EP1794334A1 - Preparation de produits chimiques a base de zinc a partir du flux secondaire d'un processus - Google Patents
Preparation de produits chimiques a base de zinc a partir du flux secondaire d'un processusInfo
- Publication number
- EP1794334A1 EP1794334A1 EP05779682A EP05779682A EP1794334A1 EP 1794334 A1 EP1794334 A1 EP 1794334A1 EP 05779682 A EP05779682 A EP 05779682A EP 05779682 A EP05779682 A EP 05779682A EP 1794334 A1 EP1794334 A1 EP 1794334A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- extraction
- preparation
- dissolving
- 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- Withdrawn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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 64
- 239000011701 zinc Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 19
- 238000004090 dissolution Methods 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000011686 zinc sulphate Substances 0.000 claims abstract description 11
- 235000009529 zinc sulphate Nutrition 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 5
- HLQQMPGKASWZPH-UHFFFAOYSA-N diethyl hexyl phosphate Chemical compound CCCCCCOP(=O)(OCC)OCC HLQQMPGKASWZPH-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003016 phosphoric acids Chemical class 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- -1 co¬ balt Chemical compound 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/385—Thiophosphoric acids, or esters thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to the preparation processes of zinc and zinc chemicals. To be more precise, the invention relates to a process arrangement and circuit for preparing zinc chemicals in connection with a hydrometallurgical purification and preparation process of zinc.
- the primary production refers to various dissolutions of zinc ores, zinc concentrates and calcines and the treatment of solutions obtained therefrom by means of various hydrometallurgical methods, including liquid- liquid extraction.
- the secondary production refers to the use of various raw ma ⁇ terials of lesser volumes, such as particulates of electric furnaces, Waeltz ox ⁇ ides and galvanizing cinders, as raw material.
- the solution ob- tained from the neutral dissolution contains bivalent iron, cadmium, copper, co ⁇ balt, nickel, calcium, manganese and chlorides.
- the solu ⁇ tion obtained from the neutral dissolution is purified by a multi-stage solution purification process.
- the solution purification comprises three stages, wherein copper, cobalt, nickel, and finally, cadmium are removed.
- the zinciferous sulphate solution obtained from the neutral dissolution is also suitable for a feed material in the leaching method of zinc.
- the liquid-liquid extraction has been used for zinc preparation mainly in small-scale processes that employ secondary raw materials.
- the US Patent 5,135,652 describes a solvent extraction that can be used to selectively sepa ⁇ rate zinc from the zinc sulphate solution, which may contain zinc sulphate up to its saturation concentration, and one or more of a group containing the follow- ing: bivalent iron, trivalent iron, calcium, magnesium, manganese, sodium, po ⁇ tassium, arsenic, antimony, copper, cadmium, germanium, and indium.
- the purpose of this invention is to provide a new kind of a process arrangement for producing pure zinc chemicals from the minor flow of a zinc preparation process of a calcining-dissolving-electrolysis type.
- the invention is based on the fact that part of the production of the zinc sulphate-containing solution ob ⁇ tained from the dissolving of the calcining-dissolving-electrolysis plant is di ⁇ rected to the preparation of zinc chemicals. As only part of the production of the zinc sulphate solution is directed to the preparation of zinc chemicals, the ac- tual recovery process of zinc that is based on the electrolysis is not disturbed.
- the preparation process of zinc chemicals is based on a selective separation of zinc by extraction with known extraction techniques.
- the known extraction process is based on the use of any organically substituted phosphoric acid or organically substituted thiophosphinic acid.
- the extraction process is con ⁇ nected to the calcining-dissolving-electrolysis process described above.
- the invention provides considerable advantages.
- the bottleneck of the production lies in the elec ⁇ trolysis process.
- the solution according to the invention for taking the minor flow to the preparation line of zinc chemicals adds value to the actual production process of zinc.
- the invention provides an advantageous process solution for the preparation of zinc chemicals of a lesser demand.
- a strong acid solution is generated as a by-product, which can simply be recycled to be exploited in the preparation process of zinc. In that case, no separate investments for the final treatment of the acid solution are needed.
- the invention comprises a process circuit and arrangement for preparing pure zinc chemicals from a zinc sulphate-containing solution by an extraction method, whereby the raw material flow of the extraction is separated as a minor flow from the calcining-dissolving-electrolysis type process line of zinc primary production after the neutral dissolving stage.
- Fig. 1 shows a simplified process chart of the calcining-dissolving-electrolysis type preparation process of zinc and the preparation stage of zinc chemicals connected thereto.
- a calcine 10 containing zinc oxide is dissolved in a sulphuric-acid solution in a neutral dissolution.
- the neutral dissolution is typi ⁇ cally carried out in several stages.
- a solution residue 12 which is not soluble in the dissolution and contains iron, among others, is directed to a strong acid dis ⁇ solution.
- a zinc sulphate-containing solution 11 is directed to a multi-stage solu ⁇ tion purification, wherein a zinc powder 14 is used to precipitate copper, cobalt, nickel and cadmium.
- The. solution-purified zinc sulphate solution 15 is directed to an electrolysis plant, wherein the zinc is recovered at cathodes 16 by means of electrolysis.
- the electrolyte, from which the zinc was recovered 17 contains a considerable amount of sulphuric acid, which is reintroduced by directing it to the strong acid dissolution, among others.
- the strong acid dissolution the acid is used up in reactions. Accordingly, in addition to the recycled acid, a cer- tain amount of pure acid is added into the process.
- the pH of the solution should not be raised too high. It is reasonable to adjust the pH of the neutral dissolution with fresh acid and, in addition, with an acid 18 that is obtained from the strong acid dissolution.
- a minor flow 13 is separated from the main flow 11 of the zinc sulphate-containing solution obtained from the neutral dissolution, and directed to the extraction of zinc.
- DEHPA diethylhexylphosphoric acid
- D2EHPA di-2-ethylhexylphosphoric acid
- Zinc is separated from the organic phase by stripping it with an acid-containing solution 21.
- the raffinate 19, which is generated in the extraction, contains sulphuric acid, among others, and is directed to the strong acid stage to be reused.
- the pure zinc can be recovered in a sul ⁇ phuric-acid solution, wherein the content of zinc can be up to 150g/l.
- Various pure zinc products can be prepared from this solution 20 by any known meth ⁇ ods, such as by chemical precipitation or evaporation.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20041163A FI117139B (fi) | 2004-09-08 | 2004-09-08 | Sinkkikemikaalien valmistaminen prosessin sivuvirrasta |
PCT/FI2005/000380 WO2006027412A1 (fr) | 2004-09-08 | 2005-09-06 | Preparation de produits chimiques a base de zinc a partir du flux secondaire d'un processus |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1794334A1 true EP1794334A1 (fr) | 2007-06-13 |
Family
ID=33041502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05779682A Withdrawn EP1794334A1 (fr) | 2004-09-08 | 2005-09-06 | Preparation de produits chimiques a base de zinc a partir du flux secondaire d'un processus |
Country Status (11)
Country | Link |
---|---|
US (1) | US20070253878A1 (fr) |
EP (1) | EP1794334A1 (fr) |
JP (1) | JP2008512569A (fr) |
CN (1) | CN100406593C (fr) |
AU (1) | AU2005281684A1 (fr) |
CA (1) | CA2577863A1 (fr) |
EA (1) | EA010853B1 (fr) |
FI (1) | FI117139B (fr) |
MX (1) | MX2007002750A (fr) |
PE (1) | PE20060757A1 (fr) |
WO (1) | WO2006027412A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102102148B (zh) * | 2010-12-15 | 2012-10-24 | 河南豫光锌业有限公司 | 铟萃余液的回收处理方法 |
CN103160688B (zh) * | 2013-04-17 | 2015-08-05 | 昆明奥赛美科技有限公司 | 锌粉置换法从含锗浸出液中制备锗精矿的方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3989607A (en) * | 1975-08-21 | 1976-11-02 | Bush Philip D | Solvent extraction and electrowinning of zinc and copper from sulfate solution |
US5084180A (en) * | 1990-10-25 | 1992-01-28 | Cominco Ltd. | Method for treating zinc-containing sulfate solution |
US5135652A (en) * | 1990-10-25 | 1992-08-04 | Cominco Ltd. | Method for the solvent extraction of zinc |
US5358700A (en) * | 1992-10-05 | 1994-10-25 | Cyprus Power Company | Method of extracting zinc from brines |
CN1040554C (zh) * | 1994-03-02 | 1998-11-04 | 张振逵 | 联产硫酸锌与铅精矿的工艺与装置 |
-
2004
- 2004-09-08 FI FI20041163A patent/FI117139B/fi active IP Right Grant
-
2005
- 2005-09-05 PE PE2005001018A patent/PE20060757A1/es not_active Application Discontinuation
- 2005-09-06 AU AU2005281684A patent/AU2005281684A1/en not_active Abandoned
- 2005-09-06 CN CNB2005800302299A patent/CN100406593C/zh not_active Expired - Fee Related
- 2005-09-06 WO PCT/FI2005/000380 patent/WO2006027412A1/fr active Application Filing
- 2005-09-06 MX MX2007002750A patent/MX2007002750A/es not_active Application Discontinuation
- 2005-09-06 EA EA200700420A patent/EA010853B1/ru not_active IP Right Cessation
- 2005-09-06 JP JP2007530727A patent/JP2008512569A/ja not_active Abandoned
- 2005-09-06 US US11/662,061 patent/US20070253878A1/en not_active Abandoned
- 2005-09-06 CA CA002577863A patent/CA2577863A1/fr not_active Abandoned
- 2005-09-06 EP EP05779682A patent/EP1794334A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2006027412A1 * |
Also Published As
Publication number | Publication date |
---|---|
PE20060757A1 (es) | 2006-09-14 |
US20070253878A1 (en) | 2007-11-01 |
FI20041163A0 (fi) | 2004-09-08 |
MX2007002750A (es) | 2007-05-18 |
CN101014723A (zh) | 2007-08-08 |
EA010853B1 (ru) | 2008-12-30 |
WO2006027412A1 (fr) | 2006-03-16 |
AU2005281684A1 (en) | 2006-03-16 |
CN100406593C (zh) | 2008-07-30 |
JP2008512569A (ja) | 2008-04-24 |
EA200700420A1 (ru) | 2007-10-26 |
FI117139B (fi) | 2006-06-30 |
FI20041163A (fi) | 2006-03-09 |
CA2577863A1 (fr) | 2006-03-16 |
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Legal Events
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