[go: up one dir, main page]

WO2005038092A1 - Reduction electrochimique d'oxydes metalliques - Google Patents

Reduction electrochimique d'oxydes metalliques Download PDF

Info

Publication number
WO2005038092A1
WO2005038092A1 PCT/AU2004/001410 AU2004001410W WO2005038092A1 WO 2005038092 A1 WO2005038092 A1 WO 2005038092A1 AU 2004001410 W AU2004001410 W AU 2004001410W WO 2005038092 A1 WO2005038092 A1 WO 2005038092A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
bath
cell
cathode
metal oxide
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/AU2004/001410
Other languages
English (en)
Inventor
Gregory David Rigby
Ivan Ratchev
Andrew Arthur Shook
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
Priority claimed from AU2003905595A external-priority patent/AU2003905595A0/en
Application filed by BHP Billiton Innovation Pty Ltd filed Critical BHP Billiton Innovation Pty Ltd
Priority to CN2004800372653A priority Critical patent/CN1894440B/zh
Priority to EA200600774A priority patent/EA009106B1/ru
Priority to EP04789581A priority patent/EP1680532A4/fr
Priority to US10/575,800 priority patent/US20080047845A1/en
Priority to JP2006534543A priority patent/JP2007509232A/ja
Priority to AU2004281296A priority patent/AU2004281296B2/en
Publication of WO2005038092A1 publication Critical patent/WO2005038092A1/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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/08—Apparatus
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts

Definitions

  • the present invention relates to electrochemical reduction of metal oxides.
  • the present invention relates particularly to continuous and semi-continuous electrochemical reduction of metal oxides in the form of powder to produce metal having a low oxygen concentration, typically no more than 0.2% by weight.
  • 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 used in the experiments 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 .
  • pellet and/or pellet as meaning particles having a particle size of 3.5 mm or less.
  • pellets as used herein is understood to mean particles that are less than 5 mm in a major dimension.
  • the term "semi-continuously” is understood in the International application and herein to mean that the process includes: (a) periods during which metal oxide powder and/or pellets are supplied to the cell and periods during which there is no such supply of metal oxide powder and/or pellets to the cell, and (b) periods during which reduced material is removed from the cell and periods during which there is no such removal of reduced material from the cell.
  • the term "batch" is understood in the International application and herein to include situations in which metal oxide is continuously supplied to a cell and reduced metal builds up in the cell until the end of a cell cycle, such as disclosed in International application WO 01/62996 in the name of The Secretary of State for Defense.
  • a commercial production cell should include a cell cathode in the form of a member, such as a plate, having an upper surface for supporting metal oxides in pellet form, as described herein, that is horizontally disposed or slightly inclined and has a forward end and a rearward end and is immersed in the electrolyte bath and is supported for movement, preferably in forward and rearward directions, so as to cause metal oxide pellets to move toward the forward end of the cathode.
  • the applicant has carried out further research and development work on the "shaker table” invention and has now designed a particular electrolytic cell in accordance with the invention.
  • the invention of the particular electrolytic cell design is the subject of an International application lodged on 27 September 2004 in the name of the applicant with a claim to priority from Australian provisional application 2003905261.
  • the particular electrolytic cell design is characterised by multiple anodes and by support structures that separately support the "shaker table” cathode and the anodes from above the cell, with the support structure enabling adjustment of the spacing of the anodes above the upper surface of the "shaker table” cathode.
  • the purged electrolyte could be cleaned to remove contaminants (such as carbides and carbonates) and that the cleaned electrolyte could be returned to the bath.
  • a process for electrochemically reducing a metal oxide feed material in a solid state in an electrolytic cell of the type that includes a molten bath of electrolyte, an anode, a cathode, and a means for applying a potential across the anode and the cathode, which process includes the steps of: (a) applying a potential across the anode and the cathode that is capable of electrochemically reducing metal oxide supplied to the molten electrolyte bath, (b) continuously or semi- continuously supplying the metal oxide feed material into the bath, (c) transporting the metal oxide feed material along a path within the bath and reducing the metal oxide as the feed material moves along the path, (d) continuously or semi-continuously removing at least partially reduced material from the bath, (e) supplying an amount of electrolyte into the bath that is greater than the amount of electrolyte that is required to compensate for loss of reduced material from the bath and electrolyte removed from the bath with the reduced material,
  • step (e) of making a deliberate addition or additions of electrolyte typically CaCl 2
  • electrolyte typically CaCl 2
  • the electrolyte addition in step (e) may be on a continuous or a periodic basis .
  • the electrolyte added to the bath in step (e) may be in a molten phase or a solid phase.
  • step (e) includes feeding electrolyte in an amount that is between 70% and 100% of the amount of metal oxide feed material supplied to the bath in step (b) on a time averaged basis.
  • electrolyte removal is via an overflow weir in the cell.
  • the removed electrolyte is treated to remove contaminants, such as carbides and carbonates.
  • the treated electrolyte is returned to the cell.
  • the metal oxide feed material is in the form of powders and/or pellets, as described herein.
  • the process includes treating the electrolyte removed from the bath in step (f) to remove contaminants and feeding the treated electrolyte to the bath.
  • the cathode is in the form of a member, such as a plate, having an upper surface for supporting metal oxides that are in powder and/or pellet form that is horizontally disposed or slightly inclined and has a forward end and a rearward end and is immersed in the electrolyte bath and is supported for movement in forward and rearward directions so as to cause metal oxide powders and/or pellets to move toward the forward end of the cathode.
  • a member such as a plate
  • step (b) includes supplying the metal oxide feed material in powder and/or pellet form to the bath so that the powders and/or pellets deposit on the upper surface of the cathode at a rearward end of the cathode.
  • the process includes the step of causing metal oxide powders and/or pellets to move over the upper surface of the cathode toward the forward end of the cathode while in contact with molten electrolyte whereby electrochemical reduction of the metal oxide occurs as the powders and/or pellets move toward the forward end.
  • step (b) includes supplying metal oxide powders and/or pellets into the molten electrolyte bath so that the powders and/or pellets form a mono-layer on an upper surface of the cathode.
  • step (c) includes transporting the metal oxide powders and/or pellets by causing metal oxide pellets to move on the upper surface of the cathode toward the forward end of the cathode as a packed mono-layer layer of powders and/or pellets .
  • step (c) includes selectively moving the cathode so as to cause metal oxide powders and/or pellets on the upper surface of the cathode to move toward the forward end of the cathode.
  • step (c) includes transporting the metal oxide powders and/or pellets by moving the cathode so as to cause powders and/or pellets across the width of the cathode to move at the same rate so that the powders and/or pellets have substantially the same residence time within the bath.
  • the process electrochemically reduces the metal oxide to metal having a concentration of oxygen that is no more than 0.3% by weight.
  • the concentration of oxygen is no more than 0.2% by weight.
  • the process may be a single or multiple stage process involving one or more than one electrolytic cell.
  • the process includes washing powders and/or pellets that are removed from the bath in step (d) to separate electrolyte that is carried from the cell with the powders and/or pellets.
  • the process includes recovering electrolyte that is washed from the powders and/or pellets and recycling the electrolyte to the cell.
  • the process includes maintaining the cell temperature below the vaporisation and/or decomposition temperatures of the electrolyte.
  • the process 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 electrolyte be a CaCl 2 - based electrolyte that includes CaO as one of the constituents .
  • the process includes maintaining the cell potential above the decomposition potential for CaO.
  • an electrolytic cell for electrochemically reducing metal oxide feed material which includes (a) a bath of a molten electrolyte, (b) a cathode, (c) an anode, (d) a means for applying a potential across the anodes and the cathode, (e) a means for supplying metal oxide feed material to the electrolyte bath, (f) a means for removing at least partially electrochemically reduced metal oxides from the electrolyte bath, (g) a means for supplying an amount of electrolyte into the bath that is greater than the amount of electrolyte that is required to compensate for loss of reduced material and electrolyte retained with reduced material removed from the bath, and (f) a means for removing molten electrolyte from the bath to maintain the bath height at a required height or within a range of required heights .
  • the cell further includes a means for treating the electrolyte removed from the bath in step (f) to remove contaminants from the electrolyte and for feeding the treated electrolyte to the bath.
  • the targeted contaminants may include carbides and carbonates .
  • the means for applying a potential across the anodes and the cathode includes (a) a power source and (b) an electrical circuit that electrically interconnects the power source, the anodes, and the cathode .
  • the cell includes a means for treating gases released from the cell.
  • the gas treatment means may include a means for removing any one or more of carbon monoxide, carbon dioxide, chlorine-containing gases, and phosgene from the gases .
  • the gas treatment means may also include a means for combusting carbon monoxide gas in the gases.
  • the electrolyte be a CaCl 2 - based electrolyte that includes CaO as one of the constituents .
  • the particle size of the powders and/or pellets is in the range of 1-4 mm.
  • the particle size of the powders and/or pellets is in the range of 1-3 mm.
  • FIG. 1 is a schematic diagram that illustrates one embodiment of an electrochemical process and apparatus in accordance with the present invention
  • FIG 2 is a perspective view of the electrolytic cell of the apparatus shown in Figure 1, with the cathode support rods removed to clarify the Figure;
  • Figure 3 a vertical section through the electrolytic cell shown in Figures 1 and 2;
  • Figure 4 is the vertical section shown in Figure
  • Figure 5 is the vertical section shown in Figure
  • the process is characterised by a step of making deliberate addition of electrolyte (typically CaCl 2 ) over and above the amount of electrolyte that is required to make up for reduced material and electrolyte that is retained by reduced material removed from the bath during operation of the cell.
  • electrolyte typically CaCl 2
  • the process is also characterised by a step of deliberately removing electrolyte from the bath to maintain bath height within the cell .
  • electrolyte addition is in the form of suitably-sized cast blocks and electrolyte removal is via an overflow weir in the cell.
  • the removed electrolyte is treated to remove CaO (by washing with HC1) and optionally contaminants, such as carbon.
  • the treated electrolyte is returned to the cell.
  • removal of electrolyte and treatment of the electrolyte removes oxygen ions from the electrolyte . This is a benefit in terms of improving the rate of diffusion of oxygen ions from the cathode to the anode.
  • the current proposal is to add 0.8kg/hr titania and 1.0 kg/hr electrolyte to the cell. This is a relatively small addition of electrolyte in the context that the bath will hold approximately 700 kg salt but is a relatively substantial addition in the context of the addition rate for titania to the cell .
  • Figure 1 is an electrolytic cell 1.
  • the cell shown in the drawings is an enclosed chamber that is rectangular in top plan and has a base wall 3, a pair of opposed end walls 5, a pair of opposed side walls 7, and a top cover 9.
  • the cell contains a bath 21 of molten electrolyte.
  • the preferred electrolyte is CaCl 2 with at least some CaO.
  • the cell includes an inlet 59 (see Figure 2) for solid electrolyte blocks in the top cover 9 at the right hand end as viewed in Figure 2 and the left hand end as viewed in the other Figures.
  • the apparatus includes a furnace 45 for melting commercially-supplied electrolyte and a casting station 47 for casting molten electrolyte from the furnace into suitably-sized blocks.
  • the cell includes a series of inlets for titania pellets in the top cover 9 near the left hand end of the cell as viewed in Figures 1, 3, 4, and 5 and near the right hand end of the cell as viewed in Figure 2. This end of the cell is hereinafter referred to as "the rearward end" of the cell.
  • the inlets are identified by the numeral 11 in Figure 2.
  • the apparatus includes a pan pelletiser 51 that forms the titania pellets in a "green” state and a sintering furnace 53 that sinters the "green" pellets to a sufficient strength to withstand subsequent processing.
  • the sintered pellets are stored in a storage bin 55 ready to be supplied via a vibratory feeder 57 to the cell inlets 11. Typically, the pellets have a size range of 1- 4 mm.
  • the cell further includes an outlet in the form of an overflow weir 49 (see Figures 3, 4, and 5) for removing excess electrolyte from the cell 1.
  • the overflow weir 49 is located at the opposite end of the cell 1 to the electrolyte inlet 59.
  • the overflow weir 49 is an effective option for ensuring that the bath of electrolyte does not exceed a predetermined maximum height.
  • the apparatus also includes a tank 57 for electrolyte removed from the cell 1 via the overflow weir 49.
  • the apparatus also includes a treatment station (not shown) for treating the electrolyte from tank 57 prior to recycling the electrolyte to the cell 1.
  • the electrolyte may be treated to remove carbides and carbonates from the electrolyte. Treatment may also include otherwise treating the electrolyte to remove other contaminants.
  • the cell further includes an outlet 13 for titanium metal pellets in the base wall 3 near the right hand end of the cell as viewed in Figures 1, 3, 4, and 5 and near the right hand end of the cell as viewed in Figure 2. This end of the cell is hereinafter referred to as "the forward end" of the cell.
  • the outlet 13 is in the form of a sump defined by downwardly converging sides 15 and an upwardly inclined auger 35 or other suitable means arranged to receive titanium pellets and retained electrolyte from a lower end of the sump and to transport the pellets away from the cell.
  • the cell further includes a cathode 25 in the form of a plate or other suitable member that is immersed in the bath 21 and is positioned a short distance above the base wall 3.
  • the cathode plate 25 is supported in the cell by a support structure so that the upper surface of the cathode plate 25 is horizontal or slightly inclined downwardly from the rearward end to the forward end of the cell .
  • the length and width dimensions of the cathode plate 25 are selected to be as large as possible to fit conveniently within the cell.
  • the cathode plate 25 is supported to move in the forward and rearward directions in an oscillating motion as described hereinafter.
  • the cathode support structure is described in detail in the International application lodged on 27 September 2004 in the name of the applicant and the disclosure in the International application is incorporated herein by cross- reference.
  • the cell further includes 6 anodes generally identified by the numeral 19 that extend into the bath 21.
  • the anodes 19 include graphite blocks 23 mounted to the ends of rods or other suitable support members 27.
  • the anode blocks 19 include lengthwise extending slots 91 (see Figure 2) that allow gas that evolves in the electrolyte bath 21 to escape from the cell.
  • the anodes 19 are arranged in pairs and the size of the anode blocks 23 is selected so that the anodes are positioned directly above substantially the whole of the upper surface of the cathode plate 25.
  • the anodes 19 are supported by a support structure so that the anode blocks 23 can be progressively lowered into the bath 21 as lower sections of the anode graphite are consumed by cell reactions at the anodes.
  • the top cover 9 of the cell includes openings 95 (see Figures 2 and 3) for the support members 27.
  • the anode support structure is described in detail in the above-mentioned International application lodged on 27 September 2004 in the name of the applicant.
  • the applicant has found that movement of the cathode plate 25 in a repeated sequence that comprises a short period of forward and backward, ie oscillating, motion and a short rest period can cause pellets on the upper surface of the cathode plate 25 to move over the upper surface in a series of short steps from the rearward end to the forward end of the cell .
  • the applicant has found that the above- described type of motion can cause pellets across the width of the cathode plate 25 to move at a constant rate so that the pellets have substantially the same residence time within the bath 21.
  • the cell further includes a power source 31 for applying a potential across the anode block 23 and the cathode plate 25 and an electrical circuit (that includes the above-described cathode support members 79) electrically interconnects the power source 31, the anodes 23, and the cathode.
  • the size and/or the positions of the cathode support members 79 is selected to supply a preselected current distribution to the cathode plate 25 to optimise electrochemical reduction of titania pellets on the cathode plate 25. Depending on the circumstances, there may be a range of current distributions required in the operation of the cell.
  • the operation of the cell generates carbon monoxide and carbon dioxide and potentially chlorine- containing gases at the anode blocks 23 and it is important to remove these gases from the cell.
  • the cell further includes an off-gas outlet 41 in the top cover 9 of the cell and a gas treatment unit 43 that treats the off-gases before releasing the treated gases to atmosphere.
  • the gas treatment includes removing carbon dioxide and any chlorine gases and may also include combustion of carbon monoxide to generate heat for the process .
  • titania pellets are supplied to the upper surface of the cathode plate 25 at the rearward end of the cell so as to form a mono-layer of pellets on the cathode plate 25 and the cathode is moved as described above and causes the pellets to step forward over the surface of the plate to the forward end of the cell and ultimately fall from the forward end of the cathode.
  • the pellets are progressively electrochemically reduced in the cell as the pellets are moved over the surface of the cathode plate 25.
  • the operating parameters of the cathode plate 25 are selected so that the pellets have sufficient residence time in the cell to achieve a required level of reduction of the titania pellets .
  • titania pellets typically require 4 hours residence time to be reduced to titanium with a concentration of 0.3 wt% oxygen at a cell operating voltage of 3 V.
  • the applicant has found that the above-described arrangement results in substantial reduction of titania pellets within a short distance from the forward end of the cell.
  • Titanium pellets together with electrolyte that is retained in the pores of the titanium pellets, are removed from the cell continuously or semi-continuously at the outlet 13.
  • the discharged material is transported via the auger 35 to a water spray chamber 37 and quenched to a temperature that is below the solidification temperature of the electrolyte, whereby the electrolyte blocks direct exposure of the metal and thereby restricts oxidation of the metal .
  • the discharged material is then washed to separate the retained electrolyte from the metal powder.
  • the metal powder is thereafter processed as required to produce end products.
  • Electrolyte in amounts greater than that required to compensate for net loss of electrolyte with discharged titanium pellets is added to the cell in the form of cast electrolyte blocks via inlet 59.
  • the purpose of the additional electrolyte is to purge the cell to maintain optimum operating conditions.
  • electrolyte is added to the cell via the inlet 59 at the rearward end of the cell, electrolyte flows over the weir 49 at the forward end of the cell and flows into the storage tank 57 and thereafter is treated by being washed with HCl to remove CaO and the treated electrolyte is returned to the cell as part of the electrolyte addition to the cell.
  • the anode blocks 23 are progressively consumed during operation of the cell by a reaction between carbon in the anode block 23 and 0 "" anions generated at the cathode plate 25, and the reaction occurs predominantly at the lower edges of the anode blocks 23.
  • the distances between the upper surface of the cathode plate 25 and the lower edges of the anode blocks 23 are maintained as required to maintain optimum operating conditions in the cell.
  • the distance between the upper surface of the cathode plate 25 and the lower edges of the anode block 23 is selected so that there is sufficient resistance heating generated to maintain the bath 21 at a required operating temperature.
  • the cell is operated at a potential that is above the decomposition potential of CaO in the electrolytic.
  • the potential may be as high as 4-5V.
  • operating above the decomposition potential of CaO facilitates deposition of Ca metal on the cathode plate 25 due to the presence of Ca ++ cations and migration of 0 " ⁇ anions to the anode block 23 as a consequence of the applied field and reaction of the 0 " anions with carbon of the anode block 23 to generate carbon monoxide and carbon dioxide and release electrons.
  • the deposition of Ca metal results in chemical reduction of titania via the mechanism described above and generates 0 " anions that migrate to the anode block 23 as a consequence of the applied field and further release of electrons.
  • the above-described cell and process are an efficient and an effective means of continuously and semi- continuously electrochemically reducing metal oxides in the form of powders and/or pellets to produce reduced material, having a low oxygen concentration
  • the electrolytic cell shown in the drawing is one example only of a large number of possible cell configurations that are within the scope of the present invention.

Landscapes

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

Abstract

L'invention concerne un procédé de réduction électrochimique d'un matière première d'oxyde métallique à l'état solide dans une cellule électrolytique. La cellule comprend un bain fondu d'électrolyte, une anode, une cathode, et un moyen pour appliquer un potentiel aux bornes de l'anode et de la cathode. Le procédé consiste à introduire dans le bain une quantité d'électrolyte supérieure à la quantité nécessaire pour remplacer l'électrolyte retiré afin de maintenir le niveau du bain à un niveau requis ou dans une gamme de niveaux requis.
PCT/AU2004/001410 2003-10-14 2004-10-14 Reduction electrochimique d'oxydes metalliques Ceased WO2005038092A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN2004800372653A CN1894440B (zh) 2003-10-14 2004-10-14 金属氧化物的电化学还原
EA200600774A EA009106B1 (ru) 2003-10-14 2004-10-14 Электрохимическое восстановление оксидов металлов
EP04789581A EP1680532A4 (fr) 2003-10-14 2004-10-14 Reduction electrochimique d'oxydes metalliques
US10/575,800 US20080047845A1 (en) 2003-10-14 2004-10-14 Electrochemical Reduction of Metal Oxides
JP2006534543A JP2007509232A (ja) 2003-10-14 2004-10-14 金属酸化物の電気化学的還元
AU2004281296A AU2004281296B2 (en) 2003-10-14 2004-10-14 Electrochemical reduction of metal oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2003905595A AU2003905595A0 (en) 2003-10-14 Electrochemical reduction of metal oxides
AU2003905595 2003-10-14

Publications (1)

Publication Number Publication Date
WO2005038092A1 true WO2005038092A1 (fr) 2005-04-28

Family

ID=34437866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2004/001410 Ceased WO2005038092A1 (fr) 2003-10-14 2004-10-14 Reduction electrochimique d'oxydes metalliques

Country Status (7)

Country Link
US (1) US20080047845A1 (fr)
EP (1) EP1680532A4 (fr)
JP (1) JP2007509232A (fr)
CN (1) CN1894440B (fr)
EA (1) EA009106B1 (fr)
WO (1) WO2005038092A1 (fr)
ZA (1) ZA200603786B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT509526B1 (de) * 2010-02-26 2012-01-15 Univ Wien Tech Verfahren und vorrichtung zur herstellung von metallen aus ihren oxiden
WO2012104640A2 (fr) 2011-02-04 2012-08-09 Metalysis Limited Procédé, appareil et produit d'électrolyse
WO2013050772A3 (fr) * 2011-10-04 2013-05-30 Metalysis Limited Production électrolytique de poudre
US9725815B2 (en) 2010-11-18 2017-08-08 Metalysis Limited Electrolysis apparatus
US11498128B2 (en) 2016-05-24 2022-11-15 Metalysis Limited Manufacturing apparatus comprising collocated reduction apparatus, processor and additive-manufacturing apparatus

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
AU2003903150A0 (en) * 2003-06-20 2003-07-03 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
EP1682696A4 (fr) * 2003-09-26 2007-06-20 Bhp Billiton Innovation Pty Reduction electrochimique d'oxydes metalliques
CN1961098A (zh) * 2004-03-22 2007-05-09 Bhp比利顿创新公司 金属氧化物的电化学还原
WO2005123986A1 (fr) * 2004-06-22 2005-12-29 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
WO2006010229A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
BRPI0513992A (pt) * 2004-07-30 2008-05-20 Bhp Billiton Innovation Pty processo para minimização da re-oxidação de material reduzido e processo para redução eletroquìmica de um material de alimentação de óxido metálico
GB201223375D0 (en) * 2012-12-24 2013-02-06 Metalysis Ltd Method and apparatus for producing metal by electrolytic reduction
CN109487302B (zh) * 2017-10-18 2021-05-28 虔东稀土集团股份有限公司 一种生产稀土金属及合金的方法
CN109487301B (zh) * 2017-10-18 2021-07-09 虔东稀土集团股份有限公司 一种稀土金属或合金的工业化生产方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045308A (en) * 1976-11-04 1977-08-30 Aluminum Company Of America Bath level set point control in an electrolytic cell and method of operating same
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
GB2362164A (en) * 2000-05-08 2001-11-14 Secr Defence Electrolytic reduction of sintered mass of metal oxide
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
US20030173228A1 (en) * 2002-03-13 2003-09-18 Lazar Strezov Reduction of metal oxides in an electrolytic cell
WO2004053201A1 (fr) * 2002-12-12 2004-06-24 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951021A (en) * 1952-03-28 1960-08-30 Nat Res Corp Electrolytic production of titanium
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
DE60130322T2 (de) * 2000-02-22 2008-06-12 Metalysis Ltd., Wath-Upon-Dearne Verfahren zur herstellung von metallschaum durch elektrolytische reduktion poröser oxidischer vorformen
AUPR602901A0 (en) * 2001-06-29 2001-07-26 Bhp Innovation Pty Ltd Removal of oxygen from metals oxides and solid metal solutions
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
GB0222382D0 (en) * 2002-09-27 2002-11-06 Qinetiq Ltd Improved process for removing oxygen from metal oxides by electrolysis in a fused salt
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
AU2003903150A0 (en) * 2003-06-20 2003-07-03 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
EP1682696A4 (fr) * 2003-09-26 2007-06-20 Bhp Billiton Innovation Pty Reduction electrochimique d'oxydes metalliques
CN1961098A (zh) * 2004-03-22 2007-05-09 Bhp比利顿创新公司 金属氧化物的电化学还原
WO2005123986A1 (fr) * 2004-06-22 2005-12-29 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
WO2006010229A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
BRPI0513992A (pt) * 2004-07-30 2008-05-20 Bhp Billiton Innovation Pty processo para minimização da re-oxidação de material reduzido e processo para redução eletroquìmica de um material de alimentação de óxido metálico

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045308A (en) * 1976-11-04 1977-08-30 Aluminum Company Of America Bath level set point control in an electrolytic cell and method of operating same
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
GB2362164A (en) * 2000-05-08 2001-11-14 Secr Defence Electrolytic reduction of sintered mass of metal oxide
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
US20030173228A1 (en) * 2002-03-13 2003-09-18 Lazar Strezov Reduction of metal oxides in an electrolytic cell
WO2004053201A1 (fr) * 2002-12-12 2004-06-24 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1680532A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT509526B1 (de) * 2010-02-26 2012-01-15 Univ Wien Tech Verfahren und vorrichtung zur herstellung von metallen aus ihren oxiden
US9725815B2 (en) 2010-11-18 2017-08-08 Metalysis Limited Electrolysis apparatus
WO2012104640A2 (fr) 2011-02-04 2012-08-09 Metalysis Limited Procédé, appareil et produit d'électrolyse
WO2013050772A3 (fr) * 2011-10-04 2013-05-30 Metalysis Limited Production électrolytique de poudre
GB2514679A (en) * 2011-10-04 2014-12-03 Metalysis Ltd Electrolytic production of powder
US9611558B2 (en) 2011-10-04 2017-04-04 Metalysis Limited Electrolytic production of powder
EA030643B1 (ru) * 2011-10-04 2018-09-28 Металисиз Лимитед Электролитическое получение порошков
US11498128B2 (en) 2016-05-24 2022-11-15 Metalysis Limited Manufacturing apparatus comprising collocated reduction apparatus, processor and additive-manufacturing apparatus

Also Published As

Publication number Publication date
EA200600774A1 (ru) 2006-10-27
US20080047845A1 (en) 2008-02-28
EP1680532A4 (fr) 2007-06-20
CN1894440B (zh) 2010-06-16
CN1894440A (zh) 2007-01-10
JP2007509232A (ja) 2007-04-12
ZA200603786B (en) 2007-09-26
EP1680532A1 (fr) 2006-07-19
EA009106B1 (ru) 2007-10-26

Similar Documents

Publication Publication Date Title
US7758740B2 (en) Electrochemical reduction of metal oxides
US20080047845A1 (en) Electrochemical Reduction of Metal Oxides
US20070193877A1 (en) Electrochemical reduction of metal oxides
EP1581672B1 (fr) Reduction electrochimique d'oxydes metalliques
US20070131560A1 (en) Electrochemical reduction of metal oxides
AU2004281296B2 (en) Electrochemical reduction of metal oxides
CN100582313C (zh) 金属氧化物的电化学还原
US6866766B2 (en) Methods and apparatus for reducing sulfur impurities and improving current efficiencies of inert anode aluminum production cells
EP1534879B1 (fr) Procedes et dispositif permettant de reduire les impuretes a base de soufre et d'ameliorer les rendements en courant de cellules de production d'aluminium a anode permanente
AU2004276372A1 (en) Electrochemical reduction of metal oxides
AU2003286000B2 (en) Electrochemical reduction of metal oxides
RU2299931C2 (ru) Способ и устройство для снижения содержания сернистых примесей и улучшения кпд тока электролизера с инертным анодом для производства алюминия
AU2005224292A1 (en) Electrochemical reduction of metal oxides

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480037265.3

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW 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 NA 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: A1

Designated state(s): GM KE LS MW MZ NA 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 PL 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
WWE Wipo information: entry into national phase

Ref document number: 2006534543

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2004281296

Country of ref document: AU

Ref document number: 200603786

Country of ref document: ZA

Ref document number: 2004789581

Country of ref document: EP

Ref document number: 2691/DELNP/2006

Country of ref document: IN

Ref document number: 200600774

Country of ref document: EA

ENP Entry into the national phase

Ref document number: 2004281296

Country of ref document: AU

Date of ref document: 20041014

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 2004281296

Country of ref document: AU

WWP Wipo information: published in national office

Ref document number: 2004789581

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10575800

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 10575800

Country of ref document: US