WO2004033760A2 - Reduction electrochimique d'oxydes metalliques - Google Patents

Reduction electrochimique d'oxydes metalliques Download PDF

Info

Publication number
WO2004033760A2
WO2004033760A2 PCT/AU2003/001330 AU0301330W WO2004033760A2 WO 2004033760 A2 WO2004033760 A2 WO 2004033760A2 AU 0301330 W AU0301330 W AU 0301330W WO 2004033760 A2 WO2004033760 A2 WO 2004033760A2
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
anode
cell
metal
metal oxide
Prior art date
Application number
PCT/AU2003/001330
Other languages
English (en)
Other versions
WO2004033760A3 (fr
Inventor
Les Stresov
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 US10/530,835 priority Critical patent/US20060191799A1/en
Priority to AU2003266842A priority patent/AU2003266842A1/en
Publication of WO2004033760A2 publication Critical patent/WO2004033760A2/fr
Publication of WO2004033760A3 publication Critical patent/WO2004033760A3/fr

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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements

Definitions

  • the present invention relates to electrochemical reduction of metal oxides.
  • the present invention was made during the course of an on-going research project on electrochemical reduction of metal oxides being carried out by the applicant.
  • the research project has focussed on the reduction of titania (Ti0 2 ) .
  • 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 cells at potentials above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the cells could electrochemically reduce titania to titanium with low concentrations of oxygen, ie concentrations less than 0.2 wt %.
  • the cell operation is dependent on decomposition of CaO, with Ca ++ cations migrating to the cathode and depositing as Ca metal and 0 " ⁇ anions migrating to the anode and forming CO and/or C0 2 (in a situation in which the anode is a graphite anode) and releasing electrons that facilitate electrolytic deposition of Ca metal on the cathode .
  • the applicant also believes that the 0 " ⁇ anions, once extracted from the titania, migrate to the anode and react with anode carbon and produce CO and/or C0 2 (and in some instances CaO) and release electrons that facilitate electrolytic deposition of Ca metal on the cathode.
  • 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 that is described and claimed in the International application provides an electrolytic cell for electrochemical reduction of a metal oxide, such as titania, 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 electrolyte.
  • a metal oxide such as titania
  • the invention that is described and claimed in the International application is a method of electrochemically reducing a metal oxide, such as titania, 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, and which method includes applying a cell potential across the anode .
  • a metal oxide such as titania
  • the present invention is an improvement of the invention described and claimed in the International application.
  • an electrochemical cell for electrochemical reduction of a metal oxide, such as titania, in a solid state which electrochemical cell includes (a) a molten electrolyte, (b) a cathode formed at least in part from the metal oxide in contact with the electrolyte, (c) an anode, and (d) a membrane that separates the electrolyte and the anode and is permeable to oxygen cations and is impermeable to dissolved metal in the electrolyte, and optionally is impermeable to any one or more of (i) electrolyte anions other that oxygen anions, (ii) anode metal cations, and
  • the above-described membrane prevents back reaction of dissolved metal in the electrolyte and oxygen atoms generated at the anode that can significantly reduce the current efficiency of the cell. Specifically, the membrane allows oxygen anions to migrate to the anode and give up electrons at the anode and prevents dissolved metal in the electrolyte migrating to the anode and reacting with oxygen atoms generated at the anode.
  • the membrane makes it possible for the cell to operate at high current efficiencies.
  • the membrane makes it possible to operate the cell at higher potentials without the disadvantages that are often associated with operating at such higher cell potentials.
  • the electrolyte includes CaCl 2 it is undesirable to operate at potentials that result in evolution of chlorine gas because of the corrosive and toxic properties of the gas.
  • the membrane prevents the migration of CI " anions to the anode and thereby prevents the evolution of chlorine gas. Operating at higher cell potentials is advantageous because it produces higher currents and therefore reduces cycle times .
  • the anode is a molten metal anode.
  • the present invention also extends to other arrangements.
  • the present invention extends to fuel cell arrangements in which there is (a) a coating of a suitable metal/metal oxide system, such as
  • Ni/NiO on the membrane that forms the anode and conducts electrons released by the oxygen anions and (b) a fuel, such as hydrogen or natural gas, that consumes oxygen that is evolved at the anode.
  • the anode may be arranged so that oxygen gas is evolved at the anode and is removed from the cell .
  • the anode may be also be arranged so that there is no oxygen gas released from the anode assembly.
  • the anode may include a means for scavenging oxygen that is generated at the anode when oxygen anions migrate to the anode and give up electrons at the anode.
  • the above-described gaseous fuel is one suitable scavenging means.
  • the scavenging means may also be a solid material that is oxidised by oxygen.
  • solid scavenging materials are preferred in situations in which the anode is a molten metal anode.
  • Suitable solid scavenging materials for molten silver anodes include iron, carbon and tungsten.
  • the use of a scavenging means reduces the need to select molten metal anodes that have high solubility of oxygen in anode metal .
  • the solid scavenging materials form the anode electrode for molten metal anodes.
  • the membrane be impermeable to the anode electrode material.
  • the present invention is based on experimental work carried out by the applicant to electrochemically reduce titania.
  • the experimental work was carried out on a cell that included a stainless steel crucible containing molten CaCl 2 -based electrolyte containing at least some CaO, a cathode extending into the electrolyte, the cathode including Ti0 2 , and an anode in the form of molten silver contained in a yttria stabilised zirconia crucible extending into the electrolyte.
  • the yttria stabilised zirconia is permeable to oxygen anions and is impermeable to calcium metal dissolved in the electrolyte, chlorine anions, and silver cations.
  • the anode electrical connection was made via a low carbon steel wire extending into the molten silver.
  • the cell was operated initially at a potential around 3V.
  • the cell was also operated at higher potentials, up to 10V. It was found that there was decomposition of CaCl 2 and no evolution of chlorine gas under • these conditions. There was also a proportional increase in current with increasing voltage.
  • the experimental work opens up the following possibilities for an electrolytic cell for electrochemically reducing metal oxides, such as titania.
  • Scavengers for molten silver anodes include iron, carbon, and tungsten.
  • the metal is chosen such that its melting point is within the operating temperature range 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 is silver or copper.
  • the membrane is formed from a solid electrolyte.
  • the solid electrolyte is an oxide.
  • the solid electrolyte is yttria stabilised zirconia.
  • the membrane includes a body and an outer lining, with the outer lining being in contact with the electrolyte, and the outer lining being formed from a • material that is inert with respect to dissolved metal in the electrolyte and is impermeable to the dissolved metal.
  • the electrolyte be a CaCl 2 - based electrolyte that includes CaO as one of the constituents.
  • CaO the electrolyte
  • the body is formed from the solid electrolyte.
  • the outer lining is formed from a rare earth oxide .
  • the rare earth oxide is yttria.
  • the lining is continuous and covers all of the surface of the membrane that is in contact with the electrolyte so that there are no sections of the body that are in contact with the electrolyte.
  • the metal oxide is a titanium oxide.
  • the metal oxide be titania.
  • a method of electrochemically reducing a metal oxide in a solid state in an electrochemical cell which electrochemical 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, (c) an anode, and (d) a membrane that separates the electrolyte and the anode and is permeable to oxygen ions and is impermeable to dissolved metal in the electrolyte, and optionally is impermeable to any one or more of (i) electrolyte anions other that oxygen anions, (ii) anode metal cations, and (iii) any other ions and atoms, and which method includes applying a cell potential across the anode and the cathode and electrochemically reducing the metal oxide .
  • the method includes electrochemically reducing the metal oxide to titanium having an oxygen concentration of less than 0.2wt.%.
  • 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 membrane is formed from a solid electrolyte.
  • the solid electrolyte is yttria stabilised zirconia.
  • 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 electrochemical cell 2 includes a graphite-free crucible 10 made of a suitable refractory material that is essentially inert with respect to the electrolyte and electrode materials described below at cell operating temperatures .
  • the electrochemical cell further includes a pool 18 of molten CaCl 2 electrolyte that contains at least some CaO within the crucible 10.
  • the electrochemical cell 2 further includes a pool 14 of molten silver or copper contained in a crucible of yttria stabilised zirconia that extends into the cell.
  • the molten Ag or Cu forms the molten metal anode 14 of the cell.
  • the yttria stabilised zirconia crucible 16 forms a membrane that allows migration of oxygen anions and prevents migration of calcium metal dissolved in the molten electrolyte into the molten anode.
  • the crucible has an outer lining of yttria.
  • the electrochemical cell 2 further includes a titania plate 12 positioned within a cage 24.
  • the cage 24 (and therefore the plate 12) is suspended into the crucible 10 by means of a lead 26. This assembly forms the cathode 20 of the cell.
  • the electrochemical cell 2 further includes a power source 22 and electrical connections between the power source 22 and the anode 14 and the cathode 20.
  • the connections include the above-described lead 26 and a further electrical lead 28.
  • the electrical lead 28 is a low carbon steel wire that is consumed during the operation of the cell - as described below.
  • power source 22 provides constant potential (voltage) settings thereby that allow the cell 2 to draw the amount of current required during the electrolytic refining of the metal oxide body at a selected potential.
  • the electrochemical cell 2 further includes thermocouples contained in suitable heat-resistant, inert sheaths (not illustrated) for monitoring temperature in the molten metal anode 14 and the molten electrolyte 18.
  • the above-described electrochemical 2 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.
  • the oxygen that passes into the electrolyte 18 by virtue of electrochemical reduction of the metal oxide is subsequently transported into the molten metal anode 14 via the membrane 16 and dissolves in the molten metal.
  • the dissolved oxygen then oxidises the steel electrode 28, and iron oxides accumulate on the surface of the molten metal anode and are periodically removed.

Landscapes

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

Abstract

L'invention concerne une pile électrochimique permettant de procéder à la réduction électrochimique d'un oxyde métallique, de type oxyde de titane, à l'état solide. La pile comprend: (a) un électrolyte en fusion (18); (b) une cathode (20) formée au moins en partie à partir d'oxyde métallique en contact avec l'électrolyte; (c) une anode (14); et (d) une membrane (16) qui sépare l'électrolyte et l'anode. La membrane est perméable aux cations d'oxygène et est imperméable au métal dissolu dans l'électrolyte. Eventuellement, la membrane est imperméable à (i) tout anion d'électrolyte autre que les anions d'oxygène, (ii) à tout cation métallique d'anode, et (iii) à tout autre ion et atome. L'invention concerne également un procédé électrochimique fondé sur ladite pile.
PCT/AU2003/001330 2002-10-09 2003-10-09 Reduction electrochimique d'oxydes metalliques WO2004033760A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/530,835 US20060191799A1 (en) 2002-10-09 2003-10-09 Electrochemical reduction of metal oxides
AU2003266842A AU2003266842A1 (en) 2002-10-09 2003-10-09 Electrochemical reduction of metal oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2002951962A AU2002951962A0 (en) 2002-10-09 2002-10-09 Electrolytic reduction of metal oxides
AU2002951962 2002-10-09

Publications (2)

Publication Number Publication Date
WO2004033760A2 true WO2004033760A2 (fr) 2004-04-22
WO2004033760A3 WO2004033760A3 (fr) 2007-11-29

Family

ID=28679592

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2003/001330 WO2004033760A2 (fr) 2002-10-09 2003-10-09 Reduction electrochimique d'oxydes metalliques

Country Status (4)

Country Link
US (1) US20060191799A1 (fr)
CN (1) CN101166838A (fr)
AU (1) AU2002951962A0 (fr)
WO (1) WO2004033760A2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006113076A2 (fr) * 2005-04-18 2006-10-26 Clean Coal Energy, Llc Pile a combustible carbone, a production directe d'electricite, dotee d'une anode fondue
WO2007011669A2 (fr) * 2005-07-15 2007-01-25 Trustees Of Boston University Anodes inertes produisant de l'oxygene pour un processus som
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
US20110014526A1 (en) * 2005-05-16 2011-01-20 Guer Turgut M High temperature direct coal fuel cell
US8758949B2 (en) 2005-06-16 2014-06-24 The Trustees Of Boston University Waste to hydrogen conversion process and related apparatus
KR20150101457A (ko) * 2012-12-24 2015-09-03 메탈리시스 리미티드 전해 환원에 의한 금속의 생성방법 및 장치

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003903150A0 (en) * 2003-06-20 2003-07-03 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US20070193877A1 (en) * 2003-09-26 2007-08-23 Rigby Gregory D Electrochemical reduction of metal oxides
WO2005038092A1 (fr) * 2003-10-14 2005-04-28 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
RU2006137273A (ru) * 2004-03-22 2008-04-27 Би Эйч Пи БИЛЛИТОН ИННОВЕЙШН ПТИ ЛТД (AU) Электрохимическое восстановление оксидов металлов
CN101006204A (zh) * 2004-06-22 2007-07-25 Bhp比利顿创新公司 金属氧化物的电化学还原
CA2575580A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
CN101068955A (zh) * 2004-07-30 2007-11-07 Bhp比利顿创新公司 金属氧化物的电化学还原
WO2008101283A1 (fr) * 2007-02-20 2008-08-28 Metalysis Limited Réduction électrochimique d'oxydes métalliques
WO2008101290A1 (fr) * 2007-02-20 2008-08-28 Metalysis Limited Réduction électrochimique d'oxydes métalliques
US8764962B2 (en) * 2010-08-23 2014-07-01 Massachusetts Institute Of Technology Extraction of liquid elements by electrolysis of oxides
GB201102023D0 (en) * 2011-02-04 2011-03-23 Metalysis Ltd Electrolysis method, apparatus and product
JP6000002B2 (ja) * 2012-07-17 2016-09-28 古河電気工業株式会社 銅微粒子の製造装置、及び銅微粒子の製造方法
DE102014111781B4 (de) * 2013-08-19 2022-08-11 Korea Atomic Energy Research Institute Verfahren zur elektrochemischen Herstellung einer Silizium-Schicht
CN103422122B (zh) * 2013-08-30 2016-08-10 昆明理工大学 一种二氧化钛直接制备金属钛的方法
US10087502B2 (en) * 2014-02-25 2018-10-02 Colorado School Of Mines Decoating of coated materials
CN105040033A (zh) * 2015-07-13 2015-11-11 鄂州汉衍新材料有限公司 一种电解脱氧制备高纯铁粉方法与装置
CN106917113A (zh) * 2015-12-27 2017-07-04 天津赫维科技有限公司 一种电化学法制备金属钛的装置及其方法
EP3427826B1 (fr) * 2016-03-08 2020-11-25 Japan Science and Technology Agency Catalyseur, et mise en oeuvre de celui-ci
CN108728870B (zh) * 2017-08-07 2021-02-12 南京佑天金属科技有限公司 晶条铪的生产系统及其方法
KR102123509B1 (ko) * 2018-08-02 2020-06-17 한국원자력연구원 미환원 산화물 분리 장치 및 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083989A1 (fr) * 2001-04-10 2002-10-24 Bhp Billiton Innovation Pty Ltd Reduction electrolytique d'oxydes metalliques
WO2002083993A1 (fr) * 2001-04-10 2002-10-24 Bhp Billiton Innovation Pty Ltd Reduction electrolytique d'oxydes metalliques
WO2003076692A1 (fr) * 2002-03-13 2003-09-18 Bhp Billiton Innovation Pty Ltd Minimisation du transfert de carbone dans une cellule electrolytique
WO2003076690A1 (fr) * 2002-03-13 2003-09-18 Bhp Billiton Innovation Pty Ltd Reduction d'oxydes metalliques dans une cellule electrolytique

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2012009C (fr) * 1989-03-16 1999-01-19 Tadashi Ogasawara Procede pour la production electrolytique du magnesium
US5006209A (en) * 1990-02-13 1991-04-09 Electrochemical Technology Corp. Electrolytic reduction of alumina
US6540902B1 (en) * 2001-09-05 2003-04-01 The United States Of America As Represented By The United States Department Of Energy Direct electrochemical reduction of metal-oxides
JP2003129268A (ja) * 2001-10-17 2003-05-08 Katsutoshi Ono 金属チタンの精錬方法及び精錬装置
AU2002952083A0 (en) * 2002-10-16 2002-10-31 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
WO2004053201A1 (fr) * 2002-12-12 2004-06-24 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
AU2003903150A0 (en) * 2003-06-20 2003-07-03 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US20070193877A1 (en) * 2003-09-26 2007-08-23 Rigby Gregory D Electrochemical reduction of metal oxides
WO2005038092A1 (fr) * 2003-10-14 2005-04-28 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
RU2006137273A (ru) * 2004-03-22 2008-04-27 Би Эйч Пи БИЛЛИТОН ИННОВЕЙШН ПТИ ЛТД (AU) Электрохимическое восстановление оксидов металлов
CN101006204A (zh) * 2004-06-22 2007-07-25 Bhp比利顿创新公司 金属氧化物的电化学还原
CA2575580A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
CN101068955A (zh) * 2004-07-30 2007-11-07 Bhp比利顿创新公司 金属氧化物的电化学还原

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083989A1 (fr) * 2001-04-10 2002-10-24 Bhp Billiton Innovation Pty Ltd Reduction electrolytique d'oxydes metalliques
WO2002083993A1 (fr) * 2001-04-10 2002-10-24 Bhp Billiton Innovation Pty Ltd Reduction electrolytique d'oxydes metalliques
WO2003076692A1 (fr) * 2002-03-13 2003-09-18 Bhp Billiton Innovation Pty Ltd Minimisation du transfert de carbone dans une cellule electrolytique
WO2003076690A1 (fr) * 2002-03-13 2003-09-18 Bhp Billiton Innovation Pty Ltd Reduction d'oxydes metalliques dans une cellule electrolytique

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
WO2006113076A2 (fr) * 2005-04-18 2006-10-26 Clean Coal Energy, Llc Pile a combustible carbone, a production directe d'electricite, dotee d'une anode fondue
WO2006113076A3 (fr) * 2005-04-18 2007-10-25 Clean Coal Energy Llc Pile a combustible carbone, a production directe d'electricite, dotee d'une anode fondue
US20110014526A1 (en) * 2005-05-16 2011-01-20 Guer Turgut M High temperature direct coal fuel cell
US8758949B2 (en) 2005-06-16 2014-06-24 The Trustees Of Boston University Waste to hydrogen conversion process and related apparatus
WO2007011669A2 (fr) * 2005-07-15 2007-01-25 Trustees Of Boston University Anodes inertes produisant de l'oxygene pour un processus som
WO2007011669A3 (fr) * 2005-07-15 2007-09-27 Univ Boston Anodes inertes produisant de l'oxygene pour un processus som
US8658007B2 (en) 2005-07-15 2014-02-25 The Trustees Of Boston University Oxygen-producing inert anodes for SOM process
KR20150101457A (ko) * 2012-12-24 2015-09-03 메탈리시스 리미티드 전해 환원에 의한 금속의 생성방법 및 장치
KR102289555B1 (ko) 2012-12-24 2021-08-13 메탈리시스 리미티드 전해 환원에 의한 금속의 생성방법 및 장치

Also Published As

Publication number Publication date
CN101166838A (zh) 2008-04-23
US20060191799A1 (en) 2006-08-31
AU2002951962A0 (en) 2002-10-24
WO2004033760A3 (fr) 2007-11-29

Similar Documents

Publication Publication Date Title
US20060191799A1 (en) Electrochemical reduction of metal oxides
Mohandas et al. FFC Cambridge process and removal of oxygen from metal-oxygen systems by molten salt electrolysis: an overview
CA2479048C (fr) Reduction d'oxydes metalliques dans une cellule electrolytique
Fray et al. Reduction of titanium and other metal oxides using electrodeoxidation
CN104919089B (zh) 通过电解还原生产金属的方法和设备
US6663763B2 (en) Reduction of metal oxides in an electrolytic cell
EP1866448A1 (fr) Procédé et dispositif électrochimiques pour l élimination de l oxygene d un composé ou d un metal
US7628904B2 (en) Minimising carbon transfer in an electrolytic cell
US20050121333A1 (en) Electrolytic reduction of metal oxides
MXPA03007326A (es) Extraccion de metales.
JP2012136766A (ja) 電気分解による金属の製造方法
RU2302482C2 (ru) Минимизация переноса углерода в электролизере
AU2003266842A1 (en) Electrochemical reduction of metal oxides
AU2003209826B2 (en) Reduction of metal oxides in an electrolytic cell
AU2002244540B2 (en) Electrolytic reduction of metal oxides
AU2003269600A1 (en) Minimising carbon transfer in an electrolytic cell
AU2002244540A1 (en) Electrolytic reduction of metal oxides
AU2003209825A1 (en) Minimising carbon transfer in an electrolytic cell
AU2002231464A1 (en) Extraction of metals

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

WWE Wipo information: entry into national phase

Ref document number: 2003266842

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 20038A53720

Country of ref document: CN

122 Ep: pct application non-entry in european phase
WWE Wipo information: entry into national phase

Ref document number: 2006191799

Country of ref document: US

Ref document number: 10530835

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 10530835

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Ref document number: JP