WO2006010229A1 - Reduction electrochimique d'oxydes metalliques - Google Patents

Reduction electrochimique d'oxydes metalliques Download PDF

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Publication number
WO2006010229A1
WO2006010229A1 PCT/AU2005/001135 AU2005001135W WO2006010229A1 WO 2006010229 A1 WO2006010229 A1 WO 2006010229A1 AU 2005001135 W AU2005001135 W AU 2005001135W WO 2006010229 A1 WO2006010229 A1 WO 2006010229A1
Authority
WO
WIPO (PCT)
Prior art keywords
reduced material
electrolyte
process defined
morphology
reduced
Prior art date
Application number
PCT/AU2005/001135
Other languages
English (en)
Inventor
Kannapar Mukunthan
Ivan Ratchev
Andrew Arthur Shook
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 AU2004904304A external-priority patent/AU2004904304A0/en
Application filed by Bhp Billiton Innovation Pty Ltd filed Critical Bhp Billiton Innovation Pty Ltd
Priority to AU2005266777A priority Critical patent/AU2005266777A1/en
Publication of WO2006010229A1 publication Critical patent/WO2006010229A1/fr
Priority to US11/668,509 priority patent/US20080149495A1/en

Links

Classifications

    • 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
    • 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
    • C22B34/1295—Refining, melting, remelting, working up 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
    • 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

Definitions

  • the present invention relates to electrochemical reduction of metal oxides.
  • the present invention relates particularly, although by no means exclusively, to electrochemical reduction of metal oxide feed material in the form of powders and/or pellets in an electrolytic cell 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 minimising the concentration of chlorine in reduced material produced by electrochemical reduction of metal oxide feed material in an electrolytic cell that operates with a chlorine-containing molten electrolyte, such as a CaCl 2 -based electrolyte.
  • the present invention was made during the course of an on-going research project on electrochemical reduction of metal oxide feed material being carried out by the applicant.
  • the research project has 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 potentials above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the applicant operated the cells under a wide range of different operating set-ups and conditions.
  • the applicant has found in a series of experiments that the conditions under which metal oxide feed material is electrochemically reduced in electrolytic cells has a significant impact on the resultant concentration of chlorine in reduced material produced in the process.
  • the conditions include temperature of molten electrolyte and reduction time.
  • the reduction conditions in electrolytic cells can have a significant impact on the morphology of the reduced material and that by appropriate selection of the conditions it is possible to produce reduced material that has a morphology that is more susceptible to subsequent washing than would otherwise be the case, with a result that the resultant washed reduced material has a lower concentration of chlorine.
  • the appropriate selection of reduction conditions in electrolytic cells include conditions that result in sintering of reduced material such that there is phase separation within the morphology of the reduced material, with one phase comprising regions of reduced material and the other phase comprising regions of retained electrolyte, and with the electrolyte-containing regions being interconnected into a continuous network so that the electrolyte can be washed more readily from the reduced material.
  • controlled sintering of reduced material in or external to an electrolytic cell may be an effective option for minimising the chlorine concentration in reduced material.
  • a process for selectively forming a morphology of reduced material formed by a process of electrochemically reducing a metal oxide feed material in a solid state in an electrolytic cell containing molten chlorine-containing electrolyte in the cell, which process includes sintering the reduced material and forming a morphology that is susceptible to subsequent washing of retained electrolyte in the reduced material.
  • the step of sintering the reduced material may be carried out in the electrolytic cell.
  • the step of sintering the reduced material may be carried out in a separate vessel that is supplied with reduced material from the electrolytic cell.
  • the process further includes removing reduced material from the cell or the separate vessel and thereafter washing the reduced material.
  • the process may be carried out on a batch basis, a semi-continuous basis, and a continuous basis.
  • the process may be carried out as a single stage or a multi-stage process.
  • the metal oxide feed material is in a powder and/or a pellet form.
  • the metal oxide feed material is a titanium oxide.
  • titanium oxide is titania.
  • the electrolyte is a CaCl 2 -based electrolyte containing CaO.
  • the electrochemical reduction process includes applying an electrical potential across the anode and the cathode that is above the decomposition potential of CaO and below the decomposition of CaCl 2 .
  • a process for electrochemically reducing a metal oxide feed material in a solid state in an electrolytic cell containing molten chlorine-containing electrolyte in the cell which process includes sintering the electrochemically reduced material and forming a morphology that is susceptible to subsequent washing of retained electrolyte in the reduced material.
  • one morphology that is susceptible to subsequent washing of the reduced material is a structure that includes a continuous network of interconnected regions of chlorine-containing electrolyte.
  • the structure is essentially a two phase structure with one phase comprising grains of reduced material having minimal amounts of electrolyte within the grains and the other phase comprising a continuous network of interconnected regions containing electrolyte.
  • the experimental work carried out by the applicant to date has focussed on evaluating the impact of the temperature of molten electrolyte and the reduction, ie residence time, of reduced material in an electrolytic cell on the subsequent washability of the resultant reduced material.
  • the experimental work indicated that the concentration of chlorine in washed electrochemically-reduced material in the form of titanium metal decreased as the temperature of the molten electrolyte in the electrolytic cell increased and as the residence time of the reduced material in the cell increased. Thus, the experimental work indicated that better washability was achieved with reduced material produced at high temperatures and longer reduction times.
  • the experimental work was carried out on metal oxide feed material in the form of titania that was supplied to the laboratory-scale electrolytic cell as a product with a relatively fine, uniform porous morphology throughout the material (typically 50% pores) .
  • Pellets of titania were electrochemically reduced in a laboratory-scale electrolytic cell under different molten electrolyte temperatures and reduction times.
  • the titania pellets were manufactured from smaller particles of titania. Typically the titania particles for pellet manufacture ranged from nanometer size up to 15 microns.
  • the pellets had an open connected pore structure with a porosity in the range of 35-60% by volume. Preferably at least 25 vol.% of the pores had a size of 0.005-10 microns measured by Mercury Intrusion porosimetry.
  • Pellets were shaped, for example by being slip cast in moulds.
  • One example of a shape was a disc with a cylindrical side wall and flat top and bottom walls, and with the diameter of the cylinder being considerably greater that the thickness of the disc between the top and bottom walls.
  • a disc is a disc that is 20 mm in diameter and 2 mm thick. In all cases, a maximum dimension of 3.5 mm applied to the minimum dimensions of pellets (and powders) tested.
  • the cell contained a commercially available source of CaCl 2 that decomposed on heating and produced a very small amount of CaO.
  • the cell was operated at an applied potential of 3 V. This is a potential above the decomposition potential of CaO under the cell operating conditions.
  • pellets of reduced titania were removed from the cell after the prescribed reduction times and were washed in pellet form or in a broken up form in deionised water near boiling point for 2-4 hours.
  • micrographs of Figures 1 to 3 are cross- sections of the reduced pellets produced with the cell operating with electrolyte temperatures of 1000 0 C, 95O 0 C, and 900 0 C, respectively.
  • Each of the micrographs show a morphology that comprises an essentially two phase structure with one phase comprising grains of reduced titania (the lighter coloured parts of the micrograph) and the other phase comprising regions containing electrolyte (the darker coloured parts of the micrograph) .
  • micrographs indicate the significantly different morphologies of the reduced pellets produced at these electrolyte temperatures.
  • the micrographs indicate that the two phase structure became increasingly pronounced as the electrolyte temperature increased.
  • the micrographs indicate that as the electrolyte temperature increased, the grains of reduced titania had smaller amounts of electrolyte within the grains and the electrolyte-containing phase increasingly formed as a continuous network of relatively large interconnected pores.
  • the molten electrolyte temperature was set at 1000 0 C.
  • a first experimental run a first set of pellets was removed from the cell after 6 hours.
  • a second set of pellets was removed after 8 hours.
  • a third experimental run a third set of pellets was removed after 12 hours.
  • the reduced pellets were washed in pellet form or in a broken up form in deionised water near boiling point for 2-4 hours.

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

Abstract

La présente invention concerne un procédé permettant de réaliser sélectivement une forme d'un matériau réduit. Le matériau réduit, tel que du titane, est formé par un procédé qui consiste à réduire par électrochimie un matériau de départ à base d'oxyde métallique, tel que de l'oxyde de titane, à l'état solide, dans une cellule électrolytique comprenant un électrolyte fondu à teneur en chlore dans la cellule. Le procédé susmentionné consiste à fritter le matériau réduit puis à façonner une forme pouvant subir un lavage ultérieur de l'électrolyte retenu dans le matériau réduit.
PCT/AU2005/001135 2004-07-30 2005-08-01 Reduction electrochimique d'oxydes metalliques WO2006010229A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2005266777A AU2005266777A1 (en) 2004-07-30 2005-08-01 Electrochemical reduction of metal oxides
US11/668,509 US20080149495A1 (en) 2004-07-30 2007-01-30 Electrochemical Reduction of Metal Oxides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2004904304 2004-07-30
AU2004904304A AU2004904304A0 (en) 2004-07-30 Electrochemical reduction of metal oxides

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/668,509 Continuation-In-Part US20080149495A1 (en) 2004-07-30 2007-01-30 Electrochemical Reduction of Metal Oxides

Publications (1)

Publication Number Publication Date
WO2006010229A1 true WO2006010229A1 (fr) 2006-02-02

Family

ID=35785855

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2005/001135 WO2006010229A1 (fr) 2004-07-30 2005-08-01 Reduction electrochimique d'oxydes metalliques

Country Status (3)

Country Link
US (1) US20080149495A1 (fr)
CN (1) CN101068955A (fr)
WO (1) WO2006010229A1 (fr)

Families Citing this family (12)

* 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
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
US9816192B2 (en) 2011-12-22 2017-11-14 Universal Technical Resource Services, Inc. System and method for extraction and refining of titanium
DE102014111781B4 (de) * 2013-08-19 2022-08-11 Korea Atomic Energy Research Institute Verfahren zur elektrochemischen Herstellung einer Silizium-Schicht
BR112019005038B1 (pt) 2016-09-14 2022-12-20 Universal Achemetal Titanium, Llc Um método para produzir liga de titânio-alumínio-vanádio
JP7139337B2 (ja) 2017-01-13 2022-09-20 ユニバーサル アケメタル タイタニウム リミテッド ライアビリティ カンパニー チタン－アルミニウム基合金のためのチタン母合金

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2004029309A1 (fr) * 2002-09-27 2004-04-08 Qinetiq Limited Processus ameliore pour eliminer l'oxygene des oxydes metalliques par electrolyse dans un sel fondu
WO2004113593A1 (fr) * 2003-06-20 2004-12-29 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques

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US2880156A (en) * 1951-06-23 1959-03-31 Nat Res Corp Production of metals
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
GB0027929D0 (en) * 2000-11-15 2001-01-03 Univ Cambridge Tech Metal and alloy powders
AUPR712101A0 (en) * 2001-08-16 2001-09-06 Bhp Innovation Pty Ltd Process for manufacture of titanium products
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
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
WO2004053201A1 (fr) * 2002-12-12 2004-06-24 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
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
AU2005256146B2 (en) * 2004-06-28 2010-11-25 Metalysis Limited Production of titanium
CA2575580A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2004029309A1 (fr) * 2002-09-27 2004-04-08 Qinetiq Limited Processus ameliore pour eliminer l'oxygene des oxydes metalliques par electrolyse dans un sel fondu
WO2004113593A1 (fr) * 2003-06-20 2004-12-29 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques

Also Published As

Publication number Publication date
US20080149495A1 (en) 2008-06-26
CN101068955A (zh) 2007-11-07

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