CN1509346A - Electrolytic reduction of metal oxides - Google Patents

Electrolytic reduction of metal oxides Download PDF

Info

Publication number
CN1509346A
CN1509346A CNA028100840A CN02810084A CN1509346A CN 1509346 A CN1509346 A CN 1509346A CN A028100840 A CNA028100840 A CN A028100840A CN 02810084 A CN02810084 A CN 02810084A CN 1509346 A CN1509346 A CN 1509346A
Authority
CN
China
Prior art keywords
metal
metal oxide
electrolytic solution
electrolyzer
definition
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.)
Pending
Application number
CNA028100840A
Other languages
Chinese (zh)
Inventor
利斯·斯特雷佐夫
���з�
伊凡·雷特切夫
史蒂夫·奥斯本
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 Billiton 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
Application filed by BHP Billiton Innovation Pty Ltd filed Critical BHP Billiton Innovation Pty Ltd
Publication of CN1509346A publication Critical patent/CN1509346A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

A method of electrolytically reducing a metal oxide (such as aluminium and magnesium oxides) to produce a metal in an electrolytic call is disclosed. The method includes electrolytically reducing the metal oxide in an electrolytic cell that includes a pool of molten metal, the metal being the metal of the metal oxide to be reduced, and the molten metal pool forming a cathode of the cell. The electrolytic cell also includes a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides. The electrolytic cell also includes an anode extending into the electrolyte and a body of metal oxide to reduced in contact with the molten metal and the electrolyte.

Description

The electrolytic reduction of metal oxide
Invention field
The present invention relates to the metal oxide electrolytic reduction to generate pure substantially metal.
Particularly, the present invention relates to use CaCl 2The aluminium of electrolytic solution and the electrolytic reduction of magnesium oxide.
Background technology
The present invention is that the applicant is implementing use based on CaCl 2Finish in the process of the metal oxide electrolytic reduction research project of electrolytic solution.
This research project is based on using CaCl in research 2The electrolytic reduction of the multiple metal oxide in the electrolyzer of electrolytic solution.
CaCl 2Electrolytic solution is commercially available CaCl 2The source, i.e. two hydration calcium chloride decompose during its heating and produce very small amount of CaO.
The applicant is lower than CaCl being higher than the CaO decomposition voltage 2The voltage of decomposition voltage is this electrolyzer of operation down.
The applicant finds that this electrolyzer can be generated as metal by the multiple metal oxide of electrolytic reduction under very low oxygen concn.
Summary of the invention
The present invention provides a kind of method that generates metal in electrolyzer with the electrolytic reduction metal oxide widely, this method is included in electrolytic reduction metal oxide in the electrolyzer, this electrolyzer comprises (a) pool of molten metal, it is the metal of wanting the reductive metal oxide, form the pool of molten metal of the negative electrode of electrolyzer, (b) with the contacted fused electrolysis of melt metal liquid pool, the halid electrolytic solution that contains basic metal and/or alkaline-earth metal, (c) extend to anode and (d) and molten metal and the contacted metal oxide main body that will be reduced of electrolytic solution in the electrolytic solution.
In aforesaid method, the electrolytic reduction of metal oxide is in (i) molten metal, (ii) metal oxide and the (iii) generation of the contact position between electrolytic solution.
Preferably, this metal oxide main body has and (i) molten metal, (ii) metal oxide and (iii) form the geometrical shape of maximum contact between the electrolytic solution.
Preferably, this method comprises the metal oxide main body is fed in the electrolyzer to keep metal oxide and melt metal is in contact with one another.
The metal oxide main body can comprise bar, plate, piece etc. by many shapes, and they can easily immerse in the electrolytic solution and with melt metal and be in contact with one another.
Preferably, this method comprises that keeping electrolyzer temperature is higher than electrolytic solution and the fusing point of wanting the metal of reductive metal oxide.
Preferably, this method is included in operates this electrolyzer under the voltage that is higher than the decomposition voltage of at least a composition in the electrolytic solution, so that have the positively charged ion rather than the cathodic metal oxide compound of metal in electrolytic solution.
Preferred metal oxide is aluminum oxide or magnesium oxide.
At metal oxide is under aluminum oxide or the magnesian situation, and preferred electrolytic solution is to contain the CaCl of CaO as one of its composition 2Base electrolytic solution.
In this case, preferably, the voltage of electrolyzer is higher than the decomposition voltage of CaO.
Equally preferably, bath voltage is lower than CaCl 2Decomposition voltage.
Preferably, bath voltage is lower than 3.0V.
Particularly preferably be, bath voltage is lower than 2.5V.
More particularly preferably be, bath voltage is lower than 2.0V.
Preferably, bath voltage is at least 1.5V.
CaCl 2The electrolytic solution of base can be commercially available CaCl 2The source, as two hydration calcium chloride, it the time partly decomposes and generates CaO or contain other material of CaO in heating.
Perhaps, or in addition, CaCl 2The electrolytic solution of base can comprise that add or premix respectively CaCl 2With CaO to form electrolytic solution.
In present stage, the applicant to electrolyzer based on CaCl 2The voltage that electrolytic solution partly the decomposes mechanism of the electrolyzer of operation down clearly is not familiar with.Yet the applicant provides following explanation to the main points of possible electrolyzer mechanism, does not wish to be limited by the explanation of this section simultaneously.The applicant thinks and is being higher than CaCl 2Operation of cells generates Ca under the voltage that base electrolytic solution partly decomposes ++Positively charged ion, calcium Ca ++Cation transport to the contacted metal oxide of melt metal negative electrode near and provide and impel O -The impellent of anionic discharge, this O -Negatively charged ion is to produce when the metal of electrolytic reduction metal oxide when contacting with the molten metal negative electrode.The applicant also thinks: this O -In a single day negatively charged ion is discharged from metal oxide, move to the reaction of anode and anode carbon and generate CO and discharge electronics, and this electronics quickens metal oxide electrolytic reduction and becomes metal.The cut-and-try work that the applicant carries out provides the evidence of Ca metal in electrolytic solution.The applicant thinks: this Ca metal is Ca ++The sedimentary result of cation electrode is as being dissolved in the electrolytic solution in the Ca of negative electrode current-carrying part metal and at least a portion and moving near the metal oxide of negative electrode and participate in the Ca metal of the chemical reduction of oxide compound.
Preferably, anode is a graphite.
Preferably, electrolyzer comprises the bottom that formed by graphite and from the upwardly extending sidewall in this bottom.
Preferably, electrolyzer is included in the discharge outlet that has a molten metal on the sidewall at least, and this method comprises the continuous or periodic melt metal of removing.
Aforesaid method can start by several different methods.
A kind of selection is that solid-state (pure) metal and electrolytic solution are introduced in the electrolyzer, heats whole system then until metal and electrolytic solution fusing.
Another selection is that melt metal and fused ionogen are introduced electrolyzer respectively.
In the process of the pure substantially aluminium of reduction-oxidation aluminium generation, use electrolyzer shown in Figure 1 among the following examples explanation the present invention.
The description of specific embodiments
Fig. 1 is the synoptic diagram of the electrolyzer 5 that can amplify in proportion in the present patent application.
Simultaneously, following example relates to the reduction of aluminium oxide, and basic principle can be applied to other metal equally, Particularly low-melting-point metal, more particularly magnesium.
Electrolyzer 5 among Fig. 1 comprise have bottom 21, sidewall 31 and the plumbago crucible 10 of discharging/outflow openings in sidewall 31 with 12 expressions.
This electrolyzer 5 further is included in the fusion CaCl in the crucible 2Graphite Electrodes 11 in the pond of electrolytic solution 13 and the immersion molten electrolyte 13.This Graphite Electrodes 11 forms the anode of this electrolyzer 5.
This electrolyzer 5 further is included in the molten aluminum bath 15 of crucible 10 bottoms.This molten aluminum bath 15 forms the negative electrode of electrolyzer.
This electrolyzer further comprises main body 14, and it is by wanting reductive aluminum oxide (Al 2O 3) constitute or be mixed with aluminum oxide (Al 2O 3), and main body stretches in the electrolytic solution 13 and with molten aluminum negative electrode 15 and contacts.The aluminum oxide main body becomes bar, plate or prism-shaped.Aluminum oxide main body 14 keeps by rights so that can move into or leave with controlling crucible inside along direction shown in the arrow 16.
Electrolyzer 5 further comprises the suitable power supply 18 that is connected to anode 11 and arrives molten aluminum negative electrode 15.
This molten aluminum negative electrode 15 is necessary, for the alumina eltrolysis in the initiated oxidation aluminium main body 14 is reduced to aluminium.The electrolytic reduction method is to carry out under about 950 ℃ high temperature, under this temperature, and CaCl 2Electrolytic solution keeps and fusion.When aluminum oxide main body 14 immersed electrolytic solution 13 and aluminum oxide main body 14 contacts with fused aluminium negative electrode 15 subsequently, the aluminum oxide reduction took place.Because process temperature is higher than the aluminium fusing point, the latter will be fused in the molten bath 15, and the bath level face in the crucible 10 will rise.
In order to keep optimum reductive condition, aluminum oxide main body 14 moves and accumulates aluminium with the speed suitable with the speed that is melted by aluminum oxide main body 14, so that make the immersion of aluminum oxide main body 14 in molten aluminum keep minimum.
This process can be by removing fused aluminium and placing other aluminum oxide main body 14 and carry out operate continuously with the main body 14 that replaces consuming in electrolytic solution 13 in reduction process through discharge outlet 12.
Can do many improvement to the embodiment of foregoing invention not breaking away under the spirit and scope of the present invention.

Claims (15)

  1. One kind in electrolyzer the electrolytic reduction metal oxide with metallic method, this method is included in electrolytic reduction metal oxide in the electrolyzer, this electrolyzer comprises the pond of molten metal, the metal of the metal oxide that is reduced, form the pool of molten metal of the negative electrode of electrolyzer, with the contacted fused electrolysis of melt metal liquid pool, the electrolytic solution that contains basic metal and/or alkaline earth metal halide, extend in the electrolytic solution anode and with molten metal and the contacted metal oxide main body that will be reduced of electrolytic solution.
  2. 2. the method for claim 1 definition is characterized in that, this metal oxide main body have with (i) molten metal, (ii) metal oxide and (iii) electrolytic solution form the geometrical shape of maximum contact.
  3. 3. the method for claim 1 or 2 definition comprises metal oxide main body feed is advanced in the electrolyzer to keep being in contact with one another of metal oxide and molten metal.
  4. 4. the method for above-mentioned arbitrary claim definition is characterized in that this metal oxide main body comprises shapes such as bar, plate, piece, and they can easily immerse in the electrolytic solution and with molten metal and be in contact with one another.
  5. 5. the method for above-mentioned arbitrary claim definition comprises and keeps the fusing point that electrolyzer temperature is higher than ionogen and wants the metal of reductive metal oxide.
  6. 6. the method for above-mentioned arbitrary claim definition is included in the voltage that is higher than the decomposition voltage of at least a composition in the electrolytic solution and operates this electrolyzer down, so that have anionic metal rather than cathodic metal oxide compound in electrolytic solution.
  7. 7. the method for above-mentioned arbitrary claim definition is characterized in that this metal oxide is an aluminum oxide or magnesian.
  8. 8. the method for claim 7 definition is characterized in that this electrolytic solution is to contain the CaCl of CaO as one of composition 2The electrolytic solution of base.
  9. 9. the method for claim 8 definition comprises and keeps the decomposition voltage that bath voltage is higher than CaO.
  10. 10. the method for claim 8 or 9 definition comprises that keeping bath voltage is lower than CaCl 2Decomposition voltage.
  11. 11. the method for claim 10 definition comprises and keeps the low 3.0V of bath voltage.
  12. 12. the method for claim 10 definition comprises and keeps the low 2.5V of bath voltage.
  13. 13. the method for claim 10 definition comprises and keeps the low 2.0V of bath voltage.
  14. 14. arbitrary method of definition comprises that keeping bath voltage is at least 1.5V in the claim 8～13.
  15. 15. the method for above-mentioned arbitrary claim definition it is characterized in that electrolyzer comprises the discharge outlet of at least one molten metal, and this method comprises through the continuous or periodic molten metal of removing of discharge outlet.
CNA028100840A 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides Pending CN1509346A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPR4439 2001-04-10
AUPR4439A AUPR443901A0 (en) 2001-04-10 2001-04-10 Method for reduction of metal oxides to pure metals

Publications (1)

Publication Number Publication Date
CN1509346A true CN1509346A (en) 2004-06-30

Family

ID=3828435

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA028100840A Pending CN1509346A (en) 2001-04-10 2002-04-10 Electrolytic reduction of metal oxides

Country Status (9)

Country Link
US (2) US20040237710A1 (en)
EP (1) EP1392890A4 (en)
JP (1) JP2004523662A (en)
CN (1) CN1509346A (en)
AU (1) AUPR443901A0 (en)
CA (1) CA2443953A1 (en)
NO (1) NO20034548L (en)
WO (1) WO2002083989A1 (en)
ZA (1) ZA200307978B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104733754A (en) * 2013-12-20 2015-06-24 现代自动车株式会社 Regeneration Method Of Raw Materials For Hydrogen Supply System Of Fuel Cell
CN109055985A (en) * 2018-09-12 2018-12-21 郑州大学 A kind of electrolytic oxidation magnesium molten salt system, preparation method and applications
CN110219021A (en) * 2019-06-19 2019-09-10 李运雄 A kind of closing down magnesium electrolysis bath and magnesium eletrolysis technique
CN110219021B (en) * 2019-06-19 2024-05-24 陕西均健佳实业有限公司 Magnesium electrolytic tank and magnesium electrolysis process

Families Citing this family (6)

* 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
US8152895B2 (en) * 2003-04-23 2012-04-10 Ut-Battelle, Llc Production of magnesium metal
WO2007102994A2 (en) * 2006-02-22 2007-09-13 University Of Utah Research Foundation Systems and methods for hydrogen storage and generation from water using lithium based materials
EP2469969A1 (en) * 2010-12-24 2012-06-27 Philip Morris Products S.A. Reduced ceramic heating element
KR102004920B1 (en) * 2019-01-28 2019-07-29 한국지질자원연구원 Metal refining method by using liquid metal cathode

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951763A (en) * 1973-06-28 1976-04-20 Aluminum Company Of America Aluminum smelting temperature selection
FR2487386A1 (en) * 1980-07-23 1982-01-29 Pechiney Aluminium METHOD AND APPARATUS FOR PRECISELY REGULATING THE INTRODUCTION RATE AND THE ALUMINUM CONTENT OF AN IGNATED ELECTROLYSIS TANK, AND APPLICATION TO THE PRODUCTION OF ALUMINUM
WO1983000171A1 (en) * 1981-07-01 1983-01-20 De Nora, Vittorio Electrolytic production of aluminum
US4455202A (en) * 1982-08-02 1984-06-19 Standard Oil Company (Indiana) Electrolytic production of lithium metal
US4597839A (en) * 1983-12-14 1986-07-01 Atlantic Richfield Company Method and apparatus for production of a metal from metallic oxide ore
GB8707781D0 (en) * 1987-04-01 1987-05-07 Shell Int Research Electrolytic production of metals
US4973390A (en) * 1988-07-11 1990-11-27 Aluminum Company Of America Process and apparatus for producing lithium from aluminum-lithium alloy scrap in a three-layered lithium transport cell
US5279715A (en) * 1991-09-17 1994-01-18 Aluminum Company Of America Process and apparatus for low temperature electrolysis of oxides
US5378325A (en) * 1991-09-17 1995-01-03 Aluminum Company Of America Process for low temperature electrolysis of metals in a chloride salt bath
US5593566A (en) * 1995-06-09 1997-01-14 General Motors Corporation Electrolytic production process for magnesium and its alloys
US7504017B2 (en) * 2001-11-22 2009-03-17 Qit-Fer Et Titane Inc. Method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104733754A (en) * 2013-12-20 2015-06-24 现代自动车株式会社 Regeneration Method Of Raw Materials For Hydrogen Supply System Of Fuel Cell
CN104733754B (en) * 2013-12-20 2019-08-20 现代自动车株式会社 The regeneration method of the raw material of hydrogen supply for fuel cell
CN109055985A (en) * 2018-09-12 2018-12-21 郑州大学 A kind of electrolytic oxidation magnesium molten salt system, preparation method and applications
CN109055985B (en) * 2018-09-12 2019-09-27 郑州大学 A kind of electrolytic oxidation magnesium molten salt system, preparation method and applications
CN110219021A (en) * 2019-06-19 2019-09-10 李运雄 A kind of closing down magnesium electrolysis bath and magnesium eletrolysis technique
CN110219021B (en) * 2019-06-19 2024-05-24 陕西均健佳实业有限公司 Magnesium electrolytic tank and magnesium electrolysis process

Also Published As

Publication number Publication date
WO2002083989A1 (en) 2002-10-24
EP1392890A1 (en) 2004-03-03
CA2443953A1 (en) 2002-10-24
JP2004523662A (en) 2004-08-05
EP1392890A4 (en) 2004-10-06
NO20034548D0 (en) 2003-10-09
NO20034548L (en) 2003-12-01
US20040237710A1 (en) 2004-12-02
ZA200307978B (en) 2004-09-03
AUPR443901A0 (en) 2001-05-17
US20080110764A1 (en) 2008-05-15

Similar Documents

Publication Publication Date Title
CN1650051B (en) Reduction of metal oxides in an electrolytic cell
AU758931B2 (en) Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt
CN1195901C (en) Molten salt bath circulation design for an electrolytic cell
CN1653210A (en) Hydrogen-assisted electrolysis processes
CN101166838A (en) Electrochemical reduction of metal oxides
US20080110764A1 (en) Electrolytic Reduction of Metal Oxides
RU2107753C1 (en) Method of production of metallic magnesium (versions) and method of production of metallic magnesium from alloy of magnesium and rare-earth metal
WO2006037999A2 (en) Electro-reduction process
CN1285771C (en) Extraction of metals
CN1711373A (en) Minimizing carbon transfer in an electrolytic cell
JP2007016293A (en) Method for producing metal by suspension electrolysis
RU2006119476A (en) METHOD FOR ELECTROLYTIC PRODUCTION OF ALUMINUM
US3725222A (en) Production of aluminum
US20030015434A1 (en) Process for purification of molten salt electrolytes
US20240141529A1 (en) Method for producing metal aluminum by molten salt electrolysis of aluminum oxide
CN100582313C (en) Electrochemical reduction of metal oxides
JP5046096B2 (en) Sodium production method and sodium production apparatus
US6866766B2 (en) Methods and apparatus for reducing sulfur impurities and improving current efficiencies of inert anode aluminum production cells
CN1650052A (en) Minimising carbon transfer in an electrolytic cell
CN1509347A (en) Arrangement of anode for utilization in electrolysis cell
CA2603095C (en) Method and apparatus for the production of aluminium
AU2002245948B2 (en) Electrolytic reduction of metal oxides
CN1659313A (en) Method and apparatus for reducing sulfur impurities and improving current efficiencies of inert anode aluminum production cells
AU2002245948A1 (en) Electrolytic reduction of metal oxides
Freidina et al. Synthesis of Pb-Ca alloys by electrolysis of CaO solution in molten salt

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication