of producing metallic tantalum
WO2021165974A1 (en) * 2020-02-20 2021-08-26 Helios Project Ltd. Liquid anode based molten oxide electrolysis/ the production of oxygen from electrolysis of molten oxide

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1492905A4 (en) * 2002-03-13 2006-06-28 Bhp Billiton Innovation Pty Reduction of metal oxides in an electrolytic cell
AU2002951962A0 (en) * 2002-10-09 2002-10-24 Bhp Billiton Innovation Pty Ltd Electrolytic reduction of metal oxides
AU2002952083A0 (en) 2002-10-16 2002-10-31 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
US7794580B2 (en) 2004-04-21 2010-09-14 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
US7410562B2 (en) 2003-08-20 2008-08-12 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
EP2109691B1 (en) 2007-01-22 2016-07-13 Materials And Electrochemical Research Corporation Metallothermic reduction of in-situ generated titanium chloride
WO2008101283A1 (en) * 2007-02-20 2008-08-28 Metalysis Limited Electrochemical reduction of metal oxides
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1354451A (en) * 1919-03-10 1920-09-28 Norsk Hydro Elektrisk Manufacture of reducing alkaline melts
US4875985A (en) * 1988-10-14 1989-10-24 Brunswick Corporation Method and appparatus for producing titanium
US5006209A (en) * 1990-02-13 1991-04-09 Electrochemical Technology Corp. Electrolytic reduction of alumina

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITTO970080A1 (en) * 1997-02-04 1998-08-04 Marco Vincenzo Ginatta PROCEDURE FOR THE ELECTROLYTIC PRODUCTION OF METALS
GB9812169D0 (en) * 1998-06-05 1998-08-05 Univ Cambridge Tech Purification method
GB2359564B (en) * 2000-02-22 2004-09-29 Secr Defence Improvements in the electrolytic reduction of metal oxides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1354451A (en) * 1919-03-10 1920-09-28 Norsk Hydro Elektrisk Manufacture of reducing alkaline melts
US4875985A (en) * 1988-10-14 1989-10-24 Brunswick Corporation Method and appparatus for producing titanium
US5006209A (en) * 1990-02-13 1991-04-09 Electrochemical Technology Corp. Electrolytic reduction of alumina

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090045070A1 (en) * 2006-02-06 2009-02-19 Becker Aaron J Cathode for electrolytic production of titanium and other metal powders
KR102289555B1 (en) * 2012-12-24 2021-08-13 메탈리시스 리미티드 Method and apparatus for producing metal by elecrolytic reduction
US9926636B2 (en) * 2012-12-24 2018-03-27 Metalysis Limited Method and apparatus for producing metal by electrolytic reduction
KR20150101457A (en) * 2012-12-24 2015-09-03 메탈리시스 리미티드 Method and apparatus for producing metal by elecrolytic reduction
US20160194773A1 (en) * 2012-12-24 2016-07-07 Metalysis Limited Method and apparatus for producing metal by electrolytic reduction
JP2016503127A (en) * 2012-12-24 2016-02-01 メタリシス リミテッド Method and apparatus for producing metal by electrolytic reduction
KR101588123B1 (en) * 2014-06-03 2016-02-15 한국원자력연구원 Electrolytic reduction method for metal oxide using liquid anode and apparatus thereof
US11261532B2 (en) 2014-06-26 2022-03-01 Metalysis Limited Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal
CN107075705A (en) * 2014-06-26 2017-08-18 金属电解有限公司 Method and apparatus for raw material of the electroreduction comprising oxygen and the first metal
US10590553B2 (en) 2014-06-26 2020-03-17 Metalysis Limited Method of producing metallic tantalum
WO2015198052A1 (en) * 2014-06-26 2015-12-30 Metalysis Limited Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal
WO2016040278A1 (en) * 2014-09-10 2016-03-17 Alcoa Inc. Systems and methods of protecting electrolysis cell sidewalls
US10151039B2 (en) 2014-09-10 2018-12-11 Alcoa Usa Corp. Systems and methods of protecting electrolysis cell sidewalls
WO2019084045A1 (en) * 2017-10-23 2019-05-02 Arconic Inc. Electrolytic-based methods for recycling titanium particles
WO2021165974A1 (en) * 2020-02-20 2021-08-26 Helios Project Ltd. Liquid anode based molten oxide electrolysis/ the production of oxygen from electrolysis of molten oxide
LU500767A1 (en) * 2020-02-20 2021-10-25 Helios Project Ltd Liquid anode based molten oxide electrolysis/ the production of oxygen from electrolysis of molten oxide
CN115516114A (en) * 2020-02-20 2022-12-23 太阳神工程有限公司 Molten oxide electrolysis/production of oxygen from molten oxide electrolysis based on liquid anodes
EP4107295A4 (en) * 2020-02-20 2024-07-03 Helios Project Ltd Liquid anode based molten oxide electrolysis/ the production of oxygen from electrolysis of molten oxide

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