EP1920087B1 - Elektrochemische reduktion von titanoxid - Google Patents

Elektrochemische reduktion von titanoxid Download PDF

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Publication number
EP1920087B1
EP1920087B1 EP06760944.6A EP06760944A EP1920087B1 EP 1920087 B1 EP1920087 B1 EP 1920087B1 EP 06760944 A EP06760944 A EP 06760944A EP 1920087 B1 EP1920087 B1 EP 1920087B1
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EP
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Prior art keywords
electrolyte
cao
concentration
titanium oxide
process defined
Prior art date
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Application number
EP06760944.6A
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English (en)
French (fr)
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EP1920087A4 (de
EP1920087A1 (de
Inventor
Ivan Ratchev
Rene Ignacio Olivares
Sergey Alexander Bliznyukov
Kannapar Mukunthan
Gregory David Rigby
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Metalysis Ltd
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Metalysis Ltd
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Priority claimed from AU2005904121A external-priority patent/AU2005904121A0/en
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    • 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
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/14—Refining in the solid state
    • 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 application relates to electrochemical reduction of metal oxides.
  • the present application relates to electrochemical reduction of metal oxides in the form of powders and/or pellets in an electrolytic cell containing a molten electrolyte to produce reduced material, namely metal having a low oxygen concentration, typically no more than 0.2% by weight.
  • the present invention is concerned with controlling electrochemical reduction of titanium oxide.
  • the present invention applies to situations in which the process is carried out on a batch basis, a continuous basis, and a semi-continuous basis.
  • the present invention was made during the course of a research project on electrochemical reduction of metal oxides carried out by the applicant.
  • the research project focussed on the reduction of titania (TiO 2 ).
  • the CaCl 2 -based electrolyte used in the experiments was a commercially available source of CaCl 2 , which 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 applicant operated the laboratory electrolytic cells under a wide range of different operating parameters and conditions.
  • the applicant operated the laboratory electrolytic cells on a batch basis with titania in the form of pellets and larger solid blocks in the early part of the laboratory work and titania powder in the later part of the work.
  • the applicant also operated the laboratory electrolytic cells on a batch basis with other metal oxides.
  • Recent pilot plant work carried out by the applicant was carried out on a pilot plant electrolytic cell that was set up to operate initially on a continuous basis and subsequently on a batch basis.
  • the concentration of CaO in the electrolyte should be controlled by maintaining the concentration above a minimum CaO concentration and below a maximum CaO concentration in order to optimise operation of the process.
  • CaO and titania react spontaneously and form perovskite (CaTiO 3 ).
  • the amount of CaO may decrease substantially as a consequence of the perovskite reaction.
  • An important physical characteristic is the surface area of titania in contact with electrolyte, particularly when this characteristic is considered in the context of a given mass of the electrolyte and a given mass of the titania.
  • the titania surface area for a given mass of titania is dependent on physical characteristics of the titania, such as powder/pellet shape and porosity.
  • the applicant also believes that the above-mentioned significance of the CaO concentration in a CaCl 2 -based electrolyte also applies to other alkali earth metal oxides, alkali metal oxides, and yttrium oxides. Specifically, the applicant believes that where one or more than one of the metal oxides is present in a CaCl 2 -based electrolyte, controlling the concentrations of the metal oxides within ranges is a means of optimising operation of an electrochemical reduction process for titanium oxide in a solid state in the electrolyte.
  • the metal oxides may be present as an impurity or impurites in the feed material used to produce the CaCl 2 -based electrolyte and/or by way of specific addition to the electrolyte.
  • the invention may therefore advantageously provide a process for electrochemically reducing a titanium oxide in a solid state in an electrolytic cell that includes an anode, a cathode, a molten CaCl 2 -based electrolyte containing CaO, and titanium oxide feed material in contact with the molten electrolyte, which electrochemical process includes applying an electrical potential across the anode and the cathode and electrochemically reducing titanium oxide feed material in contact with the molten electrolyte and producing reduced material, and which process is characterised by controlling the process by controlling the concentration of CaO in the electrolyte.
  • the process includes controlling the concentration of CaO in the electrolyte by maintaining the concentration of CaO in the electrolyte between lower and upper concentration limits.
  • the maximum CaO concentration in the electrolyte is 0.5 wt.%.
  • the maximum CaO concentration in the electrolyte is 0.3 wt.%.
  • the minimum CaO concentration in the electrolyte is 0.005 wt.%.
  • the minimum CaO concentration in the electrolyte is 0.05 wt.%.
  • the minimum CaO concentration in the electrolyte is 0.1 wt.%.
  • the CaO concentration in the electrolyte is in the range of 0.1-0.3 wt.%.
  • the CaO concentration in the electrolyte is in the range of 0.15-0.25 wt.%.
  • the process includes controlling the concentration of CaO in the electrolyte by reference to the surface area of contact of the titanium oxide with the electrolyte.
  • the process includes controlling the concentration of CaO in the electrolyte by reference to the surface area of contact of the titanium oxide with the electrolyte when considered in the context of the mass of the electrolyte and the mass of the titanium oxide.
  • the practical option for controlling the CaO concentration in the electrolyte is to control the mass ratio of the electrolyte and the titanium oxide in the cell.
  • the process includes controlling the mass ratio of the electrolyte and titanium oxide in the cell to be at least 10:1 in situations where the initial CaO concentration is below 0.3, more preferably below 0.2 wt.% in the electrolyte and the titanium oxide is in a form of pellets and/or powders having a specific surface area of 0.1 to 100 m 2 /g of titanium oxide.
  • the process may include controlling the CaO concentration in the electrolyte by adding CaO to the electrolyte during the course of the process.
  • the process may include controlling the CaO concentration in the electrolyte by selecting an initial CaO concentration that is sufficiently high.
  • the electrochemical process may be carried out on any one of a batch basis, a semi-continuous basis, or a continuous basis.
  • the titanium oxide feed material is in a powder and/or a pellet form.
  • the titanium oxide feed material is titania.
  • the electrochemical reduction process includes applying a potential across the anode and the cathode that is above the decomposition potential of CaO and below the decomposition of CaCl 2 .
  • the electrochemical reduction process may be carried out as a single stage or a multi-stage process.
  • a process for electrochemically reducing a titanium oxide in a solid state in an electrolytic cell that includes (a) an anode, (b) a cathode, (c) a molten CaCl 2 -based electrolyte containing any one or more than one metal oxide selected from the group including alkali earth metal oxides, alkali metal oxides, and yttrium oxides, and (d) a titanium oxide feed material in contact with the molten electrolyte, which electrochemical process includes applying an electrical potential across the anode and the cathode and electrochemically reducing titanium oxide feed material in contact with the molten electrolyte and producing reduced material, and which process is characterised by controlling the process by controlling the concentration of the selected metal oxide or metal oxides in the electrolyte.
  • the selected metal oxide is CaO.
  • the cell comprised a reaction vessel, a furnace, a crucible assembly, an electrode assembly, and a power supply.
  • the reaction vessel was manufactured from a high temperature stainless steel and had an internal diameter of 110mm and height of 430mm, and a water-cooled flange.
  • the vessel was contained within a resistance-heated furnace capable of reaching 1400°K.
  • a positioning pedestal within the vessel allowed for the crucible containing the molten salt to be properly fixed within the vessel.
  • a water-cooled lid was a critical feature of the reaction vessel and had provision for a viewing port which facilitated accurate positioning of the electrodes and the thermocouple within the molten salt bath.
  • the viewing port also allowed the surface of the molten salt to be monitored during the reaction.
  • Carbon monoxide and carbon dioxide are the main by-products of the electrochemical reduction process.
  • special care was taken in controlling the gas atmosphere.
  • a measured flow of high purity argon gas was passed through a furnace containing copper turnings at 873°K, then through a furnace containing magnesium flakes at 673°K before entering the vessel. After passing through the vessel, the gas stream was stripped of any chlorine-containing species and moisture and continuously analysed for CO and CO 2 .
  • a solid electrolyte based oxygen analyser monitored the partial pressure of O 2 in the off-gas immediately after the furnace.
  • Furnace pressure, applied voltage, reference voltage, cell current, electrolyte temperature, oxygen, carbon monoxide and carbon dioxide content of the off-gas were monitored and logged for subsequent analysis as a function of time.
  • the chemistry of the molten electrolyte was found to have a significant impact on the process operation. Consequently, the applicant ensured that the composition of the electrolyte at the start of a run was well controlled.
  • the electrolyte was prepared from analytical grade dihydrate, CaCl 2 .H 2 O obtained from APS Chemicals. Typically, 680g of molten salt were used in the experiments. Prior to melting, a dehydration step was carried out as follows.
  • the CaCl 2 .H 2 O was slowly heated under vacuum to 525K and kept at this temperature for at least 12 hours during which time the weight loss due to water removal was monitored. Once there was no more weight loss, the anhydrous salt was transferred from the vacuum oven into a platinum crucible and placed in a melting furnace. The salt was melted at 1275°K and kept at this temperature for 30 minutes to allow further removal of any residual water. The molten salt was then cast into a preheated steel mould, removed once solid, and transferred while hot to a drying oven held at 400K.
  • titania pellets were prepared from 99.5% minimum purity rutile (Alfa Aesar) although occasionally other titania sources were used.
  • the titania pellets were prepared so that control of the total porosity and pore size was exercised by sintering at a predetermined temperature.
  • the concentration of CaO in the electrolyte was systematically increased up to 2.5 wt.%.
  • Figure 1 is a plot of cell current (in Amps) versus time (in seconds) for each of the above-mentioned experiments. The Figure shows that there was a decrease in cell current over time with each of the CaO concentrations in the electrolyte. The Figure also shows that the cell passed more current with increased concentrations of CaO in the electrolyte. This finding, of itself does not indicate that there was increased molection of titania at increased CaO concentrations.
  • Figure 2 is a plot of the concentration of oxygen in titanium in the reduced pellets versus the CaO concentration in the electrolyte at the end of the experimental runs of 4 hours.
  • the Figure shows that reduction of titania to titanium was inhibited as the concentration of CaO in the electrolyte increased.
  • the Figure shows that there were higher concentrations of oxygen in the titanium produced in the cell as the CaO concentrations in the electrolyte increased.
  • the Figure shows that the rate of reduction decreased as the concentration of CaO in the electrolyte increased.
  • Figures 1 and 2 indicate that significantly higher current consumption was required to achieve lower levels of reduction of titania at increased CaO concentrations.
  • operating at CaO concentrations of 0.5 wt.% or less produced high levels of reduction - to less than about 0.5 wt.% oxygen - with reasonable current consumption
  • Figure 3 is a plot of the amount of carbon removed from the anode in grams and the overall current efficiency versus the CaO concentration in the electrolyte at the end of the experimental runs of 4 hours.
  • the Figure shows that the amounts of electricity and carbon consumed in the process were proportionally higher as the concentration of CaO in the electrolyte increased.
  • the Figure shows that the current efficiency decreased as the concentration of CaO in the electrolyte increased.

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  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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Claims (15)

  1. Prozess zum elektrochemischen Reduzieren eines Titanoxids in einem festen Zustand in einer elektrolytischen Zelle, die eine Anode, eine Kathode, einen geschmolzenen Elektrolyt auf CaCl2-Basis, der CaO enthält, und ein Titanoxid-Ausgangsmaterial, das mit dem geschmolzenen Elektrolyt in Kontakt ist, beinhaltet, wobei der elektrochemische Prozess das Anlegen eines elektrischen Potentials an die Anode und die Kathode und das elektrochemische Reduzieren von mit dem geschmolzenen Elektrolyt in Kontakt befindlichem Titanoxid-Ausgangsmaterial und Erzeugen von reduziertem Material beinhaltet und wobei der Prozess dadurch gekennzeichnet ist, dass der Prozess durch Regeln der Konzentration von CaO in dem Elektrolyt durch Regeln des Massenverhältnisses des Elektrolyts und Titanoxids in der Zelle, so dass es wenigstens 10:1 beträgt, die anfängliche CaO-Konzentration unter 0,3 Gew.-% in dem Elektrolyt ist und das Titanoxid in einer Form von Pellets und/oder Pulvern mit einer spezifischen Oberfläche von 0,1 bis 100 m2/g Titanoxid ist, gesteuert wird.
  2. Prozess nach Anspruch 1, der das Regeln der Konzentration von CaO in dem Elektrolyt durch Halten der Konzentration von CaO in dem Elektrolyt zwischen einer unteren und einer oberen Konzentrationsgrenze beinhaltet.
  3. Prozess nach Anspruch 2, der das Halten der Konzentration von CaO in dem Elektrolyt auf oder unter einer maximalen CaO-Konzentration von 0,5 Gew.-% beinhaltet.
  4. Prozess nach Anspruch 2, der das Halten der Konzentration von CaO in dem Elektrolyt auf oder unter einer maximalen CaO-Konzentration von 0,3 Gew.-% beinhaltet.
  5. Prozess nach Anspruch 2, der das Halten der Konzentration von CaO in dem Elektrolyt auf oder über einer Mindest-CaO-Konzentration von 0,005 Gew.-% beinhaltet.
  6. Prozess nach einem der Ansprüche 2 bis 4, der das Halten der Konzentration von CaO in dem Elektrolyt auf oder über einer Mindest-CaO-Konzentration von 0,05 Gew.-% beinhaltet.
  7. Prozess nach einem der Ansprüche 2 bis 4, der das Halten der Konzentration von CaO in dem Elektrolyt auf oder über einer Mindest-CaO-Konzentration von 0,1 Gew.-% beinhaltet.
  8. Prozess nach Anspruch 2, der das Halten der Konzentration von CaO in dem Elektrolyt in dem Bereich von 0,1 bis 0,3 Gew.-% beinhaltet.
  9. Prozess nach Anspruch 2, der das Halten der Konzentration von CaO in dem Elektrolyt in dem Bereich von 0,15 bis 0,25 Gew.-% beinhaltet.
  10. Prozess nach einem der vorhergehenden Ansprüche, der das Regeln der Konzentration von CaO in dem Elektrolyt durch Bezug auf den Flächeninhalt der Kontaktfläche des Titanoxids mit dem Elektrolyt beinhaltet.
  11. Prozess nach einem der vorhergehenden Ansprüche, der das Regeln der Konzentration von CaO in dem Elektrolyt durch Bezug auf den Flächeninhalt der Kontaktfläche des Titanoxids mit dem Elektrolyt beinhaltet, wenn im Zusammenhang mit der Masse des Elektrolyts und der Masse des Titanoxids betrachtet.
  12. Prozess nach einem der vorhergehenden Ansprüche, der das Regeln der CaO-Konzentration in dem Elektrolyt durch Regeln des Massenverhältnisses des Elektrolyts und des Titanoxids in der Zelle beinhaltet.
  13. Prozess nach einem der vorhergehenden Ansprüche, bei dem die anfängliche CaO-Konzentration in dem Elektrolyt unter 0,2 Gew.-% ist.
  14. Prozess nach einem der vorhergehenden Ansprüche, der das Regeln der CaO-Konzentration in dem Elektrolyt durch Zugeben von CaO zu dem Elektrolyt während des Prozessverlaufs beinhaltet.
  15. Prozess nach einem der vorhergehenden Ansprüche, der das Regeln der CaO-Konzentration in dem Elektrolyt durch Auswählen einer anfänglichen CaO-Konzentration, die hoch genug ist, beinhaltet.
EP06760944.6A 2005-08-01 2006-08-01 Elektrochemische reduktion von titanoxid Active EP1920087B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2005904121A AU2005904121A0 (en) 2005-08-01 Electrochemical reduction of metal oxides
PCT/AU2006/001088 WO2007014422A1 (en) 2005-08-01 2006-08-01 Electrochemical reduction of metal oxides

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EP1920087A1 EP1920087A1 (de) 2008-05-14
EP1920087A4 EP1920087A4 (de) 2011-07-27
EP1920087B1 true EP1920087B1 (de) 2017-03-22

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EP (1) EP1920087B1 (de)
EA (1) EA014138B1 (de)
WO (1) WO2007014422A1 (de)

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US8129414B2 (en) 2006-06-19 2012-03-06 Adeboye Adejare Non-competitive NMDA receptor antagonists
GB201208698D0 (en) 2012-05-16 2012-06-27 Metalysis Ltd Electrolytic method,apparatus and product
CN106947874B (zh) * 2017-04-18 2018-11-27 北京科技大学 一种两步法制备高纯钛的方法

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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
AUPS107102A0 (en) * 2002-03-13 2002-04-11 Bhp Billiton Innovation Pty Ltd Electrolytic reduction of metal oxides
MXPA04008887A (es) * 2002-03-13 2004-11-26 Bhp Billiton Innovation Pty Reduccion de oxidos de metal en una celda electrolitica.
AUPS117002A0 (en) * 2002-03-13 2002-04-18 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
AU2002952083A0 (en) * 2002-10-16 2002-10-31 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
JP2004360025A (ja) * 2003-06-05 2004-12-24 Sumitomo Titanium Corp 直接電解法による金属チタンの製造方法

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Publication number Publication date
EA200800526A1 (ru) 2008-08-29
EP1920087A4 (de) 2011-07-27
EA014138B1 (ru) 2010-10-29
WO2007014422A1 (en) 2007-02-08
EP1920087A1 (de) 2008-05-14

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