WO2002083989A1 - Electrolytic reduction of metal oxides - Google Patents

Electrolytic reduction of metal oxides Download PDF

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Publication number
WO2002083989A1
WO2002083989A1 PCT/AU2002/000456 AU0200456W WO02083989A1 WO 2002083989 A1 WO2002083989 A1 WO 2002083989A1 AU 0200456 W AU0200456 W AU 0200456W WO 02083989 A1 WO02083989 A1 WO 02083989A1
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WO
WIPO (PCT)
Prior art keywords
metal
electrolyte
cell
metal oxide
method defined
Prior art date
Application number
PCT/AU2002/000456
Other languages
French (fr)
Inventor
Les Strezov
Ivan Ratchev
Steve Osborn
Original Assignee
Bhp Billiton Innovation Pty Ltd
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 Bhp Billiton Innovation Pty Ltd filed Critical Bhp Billiton Innovation Pty Ltd
Priority to AU2002245948A priority Critical patent/AU2002245948B2/en
Priority to JP2002581721A priority patent/JP2004523662A/en
Priority to EP02713941A priority patent/EP1392890A4/en
Priority to CA002443953A priority patent/CA2443953A1/en
Priority to US10/474,746 priority patent/US20040237710A1/en
Publication of WO2002083989A1 publication Critical patent/WO2002083989A1/en
Priority to NO20034548A priority patent/NO20034548L/en
Priority to US11/924,808 priority patent/US20080110764A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium

Definitions

  • the present invention relates to electrolytic reduction of metal oxides to produce substantially pure metals.
  • the present invention relates to electrolytic reduction of aluminium and magnesium oxides using a CaCl 2 electrolyte.
  • the present invention was made during the course of an on-going research project on the electrolytic reduction of metal oxides using CaCl 2 -based electrolyte being carried out by the applicant.
  • the research project investigated electrolytic reduction of a range of metal oxides in electrolyte cells based on the use of using CaCl 2 electrolyte.
  • the CaCl 2 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 cells at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the present invention provides, in broad terms, a method of electrolytically reducing a metal oxide to produce a metal in an electrolytic cell, which method includes electrolytically reducing the metal oxide in an electrolytic cell that includes (a) a pool of molten metal, the metal being the metal of the metal oxide to be reduced, the molten metal pool forming a cathode of the cell, (b) a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides, (c) an anode extending into the electrolyte, and (d) a body of metal oxide to reduced in contact with the molten metal and the electrolyte.
  • electrolytic reduction of metal oxide takes place where there is contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
  • the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte..
  • the method includes feeding the metal oxide body into the electrolytic cell to maintain contact of the metal oxide and the molten metal.
  • the metal oxide body may be in many forms, including rods, plates, blocks and the like, which can be readily immersed into the electrolyte and brought into contact with the molten metal.
  • the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced.
  • the method includes operating the cell at a potential that is 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 an aluminium oxide or a magnesium oxide.
  • the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents.
  • the cell potential be above the decomposition potential for CaO.
  • the cell potential be below the decomposition potential for CaCl 2 .
  • the cell potential be less than 3.0V.
  • the cell potential be below 2.5V.
  • the cell potential be below 2.0V.
  • the cell potential be at least 1.5V.
  • the CaCl 2 -based electrolyte may be a commercially available source of CaCl 2 , such as calcium chloride dihydrate, that partially decomposes on heating and produces CaO or otherwise includes CaO.
  • the CaCl 2 -based electrolyte may include CaCl 2 and CaO that are added separately or pre-mised to form the electrolyte.
  • the applicant does not have a clear understanding of the electrolytic cell mechanism when the cell is operated at a potential at which CaCl 2 - based electrolyte partially decomposes. 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 electrolytic cell above a potential at which CaCl 2 -based electrolyte partially decomposes produces Ca ++ cations that migrate to the vicinity of the metal oxide in contact with the molten metal cathode and provide a driving force that facilitates extraction of O " anions produced by electrolytic reduction to metal of metal oxide in contact with the molten metal cathode.
  • the applicant also believes that the 0 "" anions, once extracted from the metal oxide, migrate to the anode and react with anode carbon and produce CO and release electrons that facilitate electrolytic reduction of metal oxide to metal .
  • the experimental work 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 metal oxide in the cathode and participated in chemical reduction of oxides.
  • the anode be graphite.
  • the cell includes a base and side walls extending upwardly from the base formed from graphite.
  • the cell includes at least one tap hole for molten metal in one of the side walls and the method includes removing molten metal continuously or periodically.
  • the above-described method may be started-up in a number of ways.
  • One option is to introduce the (pure) metal and the electrolyte in solid state into the cell and subsequently heat the entire system to melt the metal and the electrolyte.
  • Another option is to introduce molten metal and molten electrolyte separately into the cell .
  • Figure 1 is a schematic illustration of an electrolytic cell 5 that can be scaled-up in application of the present invention.
  • the electrolytic cell 5 of Figure 1 includes a graphite crucible 10 that has a base 21, side walls 31, and a tapping/discharge opening indicated as 12 in one of the side walls 31.
  • the electrolytic cell 5 further includes a bath of molten CaCl electrolyte 13 in the crucible and a graphite electrode 11 immersed in the molten electrolyte 13.
  • the graphite electrode 11 forms the anode of the cell 5.
  • the electrolytic cell 5 further includes a pool 15 of molten aluminium in a lower section of the crucible 10.
  • the molten aluminium pool 15 forms the cathode of the cell.
  • the electrolytic cell further includes a body 14 that consists of or incorporates alumina (A1 2 0 3 ) to be reduced and extends into the electrolyte 13 and contacts the molten aluminium cathode 15.
  • the alumina is shaped as a rod, sheet or prismatic body. Alumina body 14 is held in an appropriate manner to allow controlled movement into and away from the crucible interior as indicated by the arrow 16.
  • the electrolytic cell 5 further includes a suitable power source 18 connected to the anode 11 and to the molten aluminium cathode 15.
  • the molten aluminium cathode 15 is required in order to initiate electrolytic reduction of the alumina in the alumina body 14 to aluminium.
  • the electrolytic reduction process is carried out at an elevated temperature of around 950°C at which the CaCl 2 electrolyte is and remains molten.
  • reduction of the alumina takes place. Since the process temperatures are above the melting point of aluminium, the latter will melt into the bath 15 and the bath level within crucible 10 will tend to rise.
  • the alumina body 14 is moved at a rate commensurate with the melting-off rate of aluminium from the alumina body 14 and the build-up of aluminium so that immersion of the alumina body 14 in the molten aluminium is kept at a minimum.
  • the process may be operated in a continuous mode by removing molten aluminium through tap hole 12 and positioning additional alumina bodies 14 in the electrolyte 13 to replace bodies 14 that are consumed in the reduction process .

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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

A method of electrolytically reducing a metal oxide (such as aluminium and magnesium oxides) to produce a metal in an electrolytic cell is disclosed. The method includes electrolytically reducing the metal oxide in an electrolytic cell that includes a pool of molten metal, the metal being the metal of the metal oxide to be reduced, and the molten metal pool forming a cathode of the cell. The electrolytic cell also includes a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides. The electrolytic cell also includes an anode extending into the electrolyte and a body of metal oxide to reduced in contact with the molten metal and the electrolyte.

Description

ELECTROLYTIC REDUCTION OF METAL OXIDES
1. Field of the Invention
The present invention relates to electrolytic reduction of metal oxides to produce substantially pure metals.
In particular, the present invention relates to electrolytic reduction of aluminium and magnesium oxides using a CaCl2 electrolyte.
2. Background Art
The present invention was made during the course of an on-going research project on the electrolytic reduction of metal oxides using CaCl2-based electrolyte being carried out by the applicant.
The research project investigated electrolytic reduction of a range of metal oxides in electrolyte cells based on the use of using CaCl2 electrolyte.
The CaCl2 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 cells at a potential above the decomposition potential of CaO and below the decomposition potential of CaCl2.
The applicant found that the cells could electrolytically reduce a range of metal oxides to metals with very low concentrations of oxygen.
3. Summary of the Invention The present invention provides, in broad terms, a method of electrolytically reducing a metal oxide to produce a metal in an electrolytic cell, which method includes electrolytically reducing the metal oxide in an electrolytic cell that includes (a) a pool of molten metal, the metal being the metal of the metal oxide to be reduced, the molten metal pool forming a cathode of the cell, (b) a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides, (c) an anode extending into the electrolyte, and (d) a body of metal oxide to reduced in contact with the molten metal and the electrolyte.
In the above method electrolytic reduction of metal oxide takes place where there is contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
Preferably the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte..
Preferably the method includes feeding the metal oxide body into the electrolytic cell to maintain contact of the metal oxide and the molten metal.
The metal oxide body may be in many forms, including rods, plates, blocks and the like, which can be readily immersed into the electrolyte and brought into contact with the molten metal.
Preferably the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced. Preferably the method includes operating the cell at a potential that is 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 an aluminium oxide or a magnesium oxide.
In a situation in which the metal oxide is a aluminium oxide or magnesium oxide 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 cell potential be above the decomposition potential for CaO.
It is also preferred that the cell potential be below the decomposition potential for CaCl2.
It is preferred that the cell potential be less than 3.0V.
It is preferred particularly that the cell potential be below 2.5V.
It is preferred more particularly that the cell potential be below 2.0V.
It is preferred that the cell potential be at least 1.5V.
The CaCl2-based electrolyte may be a commercially available source of CaCl2, such as calcium chloride dihydrate, that partially decomposes on heating and produces CaO or otherwise includes CaO. Alternatively, or in addition, the CaCl2-based electrolyte may include CaCl2 and CaO that are added separately or pre-mised to form the electrolyte.
At this stage, the applicant does not have a clear understanding of the electrolytic cell mechanism when the cell is operated at a potential at which CaCl2- based electrolyte partially decomposes. 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 electrolytic cell above a potential at which CaCl2-based electrolyte partially decomposes produces Ca++ cations that migrate to the vicinity of the metal oxide in contact with the molten metal cathode and provide a driving force that facilitates extraction of O" anions produced by electrolytic reduction to metal of metal oxide in contact with the molten metal cathode. The applicant also believes that the 0""anions, once extracted from the metal oxide, migrate to the anode and react with anode carbon and produce CO and release electrons that facilitate electrolytic reduction of metal oxide to metal . The experimental work 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 metal oxide in the cathode and participated in chemical reduction of oxides.
It is preferred that the anode be graphite.
Preferably the cell includes a base and side walls extending upwardly from the base formed from graphite. Preferably the cell includes at least one tap hole for molten metal in one of the side walls and the method includes removing molten metal continuously or periodically.
The above-described method may be started-up in a number of ways.
One option is to introduce the (pure) metal and the electrolyte in solid state into the cell and subsequently heat the entire system to melt the metal and the electrolyte.
Another option is to introduce molten metal and molten electrolyte separately into the cell .
The following example illustrates an application of the invention in the process of reducing aluminium oxide (alumina) into substantially pure aluminium using an electrolytic cell as illustrated in Figure 1.
4. Description of Exemplary Embodiment
Figure 1 is a schematic illustration of an electrolytic cell 5 that can be scaled-up in application of the present invention.
Whilst the example described below relates to the reduction of alumina, the basic principle is equally applicable to other metals, particularly low melting point metals, more particularly magnesium.
The electrolytic cell 5 of Figure 1 includes a graphite crucible 10 that has a base 21, side walls 31, and a tapping/discharge opening indicated as 12 in one of the side walls 31. The electrolytic cell 5 further includes a bath of molten CaCl electrolyte 13 in the crucible and a graphite electrode 11 immersed in the molten electrolyte 13. The graphite electrode 11 forms the anode of the cell 5.
The electrolytic cell 5 further includes a pool 15 of molten aluminium in a lower section of the crucible 10. The molten aluminium pool 15 forms the cathode of the cell.
The electrolytic cell further includes a body 14 that consists of or incorporates alumina (A1203) to be reduced and extends into the electrolyte 13 and contacts the molten aluminium cathode 15. The alumina is shaped as a rod, sheet or prismatic body. Alumina body 14 is held in an appropriate manner to allow controlled movement into and away from the crucible interior as indicated by the arrow 16.
The electrolytic cell 5 further includes a suitable power source 18 connected to the anode 11 and to the molten aluminium cathode 15.
The molten aluminium cathode 15 is required in order to initiate electrolytic reduction of the alumina in the alumina body 14 to aluminium. The electrolytic reduction process is carried out at an elevated temperature of around 950°C at which the CaCl2 electrolyte is and remains molten. On immersion of the alumina body 14 into the electrolyte 13 and subsequent contact of the alumina body 14 with the molten aluminium cathode 15, reduction of the alumina takes place. Since the process temperatures are above the melting point of aluminium, the latter will melt into the bath 15 and the bath level within crucible 10 will tend to rise. In order to maintain optimum reduction conditions, the alumina body 14 is moved at a rate commensurate with the melting-off rate of aluminium from the alumina body 14 and the build-up of aluminium so that immersion of the alumina body 14 in the molten aluminium is kept at a minimum.
The process may be operated in a continuous mode by removing molten aluminium through tap hole 12 and positioning additional alumina bodies 14 in the electrolyte 13 to replace bodies 14 that are consumed in the reduction process .
Many modifications may be made to the embodiment of the present invention described above without departing from the spirit and scope of the present invention.

Claims

CLAIMS :
1. A method of electrolytically reducing a metal oxide to produce a metal in an electrolytic cell, which method includes electrolytically reducing the metal oxide in an electrolytic cell that includes a pool of molten metal, the metal being the metal of the metal oxide to be reduced, the molten metal pool forming a cathode of the cell, a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides, an anode extending into the electrolyte, and a body of metal oxide to reduced in contact with the molten metal and the electrolyte.
2. The method defined in claim 1 wherein the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
3. The method defined in claim 1 or claim 2 includes feeding the metal oxide body into the electrolytic cell to maintain contact of the metal oxide and the molten metal .
4. The method defined in any one of the preceding claims wherein the metal oxide body includes rods, plates and blocks that can be readily immersed into the electrolyte and brought into contact with the molten metal .
5. The method defined in any one of the preceding claims includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced.
6. The method defined in any one of the preceding claims includes operating the cell at a potential that is 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.
7. The method defined in any one of the preceding claims wherein the metal oxide is an aluminium oxide or a magnesium oxide.
8. The method defined in claim 7 wherein the electrolyte is a CaCl2-based electrolyte that includes CaO as one of the constituents.
9. The method defined in claim 8 includes maintaining the cell potential above the decomposition potential for CaO.
10. The method defined in claim 8 or claim 9 includes maintaining the cell potential below the decomposition potential for CaCl2.
11. The method defined in claim 10 includes maintaining the cell potential less than 3.0V.
12. The method defined in claim 10 includes maintaining the cell potential less than 2.5V.
13. The method defined in claim 10 includes maintaining the cell potential less than 2.0V.
14. The method defined in any one of claims 8 to 13 includes maintaining the cell potential to be at least
1.5V.
15. The method defined in any one of the preceding claims wherein the cell includes at least one tap hole for molten metal and the method includes removing molten metal continuously or periodically via the tap hole.
PCT/AU2002/000456 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides WO2002083989A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU2002245948A AU2002245948B2 (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides
JP2002581721A JP2004523662A (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides
EP02713941A EP1392890A4 (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides
CA002443953A CA2443953A1 (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides
US10/474,746 US20040237710A1 (en) 2001-04-10 2002-04-10 Electrolytic reducion of metal oxides
NO20034548A NO20034548L (en) 2001-04-10 2003-10-09 Electrolytic reduction of metal oxides
US11/924,808 US20080110764A1 (en) 2001-04-10 2007-10-26 Electrolytic Reduction of Metal Oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPR4439 2001-04-10
AUPR4439A AUPR443901A0 (en) 2001-04-10 2001-04-10 Method for reduction of metal oxides to pure metals

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/924,808 Continuation US20080110764A1 (en) 2001-04-10 2007-10-26 Electrolytic Reduction of Metal Oxides

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WO2002083989A1 true WO2002083989A1 (en) 2002-10-24

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US (2) US20040237710A1 (en)
EP (1) EP1392890A4 (en)
JP (1) JP2004523662A (en)
CN (1) CN1509346A (en)
AU (1) AUPR443901A0 (en)
CA (1) CA2443953A1 (en)
NO (1) NO20034548L (en)
WO (1) WO2002083989A1 (en)
ZA (1) ZA200307978B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004033760A2 (en) * 2002-10-09 2004-04-22 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
KR20150072850A (en) * 2013-12-20 2015-06-30 현대자동차주식회사 Regeneration method of raw materials for hydrogen supply system of fuel cell
WO2024177534A1 (en) * 2023-02-20 2024-08-29 Общество с ограниченной ответственностью "Институт легких материалов и технологий" Method and device for electrorefining aluminium in electrolysis cells (embodiments)
EP4249643A4 (en) * 2020-11-17 2024-10-23 Ksm Tech Co Ltd Reduction system and method for high-melting point metal oxides, using liquid metal crucible
EP4249644A4 (en) * 2020-11-17 2024-10-30 Ksm Tech Co Ltd Reduction method and system for high-melting-point metal oxide, using fluoride-based electrolytes

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US8152895B2 (en) * 2003-04-23 2012-04-10 Ut-Battelle, Llc Production of magnesium metal
US20100323253A1 (en) * 2006-02-22 2010-12-23 University Of Utah Resarch Foundation Systems and Methods for Hydrogen Storage and Generation from Water Using Lithium Based Materials
EP2469969A1 (en) 2010-12-24 2012-06-27 Philip Morris Products S.A. Reduced ceramic heating element
CN109055985B (en) * 2018-09-12 2019-09-27 郑州大学 A kind of electrolytic oxidation magnesium molten salt system, preparation method and applications
KR102004920B1 (en) * 2019-01-28 2019-07-29 한국지질자원연구원 Metal refining method by using liquid metal cathode
CN110219021B (en) * 2019-06-19 2024-05-24 陕西均健佳实业有限公司 Magnesium electrolytic tank and magnesium electrolysis process

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
WO2004033760A2 (en) * 2002-10-09 2004-04-22 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
WO2004033760A3 (en) * 2002-10-09 2007-11-29 Bhp Billiton Innovation Pty Electrochemical reduction of metal oxides
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
KR20150072850A (en) * 2013-12-20 2015-06-30 현대자동차주식회사 Regeneration method of raw materials for hydrogen supply system of fuel cell
US9340419B2 (en) 2013-12-20 2016-05-17 Hyundai Motor Company Regeneration method of raw materials for hydrogen supply system of fuel cell
KR101655143B1 (en) 2013-12-20 2016-09-07 현대자동차 주식회사 Regeneration method of raw materials for hydrogen supply system of fuel cell
DE102014225400B4 (en) 2013-12-20 2022-02-17 Hyundai Motor Company Regeneration method of raw materials for a hydrogen supply system of a fuel cell
EP4249643A4 (en) * 2020-11-17 2024-10-23 Ksm Tech Co Ltd Reduction system and method for high-melting point metal oxides, using liquid metal crucible
EP4249644A4 (en) * 2020-11-17 2024-10-30 Ksm Tech Co Ltd Reduction method and system for high-melting-point metal oxide, using fluoride-based electrolytes
WO2024177534A1 (en) * 2023-02-20 2024-08-29 Общество с ограниченной ответственностью "Институт легких материалов и технологий" Method and device for electrorefining aluminium in electrolysis cells (embodiments)

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Publication number Publication date
JP2004523662A (en) 2004-08-05
EP1392890A1 (en) 2004-03-03
NO20034548D0 (en) 2003-10-09
US20040237710A1 (en) 2004-12-02
AUPR443901A0 (en) 2001-05-17
CA2443953A1 (en) 2002-10-24
ZA200307978B (en) 2004-09-03
NO20034548L (en) 2003-12-01
CN1509346A (en) 2004-06-30
US20080110764A1 (en) 2008-05-15
EP1392890A4 (en) 2004-10-06

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