EP1458906A2 - Elektrochemischer prozess zur herstellung von metallischem zink - Google Patents
Elektrochemischer prozess zur herstellung von metallischem zinkInfo
- Publication number
- EP1458906A2 EP1458906A2 EP02785828A EP02785828A EP1458906A2 EP 1458906 A2 EP1458906 A2 EP 1458906A2 EP 02785828 A EP02785828 A EP 02785828A EP 02785828 A EP02785828 A EP 02785828A EP 1458906 A2 EP1458906 A2 EP 1458906A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrochemical process
- zinc
- electrochemical
- zinc oxide
- solution
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011701 zinc Substances 0.000 title claims abstract description 35
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011787 zinc oxide Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 239000002585 base Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000003637 basic solution Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- PENRVBJTRIYHOA-UHFFFAOYSA-L zinc dithionite Chemical compound [Zn+2].[O-]S(=O)S([O-])=O PENRVBJTRIYHOA-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
Definitions
- the present invention provides an electrochemical process for the preparation of zinc metal.
- Zinc powder is widely used in the chemical industry in various industries. Zinc oxide containing other zinc salts, metal impurities, etc. is produced as a byproduct. Recycling of the zinc oxide to produce pure zinc powder is highly desirable from a cost as well as an environmental point of view.
- the electrodeposition of zinc metal is a well-known reaction in electrochemical technology (See, for example, D. Pletcher and F.C. Walsh, Industrial Electrochemistry, Blackie Academic, 1993).
- the electrogalvanizing of steel is a process carried out on a very large scale and aqueous acid is the normal medium.
- High speed, reel to reel galvanizing of steel is carried out in sulfuric acid with dimensionally stable anodes and uniform deposition is achieved at high current density by inducing very efficient mass transport by rapid movement of the steel surface.
- the deposition of zinc metal is also the critical electrode reaction in the electrowinning and electrorefining of zinc.
- Zinc metal can be produced by electrolysis either in strong alkaline or neutral zinc containing solutions.
- the first patents obtained on the alkaline electrolysis process date back to the early thirties (German Patents, 581013, 506590, 653557). In these methods, a low current density of 1200-1500 amperes/sq. meter (Mm 2 ) was used. Volume efficiency and current density of these batch type processes are too low to be industrially attractive.
- I. Orszagh and B. Vass Hung. J. Ind. Chem., 13, (1985) 287) used these methods to recycle zinc oxide byproduct from zinc dithionite production. There is at present a need to carry out an electrolysis reaction to produce zinc metal under conditions where corrosion of the electrodes is minimized.
- the present invention fulfils this and other needs.
- the present invention provides a low corrosion electrochemical process for preparing zinc metal wherein air or nitrogen is bubbled in during the electrochemical reduction process producing the zinc metal. It has been unexpectedly found that bubbling of air or nitrogen reduces electrode corrosion during the electrochemical process.
- U.S. Patent No. 5,958,210 discloses a method for electrowinning metallic zinc from zinc ion in aqueous solution, said method comprising performing electrolysis on a mixture of solid conductive particles and aqueous alkali solution, said solution ranging in concentration from about 3N to about 20N alkali and containing dissolved zinc ion at an initial concentration ranging from about 50 to about 500 grams of zinc ion per liter of said solution, in an electrolytic cell containing first and second vertically arranged, parallel flat plates defined as a current feeder and a counter electrode, respectively, said counter electrode coated with a substance that is catalytic for oxygen evolution, said cell further containing an ion-permeable diaphragm parallel to each of said plates and interposed therebetween to define a gap between said current feeder and said diaphragm, by passing said mixture of particles and solution through said gap such that said particles contact said current feeder and passing a current across said gap, thereby depositing metallic zinc from said solution onto said particles.
- U.S. Patent Application serial number 09/776,518 discloses an electrochemical process for preparing zinc powder which involves: a) providing to an electrochemical cell a basic solution of zinc oxide or any other zinc compound that reacts with an aqueous base to produce zinc oxide, the basic solution prepared by dissolving the zinc oxide or the other zinc compound in an aqueous 2.5 to 10.0 M base solution; and b) passing current to the cell at a current density of about 10,000 to about 40,000 A/m 2 for a time period sufficient to electrochemically reduce the zinc oxide to zinc powder, wherein the electrochemical process has a current efficiency of at least 70% and is substantially free from electrode corrosion.
- U.S. Patent Application serial number 09/776,644 discloses a continuous electrochemical process for preparing zinc powder which involves: providing to an electrochemical cell a solution or suspension in an aqueous 1.25 Molar to 10.0 Molar base solution of zinc oxide or any other zinc compound that reacts with an aqueous base to produce zinc oxide, the solution or suspension containing at least 2 millimoles of solubilized zinc based species per 100 grams of electrolyte; and b) passing current to the cell at a current density of about 500 to 40,000 A/m 2 , for a time period sufficient to electrochemically reduce the solubilized zinc based species to zinc powder, while continuously or intermittently adding a sufficient amount of the zinc oxide or the other zinc compound to the cell to maintain the concentration of the solubilized zinc based species at a level of at least 2 millimoles per 100 grams of electrolyte and continuously or intermittently removing at least a portion of the zinc powder formed; wherein the electrolyte includes the aqueous 1.25 Molar to
- the present invention provides a low corrosion electrochemical process for preparing zinc metal which comprises electrochemically reducing an aqueous basic solution or slurry of zinc oxide or any other zinc compound that reacts with an aqueous base to produce zinc oxide, wherein the electrochemical process is carried out in an undivided electrochemical cell, and wherein air or nitrogen is bubbled in through the solution or slurry of zinc oxide or said other zinc compound during said electrochemical process.
- the present invention provides a low corrosion electrochemical process for preparing zinc metal which comprises electrochemically reducing an aqueous basic solution or slurry of zinc oxide or any other zinc compound (such as zinc sulfate) that reacts with an aqueous base to produce zinc oxide, wherein the electrochemical process is carried out in an undivided electrochemical cell, and wherein air or nitrogen is bubbled in through the solution or slurry of zinc oxide or said other zinc compound during said electrochemical process.
- any other zinc compound such as zinc sulfate
- the anode may be made from any conventional suitable material such as platinum, or iridium, either of which may be coated over an inert support such as niobium or titanium.
- the anode may also be made of nickel, or from conventional materials having good alkali corrosion resistance, e.g., lead or stainless steel.
- the cathode may be made from any conventional suitable materials having good alkali corrosion resistance, such as magnesium, magnesium alloy, copper, lead and stainless steel.
- the anode in the present invention is formed of stainless steel or nickel and the cathode is formed of stainless steel, magnesium, magnesium alloy or copper.
- the cathode and the anode are stainless steel and copper respectively, and in one embodiment nickel and copper respectively.
- aqueous base solutions employed in the process of the invention are prepared by combining water with a source of alkali metal or alkaline earth metal ions, such as lithium, sodium, and potassium, and a source of hydroxyl (OH " ions).
- a source of alkali metal or alkaline earth metal ions such as lithium, sodium, and potassium
- OH " ions hydroxyl
- a single source may of course provide both types of ions.
- the various alkali or alkaline earth metal ions are preferably supplied from various compounds such as hydroxides and oxides.
- Preferred base solutions are sodium and potassium hydroxide solutions.
- temperatures higher than ambient are generally desired because of the beneficial effects on the kinetics of all steps in an electrode process.
- the diffusion coefficient, the exchange current density and the rates of chemical reactions generally are increased.
- the decrease in viscosity and increase in diffusion coefficient leads to the increased mass transport rates.
- This increased mass transport of zinc ions from the bulk of the solution to the cathodic region is highly desirable.
- increase in the rate of chemical reaction such as the oxidation of zinc produced with oxygen and mass transport of the byproduct oxygen to the bulk of the solution may not be desirable.
- higher than ambient temperatures are found to be favorable for the electrolytic reduction of zinc oxide to zinc, and are preferred.
- the presently claimed electrochemical reduction process is conducted at a temperature of from 10°C to 105°C, preferably from 40° to 80°C, and more preferably from 60° to 75°C.
- the electrochemical process of the present invention is a continuous process.
- continuous in the present context is well understood by one of ordinary skill in the art.
- it relates a process wherein zinc oxide or the other zinc compound can be added continuously to the electrochemical cell and at least a portion of the zinc metal formed is removed continuously or intermittently during the electrochemical process.
- a continuous electrochemical process has been disclosed in U.S. Application serial number 09/776,664 (filed February 2, 2001).
- a resin Kettle (5 inch in diameter and 18 inch high) is used as the cell.
- a solution or slurry of zinc oxide in the aqueous sodium hydroxide solution (3 to 3.5 liters) at 20 to 80°C is charged into the resin kettle.
- a thermometer, desired cathodes and anodes are positioned in the cell using laboratory clamps. Mixing is achieved by bubbling air or nitrogen through the solution or slurry of ZnO. In some experiments mechanical stirring in addition to bubbling of air or nitrogen is used. Control experiments use only mechanical stirring for mixing (no air or nitrogen bubbling). Parts of the cathode and anode surfaces are covered with Teflon tape to achieve the desired active cathode and anode surface areas.
- Electrolysis is carried out at a current density of about 5000 Amps/m 2 . A portion of the zinc deposited on the cathode is removed periodically. At the end of the experiment, zinc particles are separated from the electrolyte by decantation, washed with water and then dried. Dried zinc particles were analyzed to determine the zinc content.
- All slurry based electrolysis contained undissolved ZnO in the electrolyte during the entire electrolysis.
- Zn particles deposited on the copper cathode were easily removable.
- the precision of the corrosion results is about ⁇ 1g/45.5 kg Zn (the values expressed in g/45.5 kg Zn are normalized values).
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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/015,185 US20030106806A1 (en) | 2001-12-07 | 2001-12-07 | Electrochemical process for preparation of zinc metal |
| US15185 | 2001-12-07 | ||
| PCT/IB2002/005133 WO2003048425A2 (en) | 2001-12-07 | 2002-12-05 | Electrochemical process for preparation of zinc metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1458906A2 true EP1458906A2 (de) | 2004-09-22 |
Family
ID=21769971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02785828A Withdrawn EP1458906A2 (de) | 2001-12-07 | 2002-12-05 | Elektrochemischer prozess zur herstellung von metallischem zink |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20030106806A1 (de) |
| EP (1) | EP1458906A2 (de) |
| AU (1) | AU2002351115A1 (de) |
| WO (1) | WO2003048425A2 (de) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2630469A1 (en) * | 2005-11-22 | 2007-05-31 | Paul R. Kruesi | Methods of recovering and purifying secondary aluminum |
| US8409419B2 (en) * | 2008-05-21 | 2013-04-02 | Paul R. Kruesi | Conversion of carbon to hydrocarbons |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE653557C (de) * | 1936-08-16 | 1937-11-27 | I G Farbenindustrie Akt Ges | Herstellung von Zinkstaub |
| DE4429195A1 (de) * | 1994-08-18 | 1996-02-22 | Dechema | Verfahren zur elektrolytischen Zinkabscheidung aus alkalischen zyanidfreien Elektrolyten |
| DE4438692C2 (de) * | 1994-10-29 | 2003-05-28 | Outokumpu Oy | Verfahren zur elektrochemischen Gewinnung der Metalle Kupfer, Zink, Blei, Nickel oder Kobalt |
| US20030183535A1 (en) * | 2002-03-28 | 2003-10-02 | Clariant International Ltd. | Process for the preparation of zinc dithionite |
-
2001
- 2001-12-07 US US10/015,185 patent/US20030106806A1/en not_active Abandoned
-
2002
- 2002-12-05 EP EP02785828A patent/EP1458906A2/de not_active Withdrawn
- 2002-12-05 WO PCT/IB2002/005133 patent/WO2003048425A2/en not_active Ceased
- 2002-12-05 AU AU2002351115A patent/AU2002351115A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03048425A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002351115A1 (en) | 2003-06-17 |
| WO2003048425A3 (en) | 2004-03-18 |
| WO2003048425A2 (en) | 2003-06-12 |
| US20030106806A1 (en) | 2003-06-12 |
| AU2002351115A8 (en) | 2003-06-17 |
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| 18W | Application withdrawn |
Effective date: 20040827 |