CA2443953A1 - Electrolytic reduction of metal oxides - Google Patents
Electrolytic reduction of metal oxides Download PDFInfo
- Publication number
- CA2443953A1 CA2443953A1 CA002443953A CA2443953A CA2443953A1 CA 2443953 A1 CA2443953 A1 CA 2443953A1 CA 002443953 A CA002443953 A CA 002443953A CA 2443953 A CA2443953 A CA 2443953A CA 2443953 A1 CA2443953 A1 CA 2443953A1
- Authority
- CA
- Canada
- 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.)
- Abandoned
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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 cell is disclosed. T he 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 th e 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 extendi ng into the electrolyte and a body of metal oxide to reduced in contact with th e molten metal and the electrolyte.
Description
ELECTROLYTIC REDUCTION OF METAL OXIDES
1. Field of the Invention The present invention relates to electrolytic reduction of metal oxides to produce substantially pure metals.
In particular, the present invention relates to electrolytic reduction of aluminium and magnesium oxides using a CaCl2 electrolyte.
1. Field of the Invention The present invention relates to electrolytic reduction of metal oxides to produce substantially pure metals.
In particular, the present invention relates to electrolytic reduction of aluminium and magnesium oxides using a CaCl2 electrolyte.
2. Background Art The present invention was made during the course of an on-going research project on the electrolytic reduction of metal oxides using CaCl2-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 CaCl2 electrolyte.
The CaCl2 electrolyte was a commercially available source of CaClz, namely calcium chloride dehydrate, 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 Ca0 and below the decomposition potential of CaCla.
The applicant found that the cells could electrolytically reduce a range of metal oxides to metals with very low concentrations of oxygen.
The research project investigated electrolytic reduction of a range of metal oxides in electrolyte cells based on the use of using CaCl2 electrolyte.
The CaCl2 electrolyte was a commercially available source of CaClz, namely calcium chloride dehydrate, 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 Ca0 and below the decomposition potential of CaCla.
The applicant found that the cells could electrolytically reduce a range of metal oxides to metals with very low concentrations of oxygen.
3. Summary of the Invention 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.
In the above method electrolytic reduction of metal oxide takes place where there is contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
Preferably the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte..
Preferably 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.
Preferably the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced.
Preferably 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.
Preferably the metal oxide is an aluminium oxide or a magnesium oxide.
In a situation in which the metal oxide is a aluminium oxide or magnesium oxide it is preferred that the electrolyte be a CaCl2-based electrolyte that includes Ca0 as one of the constituents.
In such a situation it is preferred that the cell potential be above the decomposition potential for CaO.
It is also preferred that the cell potential be below the decomposition potential for CaCl2.
It is preferred that the cell potential be less than 3.0V.
It is preferred particularly that the cell potential be below 2.5V.
It is preferred more particularly that the cell potential be below 2.0V.
It is preferred that the cell potential be at least 1.5V.
The CaCl2-based electrolyte may be a commercially available source of CaCl2, such as calcium chloride dehydrate, that partially decomposes on heating and produces Ca0 or otherwese includes CaO.
In the above method electrolytic reduction of metal oxide takes place where there is contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
Preferably the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte..
Preferably 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.
Preferably the method includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced.
Preferably 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.
Preferably the metal oxide is an aluminium oxide or a magnesium oxide.
In a situation in which the metal oxide is a aluminium oxide or magnesium oxide it is preferred that the electrolyte be a CaCl2-based electrolyte that includes Ca0 as one of the constituents.
In such a situation it is preferred that the cell potential be above the decomposition potential for CaO.
It is also preferred that the cell potential be below the decomposition potential for CaCl2.
It is preferred that the cell potential be less than 3.0V.
It is preferred particularly that the cell potential be below 2.5V.
It is preferred more particularly that the cell potential be below 2.0V.
It is preferred that the cell potential be at least 1.5V.
The CaCl2-based electrolyte may be a commercially available source of CaCl2, such as calcium chloride dehydrate, that partially decomposes on heating and produces Ca0 or otherwese includes CaO.
Alternatively, or in addition, the CaClz-based electrolyte may include CaCl2 and Ca0 that are added separately or pre-mised to form the electrolyte.
At this stage, the applicant does not have a clear understanding of the electrolytic cell mechanism when the cell is operated at a potential at which CaCl2-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 CaClz-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 O'-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.
It is preferred that the anode be graphite.
Preferably the cell includes a base and side walls extending upwardly from the base formed from graphite.
At this stage, the applicant does not have a clear understanding of the electrolytic cell mechanism when the cell is operated at a potential at which CaCl2-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 CaClz-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 O'-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.
It is preferred that the anode be graphite.
Preferably the cell includes a base and side walls extending upwardly from the base formed from graphite.
Preferably 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.
The following example illustrates an application of the invention in the process of reducing aluminium oxide (alumina) into substantially pure aluminium using an electrolytic cell as illustrated in Figure 1.
4. Description of Exemplary Embodiment Figure 1 is a schematic illustration of an electrolytic cell 5 that can be scaled-up in application of the present invention.
Whilst the example described below relates to the reduction of alumina, the basic principle is equally applicable to other metals, particularly low melting point metals, more particularly magnesium.
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 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.
The following example illustrates an application of the invention in the process of reducing aluminium oxide (alumina) into substantially pure aluminium using an electrolytic cell as illustrated in Figure 1.
4. Description of Exemplary Embodiment Figure 1 is a schematic illustration of an electrolytic cell 5 that can be scaled-up in application of the present invention.
Whilst the example described below relates to the reduction of alumina, the basic principle is equally applicable to other metals, particularly low melting point metals, more particularly magnesium.
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 CaCl2 electrolyte 13 a.n 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 of molten aluminium in a lower section of the crucible 10 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 (A1203) to be 15 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 CaCl2 electrolyte is and remains molten. On immersion of the alumina body 14 into the electrolyte 13 and subsequent contact of the alumina body 14 with the molten aluminium cathode 15, 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.
In order to maintain optimum reduction COnd7.tlonS, 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 i.s 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.
Many modifications may be made to the embodiment of the present invention described above without departing from the spirit and scope of the present invention.
The electrolytic cell 5 further includes a pool of molten aluminium in a lower section of the crucible 10 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 (A1203) to be 15 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 CaCl2 electrolyte is and remains molten. On immersion of the alumina body 14 into the electrolyte 13 and subsequent contact of the alumina body 14 with the molten aluminium cathode 15, 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.
In order to maintain optimum reduction COnd7.tlonS, 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 i.s 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.
Many modifications may be made to the embodiment of the present invention described above without departing from the spirit and scope of the present invention.
Claims (15)
1. 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 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, a pool of molten electrolyte in contact with the molten metal, the electrolyte containing alkali and/or alkaline earth halides, an anode extending into the electrolyte, and a body of metal oxide to reduced in contact with the molten metal and the electrolyte.
2. The method defined in claim 1 wherein the metal oxide body has a geometric shape that maximises contact between (i) the molten metal, (ii) the metal oxide, and (iii) the electrolyte.
3. The method defined in claim 1 or claim 2 includes feeding the metal oxide body into the electrolytic cell to maintain contact of the metal oxide and the molten metal.
4. The method defined in any one of the preceding claims wherein the metal oxide body includes rods, plates and blocks that can be readily immersed into the electrolyte and brought into contact with the molten metal.
5. The method defined in any one of the preceding claims includes maintaining the cell temperature above the melting points of the electrolyte and the metal of the metal oxide to be reduced.
6. The method defined in any one of the preceding claims 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.
7. The method defined in any one of the preceding claims wherein the metal oxide is an aluminium oxide or a magnesium oxide.
8. The method defined in claim 7 wherein the electrolyte is a CaCl2-based electrolyte that includes CaO
as one of the constituents.
as one of the constituents.
9. The method defined in claim 8 includes maintaining the cell potential above the decomposition potential for CaO.
10. The method defined in claim 8 or claim 9 includes maintaining the cell potential below the decomposition potential for CaCl2.
11. The method defined in claim 10 includes maintaining the cell potential less than 3.0V.
12. The method defined in claim 10 includes maintaining the cell potential less than 2.5V.
13. The method defined in claim 10 includes maintaining the cell potential less than 2.0V.
14. The method defined in any one of claims 8 to 13 includes maintaining the cell potential to be at least 1.5V.
15. The method defined in any one of the preceding claims wherein the cell includes at least one tap hole for molten metal and the method includes removing molten metal continuously or periodically via the tap hole.
Applications Claiming Priority (3)
| 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 |
| PCT/AU2002/000456 WO2002083989A1 (en) | 2001-04-10 | 2002-04-10 | Electrolytic reduction of metal oxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2443953A1 true CA2443953A1 (en) | 2002-10-24 |
Family
ID=3828435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002443953A Abandoned CA2443953A1 (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) |
Families Citing this family (12)
| 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 |
| US20100323253A1 (en) * | 2006-02-22 | 2010-12-23 | University Of Utah Resarch 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 |
| KR101655143B1 (en) * | 2013-12-20 | 2016-09-07 | 현대자동차 주식회사 | Regeneration method of raw materials for hydrogen supply system of fuel cell |
| 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 |
| KR102004920B1 (en) * | 2019-01-28 | 2019-07-29 | 한국지질자원연구원 | Metal refining method by using liquid metal cathode |
| 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 |
| KR102386696B1 (en) * | 2020-11-17 | 2022-04-15 | 주식회사 케이에스엠테크놀로지 | Reduction System and Method of Refractory Metal Oxides Using Liquid Metal Crucible |
| EP4249644A4 (en) * | 2020-11-17 | 2024-10-30 | Ksm Tech Co Ltd | Reduction method and system for high-melting-point metal oxide, using fluoride-based electrolytes |
| WO2024177534A1 (en) * | 2023-02-20 | 2024-08-29 | Общество с ограниченной ответственностью "Институт легких материалов и технологий" | Method and device for electrorefining aluminium in electrolysis cells (embodiments) |
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 (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 |
| 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 |
| WO2003046258A2 (en) * | 2001-11-22 | 2003-06-05 | 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 US US10/474,746 patent/US20040237710A1/en not_active Abandoned
- 2002-04-10 EP EP02713941A patent/EP1392890A4/en not_active Withdrawn
- 2002-04-10 WO PCT/AU2002/000456 patent/WO2002083989A1/en active Application Filing
- 2002-04-10 JP JP2002581721A patent/JP2004523662A/en active Pending
- 2002-04-10 CN CNA028100840A patent/CN1509346A/en active Pending
- 2002-04-10 CA CA002443953A patent/CA2443953A1/en not_active Abandoned
-
2003
- 2003-10-09 NO NO20034548A patent/NO20034548L/en 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
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004523662A (en) | 2004-08-05 |
| EP1392890A1 (en) | 2004-03-03 |
| NO20034548D0 (en) | 2003-10-09 |
| US20040237710A1 (en) | 2004-12-02 |
| AUPR443901A0 (en) | 2001-05-17 |
| ZA200307978B (en) | 2004-09-03 |
| NO20034548L (en) | 2003-12-01 |
| CN1509346A (en) | 2004-06-30 |
| US20080110764A1 (en) | 2008-05-15 |
| EP1392890A4 (en) | 2004-10-06 |
| WO2002083989A1 (en) | 2002-10-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |