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WO2002083993A1 - Reduction electrolytique d'oxydes metalliques - Google Patents

Reduction electrolytique d'oxydes metalliques Download PDF

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Publication number
WO2002083993A1
WO2002083993A1 PCT/AU2002/000457 AU0200457W WO02083993A1 WO 2002083993 A1 WO2002083993 A1 WO 2002083993A1 AU 0200457 W AU0200457 W AU 0200457W WO 02083993 A1 WO02083993 A1 WO 02083993A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
cell
metal
anode
molten
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.)
Ceased
Application number
PCT/AU2002/000457
Other languages
English (en)
Inventor
Les Stresov
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.)
BHP Innovation Pty Ltd
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 EP02712654A priority Critical patent/EP1412558A4/fr
Priority to CA002443960A priority patent/CA2443960A1/fr
Priority to AU2002244540A priority patent/AU2002244540B2/en
Priority to US10/474,745 priority patent/US20050121333A1/en
Publication of WO2002083993A1 publication Critical patent/WO2002083993A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic 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 (Ti0 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 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-0 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.
  • Figure 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 12b.
  • the cage 12b (and therefore the plate 12) is suspended into the crucible 10 by means of a lead 12a. 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 12a 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 0 into the surrounding atmosphere.
  • this transport mechanism is effective for as long as oxygen in the molten metal anode is below the saturation level .

Landscapes

  • 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

La présente invention concerne une cellule électrolytique et un procédé permettant la réduction électrolytique d'un oxyde métallique (tel que le dioxyde de titane) à l'état solide. La cellule électrolytique comprend: (a) un électrolyte fondu; (b) une cathode en contact avec l'électrolyte, la cathode étant formée au moins en partie à partir de l'oxyde métallique; et (c) une anode de métal fondu (tel que de l'argent ou du cuivre) en contact avec l'électrolyte.
PCT/AU2002/000457 2001-04-10 2002-04-10 Reduction electrolytique d'oxydes metalliques Ceased WO2002083993A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP02712654A EP1412558A4 (fr) 2001-04-10 2002-04-10 Reduction electrolytique d'oxydes metalliques
CA002443960A CA2443960A1 (fr) 2001-04-10 2002-04-10 Reduction electrolytique d'oxydes metalliques
AU2002244540A AU2002244540B2 (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides
US10/474,745 US20050121333A1 (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPR4438A AUPR443801A0 (en) 2001-04-10 2001-04-10 Removal of oxygen from metal oxides and solid metal solutions
AUPR4438 2001-04-10

Publications (1)

Publication Number Publication Date
WO2002083993A1 true WO2002083993A1 (fr) 2002-10-24

Family

ID=3828434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2002/000457 Ceased WO2002083993A1 (fr) 2001-04-10 2002-04-10 Reduction electrolytique d'oxydes metalliques

Country Status (6)

Country Link
US (1) US20050121333A1 (fr)
EP (1) EP1412558A4 (fr)
AU (1) AUPR443801A0 (fr)
CA (1) CA2443960A1 (fr)
WO (1) WO2002083993A1 (fr)
ZA (1) ZA200307914B (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076690A1 (fr) * 2002-03-13 2003-09-18 Bhp Billiton Innovation Pty Ltd Reduction d'oxydes metalliques dans une cellule electrolytique
RU2284376C2 (ru) * 2004-01-05 2006-09-27 Открытое акционерное общество "Сибирский научно-исследовательский, конструкторский и проектный институт алюминиевой и электродной промышленности" (ОАО "СибВАМИ") Способ питания алюминиевого электролизера фтористыми солями
WO2004033760A3 (fr) * 2002-10-09 2007-11-29 Bhp Billiton Innovation Pty Reduction electrochimique d'oxydes metalliques
US7410562B2 (en) 2003-08-20 2008-08-12 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
WO2008101283A1 (fr) * 2007-02-20 2008-08-28 Metalysis Limited Réduction électrochimique d'oxydes métalliques
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited 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
WO2014102223A1 (fr) 2012-12-24 2014-07-03 Metalysis Limited Procédé et appareil de production de métal par réduction électrolytique
US9150943B2 (en) 2007-01-22 2015-10-06 Materials & Electrochemical Research Corp. Metallothermic reduction of in-situ generated titanium chloride
WO2015198052A1 (fr) 2014-06-26 2015-12-30 Metalysis Limited Procédé et appareil pour la réduction électrolytique d'une charge d'alimentation comprenant de l'oxygène et un premier métal
GB2534332A (en) * 2014-06-26 2016-07-27 Metalysis Ltd Method and apparatus for producing metallic tantalum by electrolytic reduction of a feedstock

Families Citing this family (7)

* 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
KR101588123B1 (ko) * 2014-06-03 2016-02-15 한국원자력연구원 액체 양극을 이용한 금속산화물의 전해환원 방법 및 그 장치
GB201411430D0 (en) 2014-06-26 2014-08-13 Metalysis Ltd Method of producing metallic tanralum
WO2016040278A1 (fr) * 2014-09-10 2016-03-17 Alcoa Inc. Systèmes et procédés de protection des parois de cellules d'électrolyse
WO2019084045A1 (fr) * 2017-10-23 2019-05-02 Arconic Inc. Procédés basés sur l'électrolyse pour le recyclage de particules de titane
WO2021165974A1 (fr) * 2020-02-20 2021-08-26 Helios Project Ltd. Électrolyse d'oxyde fondu à base d'anode liquide/production d'oxygène à partir de l'électrolyse d'oxyde fondu
US20250135430A1 (en) * 2023-11-01 2025-05-01 Airbus Defence and Space GmbH Reactor Device for Converting Powdered Metal Oxides and Conversion System Comprising Same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO1998033956A1 (fr) * 1997-02-04 1998-08-06 Cathingots Limited Procede pour la production electrolytique de metaux
WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
GB2359564A (en) * 2000-02-22 2001-08-29 Secr Defence Electrolytic reduction of metal oxides

Family Cites Families (1)

* 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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO1998033956A1 (fr) * 1997-02-04 1998-08-06 Cathingots Limited Procede pour la production electrolytique de metaux
WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
GB2359564A (en) * 2000-02-22 2001-08-29 Secr Defence Electrolytic reduction of metal oxides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1412558A4 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003076690A1 (fr) * 2002-03-13 2003-09-18 Bhp Billiton Innovation Pty Ltd Reduction d'oxydes metalliques dans une cellule electrolytique
WO2004033760A3 (fr) * 2002-10-09 2007-11-29 Bhp Billiton Innovation Pty Reduction electrochimique d'oxydes metalliques
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
US7410562B2 (en) 2003-08-20 2008-08-12 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
EP2322693A1 (fr) 2003-08-20 2011-05-18 Materials And Electrochemical Research Corporation Procédé électrochimique pour la production de titane
US7985326B2 (en) 2003-08-20 2011-07-26 Materials And Electrochemical Research Corp. Thermal and electrochemical process for metal production
RU2284376C2 (ru) * 2004-01-05 2006-09-27 Открытое акционерное общество "Сибирский научно-исследовательский, конструкторский и проектный институт алюминиевой и электродной промышленности" (ОАО "СибВАМИ") Способ питания алюминиевого электролизера фтористыми солями
US7794580B2 (en) 2004-04-21 2010-09-14 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
US9150943B2 (en) 2007-01-22 2015-10-06 Materials & Electrochemical Research Corp. Metallothermic reduction of in-situ generated titanium chloride
WO2008101283A1 (fr) * 2007-02-20 2008-08-28 Metalysis Limited Réduction électrochimique d'oxydes métalliques
WO2014102223A1 (fr) 2012-12-24 2014-07-03 Metalysis Limited Procédé et appareil de production de métal par réduction électrolytique
JP2016503127A (ja) * 2012-12-24 2016-02-01 メタリシス リミテッド 電解還元による金属を製造するための方法及び装置
CN104919089B (zh) * 2012-12-24 2017-09-26 金属电解有限公司 通过电解还原生产金属的方法和设备
US9926636B2 (en) 2012-12-24 2018-03-27 Metalysis Limited Method and apparatus for producing metal by electrolytic reduction
WO2015198052A1 (fr) 2014-06-26 2015-12-30 Metalysis Limited Procédé et appareil pour la réduction électrolytique d'une charge d'alimentation comprenant de l'oxygène et un premier métal
GB2534332A (en) * 2014-06-26 2016-07-27 Metalysis Ltd Method and apparatus for producing metallic tantalum by electrolytic reduction of a feedstock

Also Published As

Publication number Publication date
EP1412558A4 (fr) 2005-08-24
AUPR443801A0 (en) 2001-05-17
CA2443960A1 (fr) 2002-10-24
US20050121333A1 (en) 2005-06-09
EP1412558A1 (fr) 2004-04-28
ZA200307914B (en) 2004-09-03

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