EP1392890A1 - Elektrolytische reduktion von metalloxiden - Google Patents
Elektrolytische reduktion von metalloxidenInfo
- Publication number
- EP1392890A1 EP1392890A1 EP02713941A EP02713941A EP1392890A1 EP 1392890 A1 EP1392890 A1 EP 1392890A1 EP 02713941 A EP02713941 A EP 02713941A EP 02713941 A EP02713941 A EP 02713941A EP 1392890 A1 EP1392890 A1 EP 1392890A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- electrolyte
- cell
- metal oxide
- method defined
- 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- Withdrawn
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 42
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 30
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 150000004820 halides Chemical class 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 16
- 239000001110 calcium chloride Substances 0.000 claims description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 16
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 15
- 235000012245 magnesium oxide Nutrition 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- -1 Ca++ cations Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 2
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 2
- 230000007248 cellular mechanism Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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
Definitions
- the present invention relates to electrolytic reduction of metal oxides to produce substantially pure metals.
- the present invention relates to electrolytic reduction of aluminium and magnesium oxides using a CaCl 2 electrolyte.
- the present invention was made during the course of an on-going research project on the electrolytic reduction of metal oxides using CaCl 2 -based electrolyte being carried out by the applicant.
- the research project investigated electrolytic reduction of a range of metal oxides in electrolyte cells based on the use of using CaCl 2 electrolyte.
- the CaCl 2 electrolyte 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 .
- the present invention provides, in broad terms, a method of electrolytically reducing a metal oxide to produce a metal in an electrolytic cell, which method includes electrolytically reducing the metal oxide in an electrolytic cell that includes (a) a pool of molten metal, the metal being the metal of the metal oxide to be reduced, the molten metal pool forming a cathode of the cell, (b) a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides, (c) an anode extending into the electrolyte, and (d) a body of metal oxide to reduced in contact with the molten metal and the electrolyte.
- electrolytic reduction of metal oxide takes place where there is contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
- the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte..
- the method includes feeding the metal oxide body into the electrolytic cell to maintain contact of the metal oxide and the molten metal.
- the metal oxide body may be in many forms, including rods, plates, blocks and the like, which can be readily immersed into the electrolyte and brought into contact with the molten metal.
- the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced.
- the method includes operating the cell at a potential that is 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 metal oxide is an aluminium oxide or a magnesium oxide.
- the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents.
- the cell potential be above the decomposition potential for CaO.
- the cell potential be below the decomposition potential for CaCl 2 .
- the cell potential be less than 3.0V.
- the cell potential be below 2.5V.
- the cell potential be below 2.0V.
- the cell potential be at least 1.5V.
- 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-mised to form the electrolyte.
- the applicant does not have a clear understanding of the electrolytic cell mechanism when the cell is operated at a potential at which CaCl 2 - based electrolyte partially decomposes. Nevertheless, whilst not wishing to be bound by the comments in this paragraph, the applicant offers the following comments by way of an outline of a possible cell mechanism. The applicant believes that operating the electrolytic cell above a potential at which CaCl 2 -based electrolyte partially decomposes produces Ca ++ cations that migrate to the vicinity of the metal oxide in contact with the molten metal cathode and provide a driving force that facilitates extraction of O " anions produced by electrolytic reduction to metal of metal oxide in contact with the molten metal cathode.
- the applicant also believes that the 0 "" anions, once extracted from the metal oxide, migrate to the anode and react with anode carbon and produce CO and release electrons that facilitate electrolytic reduction of metal oxide to metal .
- the experimental work carried out by the applicant produced evidence of Ca metal in the electrolyte.
- the applicant believes that the Ca metal was the result of electrodeposition of Ca ++ cations as Ca metal on electrically conductive sections of the cathode and that at least part of the Ca metal dissolved in the electrolyte and migrated to the vicinity of the metal oxide in the cathode and participated in chemical reduction of oxides.
- the anode be graphite.
- the cell includes a base and side walls extending upwardly from the base formed from graphite.
- the cell includes at least one tap hole for molten metal in one of the side walls and the method includes removing molten metal continuously or periodically.
- the above-described method may be started-up in a number of ways.
- One option is to introduce the (pure) metal and the electrolyte in solid state into the cell and subsequently heat the entire system to melt the metal and the electrolyte.
- Another option is to introduce molten metal and molten electrolyte separately into the cell .
- Figure 1 is a schematic illustration of an electrolytic cell 5 that can be scaled-up in application of the present invention.
- the electrolytic cell 5 of Figure 1 includes a graphite crucible 10 that has a base 21, side walls 31, and a tapping/discharge opening indicated as 12 in one of the side walls 31.
- the electrolytic cell 5 further includes a bath of molten CaCl electrolyte 13 in the crucible and a graphite electrode 11 immersed in the molten electrolyte 13.
- the graphite electrode 11 forms the anode of the cell 5.
- the electrolytic cell 5 further includes a pool 15 of molten aluminium in a lower section of the crucible 10.
- the molten aluminium pool 15 forms the cathode of the cell.
- the electrolytic cell further includes a body 14 that consists of or incorporates alumina (A1 2 0 3 ) to be reduced and extends into the electrolyte 13 and contacts the molten aluminium cathode 15.
- the alumina is shaped as a rod, sheet or prismatic body. Alumina body 14 is held in an appropriate manner to allow controlled movement into and away from the crucible interior as indicated by the arrow 16.
- the electrolytic cell 5 further includes a suitable power source 18 connected to the anode 11 and to the molten aluminium cathode 15.
- the molten aluminium cathode 15 is required in order to initiate electrolytic reduction of the alumina in the alumina body 14 to aluminium.
- the electrolytic reduction process is carried out at an elevated temperature of around 950°C at which the CaCl 2 electrolyte is and remains molten.
- reduction of the alumina takes place. Since the process temperatures are above the melting point of aluminium, the latter will melt into the bath 15 and the bath level within crucible 10 will tend to rise.
- the alumina body 14 is moved at a rate commensurate with the melting-off rate of aluminium from the alumina body 14 and the build-up of aluminium so that immersion of the alumina body 14 in the molten aluminium is kept at a minimum.
- the process may be operated in a continuous mode by removing molten aluminium through tap hole 12 and positioning additional alumina bodies 14 in the electrolyte 13 to replace bodies 14 that are consumed in the reduction process .
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)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPR443901 | 2001-04-10 | ||
AUPR4439A AUPR443901A0 (en) | 2001-04-10 | 2001-04-10 | Method for reduction of metal oxides to pure metals |
PCT/AU2002/000456 WO2002083989A1 (en) | 2001-04-10 | 2002-04-10 | Electrolytic reduction of metal oxides |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1392890A1 true EP1392890A1 (de) | 2004-03-03 |
EP1392890A4 EP1392890A4 (de) | 2004-10-06 |
Family
ID=3828435
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02713941A Withdrawn EP1392890A4 (de) | 2001-04-10 | 2002-04-10 | Elektrolytische reduktion von metalloxiden |
Country Status (9)
Country | Link |
---|---|
US (2) | US20040237710A1 (de) |
EP (1) | EP1392890A4 (de) |
JP (1) | JP2004523662A (de) |
CN (1) | CN1509346A (de) |
AU (1) | AUPR443901A0 (de) |
CA (1) | CA2443953A1 (de) |
NO (1) | NO20034548L (de) |
WO (1) | WO2002083989A1 (de) |
ZA (1) | ZA200307978B (de) |
Families Citing this family (9)
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 (de) * | 2010-12-24 | 2012-06-27 | Philip Morris Products S.A. | Reduziertes keramisches Heizelement |
KR101655143B1 (ko) * | 2013-12-20 | 2016-09-07 | 현대자동차 주식회사 | 연료 전지 수소 공급 시스템의 원료 재생 방법 |
CN109055985B (zh) * | 2018-09-12 | 2019-09-27 | 郑州大学 | 一种电解氧化镁用熔盐体系、制备方法及其应用 |
KR102004920B1 (ko) * | 2019-01-28 | 2019-07-29 | 한국지질자원연구원 | 액체금속 음극을 이용한 금속 제련 방법 |
CN110219021B (zh) * | 2019-06-19 | 2024-05-24 | 陕西均健佳实业有限公司 | 一种镁电解槽及镁电解工艺 |
Family Cites Families (11)
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 (fr) * | 1980-07-23 | 1982-01-29 | Pechiney Aluminium | Procede et appareillage pour reguler de facon precise la cadence d'introduction et la teneur en alumine d'une cuve d'electrolyse ignee, et application a la production d'aluminium |
BR8207776A (pt) * | 1981-07-01 | 1983-05-31 | Diamond Shamrock Corp | Producao eletrolitica de aluminio |
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 |
US5378325A (en) * | 1991-09-17 | 1995-01-03 | Aluminum Company Of America | Process for low temperature electrolysis of metals in a chloride salt bath |
US5279715A (en) * | 1991-09-17 | 1994-01-18 | Aluminum Company Of America | Process and apparatus for low temperature electrolysis of oxides |
US5593566A (en) * | 1995-06-09 | 1997-01-14 | General Motors Corporation | Electrolytic production process for magnesium and its alloys |
AU2002349216B2 (en) * | 2001-11-22 | 2006-04-27 | Qit-Fer Et Titane Inc. | A method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state |
-
2001
- 2001-04-10 AU AUPR4439A patent/AUPR443901A0/en not_active Abandoned
-
2002
- 2002-04-10 JP JP2002581721A patent/JP2004523662A/ja active Pending
- 2002-04-10 US US10/474,746 patent/US20040237710A1/en not_active Abandoned
- 2002-04-10 CN CNA028100840A patent/CN1509346A/zh active Pending
- 2002-04-10 EP EP02713941A patent/EP1392890A4/de not_active Withdrawn
- 2002-04-10 CA CA002443953A patent/CA2443953A1/en not_active Abandoned
- 2002-04-10 WO PCT/AU2002/000456 patent/WO2002083989A1/en active Application Filing
-
2003
- 2003-10-09 NO NO20034548A patent/NO20034548L/no not_active Application Discontinuation
- 2003-10-14 ZA ZA200307978A patent/ZA200307978B/en unknown
-
2007
- 2007-10-26 US US11/924,808 patent/US20080110764A1/en not_active Abandoned
Non-Patent Citations (2)
Title |
---|
No further relevant documents disclosed * |
See also references of WO02083989A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2443953A1 (en) | 2002-10-24 |
NO20034548D0 (no) | 2003-10-09 |
AUPR443901A0 (en) | 2001-05-17 |
US20080110764A1 (en) | 2008-05-15 |
CN1509346A (zh) | 2004-06-30 |
US20040237710A1 (en) | 2004-12-02 |
NO20034548L (no) | 2003-12-01 |
JP2004523662A (ja) | 2004-08-05 |
EP1392890A4 (de) | 2004-10-06 |
WO2002083989A1 (en) | 2002-10-24 |
ZA200307978B (en) | 2004-09-03 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 20031020 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
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AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
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A4 | Supplementary search report drawn up and despatched |
Effective date: 20040824 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20091103 |