EP2770086A2 - Reduktion von Metalloxiden in einer Elektrolysezelle - Google Patents

Reduktion von Metalloxiden in einer Elektrolysezelle Download PDF

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Publication number
EP2770086A2
EP2770086A2 EP20140163470 EP14163470A EP2770086A2 EP 2770086 A2 EP2770086 A2 EP 2770086A2 EP 20140163470 EP20140163470 EP 20140163470 EP 14163470 A EP14163470 A EP 14163470A EP 2770086 A2 EP2770086 A2 EP 2770086A2
Authority
EP
European Patent Office
Prior art keywords
metal
electrolyte
cathode
metal oxide
potential
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.)
Withdrawn
Application number
EP20140163470
Other languages
English (en)
French (fr)
Other versions
EP2770086A3 (de
Inventor
Les Stretzov
Ivan Ratchev
Steve Osborn
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.)
Metalysis Ltd
Original Assignee
Metalysis 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 AUPS1071A external-priority patent/AUPS107102A0/en
Priority claimed from AUPS3049A external-priority patent/AUPS304902A0/en
Application filed by Metalysis Ltd filed Critical Metalysis Ltd
Publication of EP2770086A2 publication Critical patent/EP2770086A2/de
Publication of EP2770086A3 publication Critical patent/EP2770086A3/de
Withdrawn legal-status Critical Current

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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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/18—Electrolytes

Definitions

  • the present invention relates to reduction of metal oxides in a solid state in an electrolytic cell.
  • the present invention was made during the course of an on-going research project on solid state reduction of titania (TiO 2 ) carried out by the applicant.
  • the Cambridge International application discloses two potential applications of a "discovery" in the field of metallurgical electrochemistry.
  • One application is the direct production of a metal from a metal oxide.
  • the "discovery” is the realisation that an electrolytic cell can be used to ionise oxygen contained in a metal oxide so that the oxygen dissolves in an electrolyte.
  • the Cambridge International application discloses that when a suitable potential is applied to an electrolytic cell with a metal oxide as a cathode, a reaction occurs whereby oxygen is ionised and is subsequently able to dissolve in the electrolyte of the cell.
  • the allowed claims of the European patent application inter alia define a method of electrolytically reducing a metal oxide (such as titania) that includes operating an electrolytic cell at a potential at an electrode formed from the metal oxide that is lower than the deposition potential of cations in the electrolyte at a surface of the electrode.
  • a metal oxide such as titania
  • the Cambridge European patent application does not define what is meant by deposition potential and does not include any specific examples that provide values of the deposition potential for particular cations.
  • page 5 of the submissions state that:
  • the experimental work was carried out using a CaCl 2 -based electrolyte at a cell potential below the decomposition potential of CaCl 2 .
  • the applicant believes that the initial deposition of Ca metal on the cathode was due to the presence of Ca ++ cations and O -- anions derived from CaO in the electrolyte.
  • the decomposition potential of CaO is less than the decomposition potential of CaCl 2 .
  • the cell operation is dependent, at least during the early stages of cell operation, on decomposition of CaO, with Ca ++ cations migrating to the cathode and depositing as Ca metal and O -- anions migrating to the anode and forming CO and/or CO 2 (in a situation in which the anode is a graphite anode).
  • the applicant also believes that at later stages of the cell operation part of the Ca metal that deposited on the cathode was deposited directly on partially deoxidised titanium and thereafter participated in chemical reduction of titanium.
  • the cathode is formed at least in part from the metal oxide.
  • the method includes operating the cell at the potential that is above the potential at which cations of the metal that is capable of chemically reducing the metal oxide deposit as the metal on the cathode so that the metal deposits on the cathode.
  • the metal deposited on the cathode is soluble in the electrolyte and can dissolve in the electrolyte and thereby migrate to the vicinity of the metal oxide.
  • the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents of the electrolyte.
  • the present invention does not require the addition of substantial amounts of CaO to the electrolyte.
  • the cell potential be above a potential at which Ca metal can deposit on the cathode, i.e. at a potential that is above the decomposition potential of CaO.
  • the decomposition potential of CaO can vary over a considerable range depending on factors such as the composition of the anode, the electrolyte temperature and electrolyte composition.
  • the cell potential be below the potential at which Cl - anions can deposit on the anode and form chlorine gas, i.e. the decomposition potential of CaCl 2 .
  • the decomposition potential of CaCl 2 can vary over a considerable range depending on factors such as the composition of the anode, the electrolyte temperature and electrolyte composition.
  • the cell potential be between 1.3 and 3.5V.
  • the CaCl 2 -based electrolyte may be a commercially available source of CaCl 2 , such as calcium chloride dihydrate, that partially decomposes on heating and produces CaO or otherwise includes CaO.
  • the CaCl 2 -based electrolyte may include CaCl 2 and CaO that are added separately or pre-mixed to form the electrolyte.
  • the anode be graphite or an inert anode.
  • Carbon in the titanium is an undesirable contaminant.
  • carbon transfer was partially responsible for low energy efficiency of the cell. Both problems could present significant barriers to commercialisation of electrolytic reduction technology.
  • the dominant mechanism of carbon transfer is electrochemical rather than erosion and that one way of minimising carbon transfer and therefore contamination of titanium produced at the cathode by electrochemical reduction of titania is to position a membrane that is permeable to oxygen anions and is impermeable to carbon in ionic and non-ionic forms between the cathode and the anode and thereby prevent migration of carbon to the cathode.
  • the electrolytic cell includes a membrane that is permeable to oxygen anions and is impermeable to carbon in ionic and non-ionic forms positioned between the cathode and the anode to thereby prevent migration of carbon to the cathode.
  • the membrane may be formed from any suitable material.
  • the membrane is formed from a solid electrolyte.
  • One solid electrolyte tested by the applicant is yttria stabilised zirconia.
  • an electrolytic cell as described above and operating in accordance with the above described method.
  • the electrolytic cell is shown in Figure 1 .
  • the electrochemical cell included a graphite crucible equipped with a graphite lid.
  • the crucible was used as the cell anode.
  • a stainless steel rod was used to secure electrical contact between a d/c power supply and the crucible.
  • the cell cathode consisted of Kanthal or platinum wire connected at one end to the power supply and TiO 2 pellets suspended from the other end of the wire.
  • An alumina tube was used as an insulator around the cathode.
  • the cell electrolyte was a commercially available source of CaCl 2 , namely calcium chloride dihydrate, that partially decomposed on heating at the operating temperature of the cell and produced CaO.
  • a thermocouple was immersed in the electrolyte in close proximity to the pellets.
  • pellets Two types were used. One type was slip-cast and the other type was pressed. Both types of pellets were made from analytical grade TiO 2 powder. Both types of pellets were sintered in air at 850°C. One pressed and one slip-cast pellet were used in the experiment.
  • the power-supply maintained a constant voltage throughout the experiment.
  • the voltage and resulting cell current were logged using LabVIEW (TM) data acquisition software.
  • the constant voltage (3V) used in the experiment produced an initial current of approximately 1.2A. A continuous drop in the current was observed during the initial 2 hours. After that a gradual increase in the current up to 1A was observed.
  • the invention is not so limited and extends to reduction of other titanium oxides and to oxides of other metals and alloys.
  • examples of other potentially important metals are aluminium, silicon, germanium, zirconium, hafnium, magnesium and molybdenum.
  • suitable electrolytes will be salts and oxides that are soluble in salts.
  • suitable electrolyte is BaCl 2 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Electrolytic Production Of Metals (AREA)
EP14163470.9A 2002-03-13 2003-03-13 Reduktion von Metalloxiden in einer Elektrolysezelle Withdrawn EP2770086A3 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPS1071A AUPS107102A0 (en) 2002-03-13 2002-03-13 Electrolytic reduction of metal oxides
AUPS3049A AUPS304902A0 (en) 2002-06-19 2002-06-19 Reduction of metal oxides in an electrolytic cell
EP03743767A EP1492905A4 (de) 2002-03-13 2003-03-13 Reduktion von metalloxiden in einer elektrolysezelle

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP03743767A Division EP1492905A4 (de) 2002-03-13 2003-03-13 Reduktion von metalloxiden in einer elektrolysezelle

Publications (2)

Publication Number Publication Date
EP2770086A2 true EP2770086A2 (de) 2014-08-27
EP2770086A3 EP2770086A3 (de) 2014-10-29

Family

ID=27805836

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14163470.9A Withdrawn EP2770086A3 (de) 2002-03-13 2003-03-13 Reduktion von Metalloxiden in einer Elektrolysezelle
EP03743767A Withdrawn EP1492905A4 (de) 2002-03-13 2003-03-13 Reduktion von metalloxiden in einer elektrolysezelle

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP03743767A Withdrawn EP1492905A4 (de) 2002-03-13 2003-03-13 Reduktion von metalloxiden in einer elektrolysezelle

Country Status (12)

Country Link
EP (2) EP2770086A3 (de)
JP (1) JP4658479B2 (de)
KR (2) KR101038701B1 (de)
CN (1) CN1650051B (de)
BR (1) BR0308384B1 (de)
CA (1) CA2479048C (de)
EA (1) EA007046B1 (de)
MX (1) MXPA04008887A (de)
NO (1) NO340277B1 (de)
NZ (1) NZ531467A (de)
WO (1) WO2003076690A1 (de)
ZA (1) ZA200407434B (de)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPS117002A0 (en) * 2002-03-13 2002-04-18 Bhp Billiton Innovation Pty Ltd Minimising carbon transfer in an electrolytic cell
GB0219640D0 (en) * 2002-08-23 2002-10-02 Univ Cambridge Tech Electrochemical method and apparatus
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
JP4513297B2 (ja) * 2003-09-30 2010-07-28 日本軽金属株式会社 金属酸化物の還元方法及び金属酸化物の還元装置
JP4502617B2 (ja) * 2003-09-30 2010-07-14 日本軽金属株式会社 金属酸化物の還元方法及び金属酸化物の還元装置
JP2007529631A (ja) * 2004-03-22 2007-10-25 ビーエイチピー ビリトン イノベーション プロプライアタリー リミテッド 金属酸化物の電気化学的還元
BRPI0512782A (pt) * 2004-06-28 2008-04-08 Bhp Billiton Innovation Pty método para produzir metal de titánio e produtos de metal de titánio semi-acabados ou prontos para o uso
EP1920087B1 (de) * 2005-08-01 2017-03-22 Metalysis Limited Elektrochemische reduktion von titanoxid
NO20062776L (no) * 2006-06-14 2007-12-17 Norsk Titanium Tech As Fremgangsmåte, apparatur samt midler for produksjon av materiale i en smeltet salt elektrolytt
CN100532653C (zh) * 2006-11-03 2009-08-26 西北有色金属研究院 一种熔盐电解提取钛的方法
GB0714021D0 (en) * 2007-07-18 2007-08-29 Green Metals Ltd Improvements in anode materials
GB0902486D0 (en) * 2009-02-13 2009-04-01 Metalysis Ltd A method for producing metal powders
GB201010772D0 (en) * 2010-06-26 2010-08-11 Fray Derek J Method for texturing silicon surfaces
GB201019615D0 (en) 2010-11-18 2010-12-29 Metalysis Ltd Electrolysis apparatus and method
EP2640871B1 (de) 2010-11-18 2018-10-17 Metalysis Limited Verfahren und system zur elektrolytischen reduktion eines festen rohstoffes
BR112013012506A2 (pt) 2010-11-18 2017-02-07 Metalysis Ltd aparelho de eletrólise
GB201102023D0 (en) 2011-02-04 2011-03-23 Metalysis Ltd Electrolysis method, apparatus and product
RU2466216C1 (ru) * 2011-06-17 2012-11-10 Государственное образовательное учреждение высшего профессионального образования "Национальный исследовательский Томский политехнический университет" Способ получения металлического титана электролизом
JP6122016B2 (ja) 2011-10-04 2017-04-26 メタリシス リミテッド 粉末の電解製造
GB201223375D0 (en) 2012-12-24 2013-02-06 Metalysis Ltd Method and apparatus for producing metal by electrolytic reduction
KR101526298B1 (ko) * 2013-04-22 2015-06-10 서울대학교산학협력단 산화티타늄 전극의 제조방법, 이를 포함하는 활성산소종 생성 시스템, 염소 생성 시스템, 염료감응형 태양전지 및 전기이중층 커패시터
GB201411433D0 (en) 2014-06-26 2014-08-13 Metalysis Ltd Method and apparatus for electrolytic reduction of a feedstock comprising oxygen and a first metal
KR101740424B1 (ko) 2015-08-18 2017-05-26 충남대학교산학협력단 일메나이트 원광을 이용한 금속 티타늄의 제조방법
NL2015759B1 (en) 2015-11-10 2017-05-26 Stichting Energieonderzoek Centrum Nederland Additive manufacturing of metal objects.
EA037801B1 (ru) * 2016-02-17 2021-05-24 Металисиз Лимитед Способ получения графеновых материалов
GB201615658D0 (en) 2016-09-14 2016-10-26 Metalysis Ltd Method of producing a composite material
GB201615659D0 (en) 2016-09-14 2016-10-26 Metalysis Ltd Method of producing a powder
GB201615660D0 (en) 2016-09-14 2016-10-26 Metalysis Ltd Method of producing a powder
NL2018890B1 (en) 2017-05-10 2018-11-15 Admatec Europe B V Additive manufacturing of metal objects
NL2021611B1 (en) 2018-09-12 2020-05-06 Admatec Europe B V Three-dimensional object and manufacturing method thereof
CN109763146B (zh) * 2019-03-27 2021-03-26 贵州省过程工业技术研究中心 一种铝电解用钛基复合材料阳极制备方法

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Publication number Priority date Publication date Assignee Title
WO1999064638A1 (en) 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt

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ITTO970080A1 (it) * 1997-02-04 1998-08-04 Marco Vincenzo Ginatta Procedimento per la produzione elettrolitica di metalli
GB2359564B (en) * 2000-02-22 2004-09-29 Secr Defence Improvements in the electrolytic reduction of metal oxides
AUPR443801A0 (en) * 2001-04-10 2001-05-17 Bhp Innovation Pty Ltd Removal of oxygen from metal oxides and solid metal solutions
AUPR602901A0 (en) * 2001-06-29 2001-07-26 Bhp Innovation Pty Ltd Removal of oxygen from metals oxides and solid metal solutions
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

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1999064638A1 (en) 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt

Also Published As

Publication number Publication date
JP4658479B2 (ja) 2011-03-23
MXPA04008887A (es) 2004-11-26
BR0308384A (pt) 2005-01-25
EP2770086A3 (de) 2014-10-29
EA007046B1 (ru) 2006-06-30
ZA200407434B (en) 2006-05-31
KR101038701B1 (ko) 2011-06-02
CA2479048C (en) 2012-07-10
NO20043857L (no) 2004-12-08
EP1492905A1 (de) 2005-01-05
NO340277B1 (no) 2017-03-27
CN1650051A (zh) 2005-08-03
CN1650051B (zh) 2011-02-23
BR0308384B1 (pt) 2014-02-04
WO2003076690A1 (en) 2003-09-18
KR20110025237A (ko) 2011-03-09
JP2005520045A (ja) 2005-07-07
EP1492905A4 (de) 2006-06-28
EA200401203A1 (ru) 2005-06-30
CA2479048A1 (en) 2003-09-18
KR20040111408A (ko) 2004-12-31
NZ531467A (en) 2007-06-29

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