EP1242653A1 - Cellule electrochimique pour electrolyseurs con ue selon la technique des elements individuels - Google Patents
Cellule electrochimique pour electrolyseurs con ue selon la technique des elements individuelsInfo
- Publication number
- EP1242653A1 EP1242653A1 EP00976055A EP00976055A EP1242653A1 EP 1242653 A1 EP1242653 A1 EP 1242653A1 EP 00976055 A EP00976055 A EP 00976055A EP 00976055 A EP00976055 A EP 00976055A EP 1242653 A1 EP1242653 A1 EP 1242653A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrochemical cell
- support
- cell according
- cathode
- support elements
- 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.)
- Granted
Links
- 238000005516 engineering process Methods 0.000 title abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 229910045601 alloy Inorganic materials 0.000 claims 2
- 239000000956 alloy Substances 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 2
- 229910001252 Pd alloy Inorganic materials 0.000 claims 1
- 229910001069 Ti alloy Inorganic materials 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000012491 analyte Substances 0.000 abstract 2
- 230000036284 oxygen consumption Effects 0.000 description 16
- 125000006850 spacer group Chemical group 0.000 description 8
- 238000003825 pressing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920001780 ECTFE Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000009420 retrofitting Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/63—Holders for electrodes; Positioning of the electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
Definitions
- the invention relates to an electrochemical cell for electrolysers with single-element technology for the membrane electrolysis process according to the preamble of claim 1.
- the cell consists of at least 2 half-shells which surround an anolyte compartment and a cathode compartment with a membrane arranged therebetween, an anode in the anolyte compartment, the cathode compartment having a Oxygen consumption cathode is provided with a plurality of pressure-compensated gas pockets arranged one above the other, a catholyte gap and optionally a back space, electrically conductive support elements in the anolyte space and support elements in the cathode space being provided in the same opposite position.
- Electrolysers e.g. for NaCl electrolysis are known for the bipolar mode of operation in two fundamentally known basic techniques.
- the cell elements are arranged half-shell welded back to back within the frame, with the anode and cathode each lying free-standing on the outside and the ion exchange membrane inserted between two elements forming the electrochemical cell.
- the current from cell to cell flows here via the weld seams between the half-shells.
- the electrochemical cell is formed by two individual half-shells, between which a membrane is placed, and which are then screwed into a single element.
- the electrical contacting from individual element to individual element takes place here by pressing one
- Gas straps as in US Pat. No. 5,963,202 in the basic principle and in German Offenlegungsschrift DE 196 22 744 AI described for gas pockets with active gas flow, is carried out with an electrolyte gap between the oxygen-consuming cathode and the membrane.
- the gas pocket itself represents an empty volume.
- Both structures, which are undefined for the force transmission, must be bridged with a system suitable for the transmission of the tension forces.
- the clamping force is to be used for a further improvement of the current distribution in the oxygen consumption cathode via press contacts.
- the gas pockets with the oxygen consumable cathodes usually extend over the entire width of the electrolytic cell.
- the structures for passing the gases usually extend over the entire width of the electrolytic cell.
- an electrochemical cell for the membrane electrolysis process consisting of at least two half-shells which surround an anolyte compartment and a cathode compartment with a membrane arranged therebetween, an anode in the anolyte compartment, the cathode compartment having one oxygen-consuming cathode and several one above the other arranged pressure-compensated gas pockets, a catholyte gap and optionally a back space is provided, which is characterized in that electrically conductive support elements are provided in the anolyte space and further support elements in the cathode space in the same, opposite position, which act on the half-shell walls
- a preferred embodiment of the electrochemical cell is characterized in that the support in the cathode compartment is carried out by means of a multi-part support element, one support part in the catholyte gap, another support part in the gas pocket and, in the presence of a rear space, a third support part is arranged in the rear space behind the gas pockets.
- the back of the gas pockets is welded in particular to the vertical support elements for power and current transmission.
- Structural beams or other types of vertically extending structural bridges are welded into the gas pocket as support elements, which are so high that they have the same level with the circumferential outer edge of the gas pocket.
- these internals must allow a horizontal gas flow through the gas pocket and at the lower edge also a horizontal drain of possible condensate.
- the oxygen consumption cathodes After installing the oxygen consumption cathodes, they lie flat on the structural beams or bridges and the edge of the gas pockets, for example, and form a flat surface over the full width and the respective height of the gas pocket.
- a support element as a support element made of electrolyte and heat-resistant material is used as a counterpart to the above.
- the support element (spacer) is preferably not installed in one piece in the cell for the following reasons.
- the segments of the support elements are attached or guided in particular at the top and bottom according to the following scheme: at the top they are attached to the edge of the gas pocket. This can be done either via a pin or a kind of push button either on the spacer or at the top of the gas pocket, whereby the opposite part must contain a corresponding hole.
- a preferred variant of the invention is therefore characterized in that the support part in the catholyte gap is formed from a plurality of bars arranged vertically one above the other, which are optionally attached at their upper end with a releasable connecting means, for example a snap connector, to cross struts which carry the electrode.
- a releasable connecting means for example a snap connector
- the support element ends in a dovetail-shaped structure which surrounds the tapering upper end of the next support element underneath and thus ensures the horizontal positioning of the support element.
- the gap between these two segments is expediently chosen so that the greater thermal expansion of the support element compared to the metallic structures is compensated for.
- the respectively adjacent ends of the support parts are therefore designed as a tongue and groove combination, the upper end of the respective lower support part being designed in particular as a spring.
- the second support part in the gas pockets particularly preferably has openings at selected points, in particular in its upper and lower region of the respective gas pocket, or leaves passages free.
- the second support part is particularly preferably designed either as a solid electrically conductive ingot or as a U-shaped profile, or else as a corresponding vertical embossing of the back of the gas pocket.
- the structural beams or bridges can be provided with slight vertical bulges either on the right and left or in the middle, which correspond to a corresponding shaping of the support elements, so that this is repeated when the electrolyzer is clamped is centered on the opposite structure.
- the back of the oxygen consumption cathode should in particular be electrically conductive.
- this creates a further electrical connection by press contact via the electrically conductive support elements, which leads to a further minimization of the ohmic losses.
- the use of the support element prevents the oxygen-consuming cathode from bulging over a large area into the catholyte gap, with the risk of local blockage of the catholyte flow due to contact with the membrane. This applies in particular to the above Structuring of the support elements through which the oxygen consumption cathode is stretched.
- the support elements in the catholyte gap are expediently made of ECTFE, FEP, MFA or PFA, in particular in the case of chloralkali electrolysis, while the electrically conductive support elements, for example structural beams or bridges, should be made of nickel or another alkali-resistant metal alloy or directly from the back wall of the gas pocket are embossed.
- the support elements in the catholyte gap on the side facing the oxygen consumption cathode can be metallic in order to obtain an improvement in the current distribution into the oxygen consumption cathode via the press contact.
- the support elements are preferably constructed in two layers, the side facing the membrane consisting of ECTFE, FEP, MFA or PFA, while the metallic part consists of alkali-resistant metal.
- Electrolysis with gas diffusion electrodes in direct contact with liquid electrolytes that require pressure compensation can be used, e.g.
- Fig. 1 shows a longitudinal section through a cathode half-shell of a cell according to the invention as a section of the upper left corner.
- Fig. 2 shows a cross section along the line A-A 'in Fig. 1 through the electrochemical cell
- FIG. 3 shows a longitudinal section through a cathode half-shell along the line BB 'in FIG. 1 Examples
- FIG. 1 the view of the cathode half-shell with the upper left corner is shown as a cutout, in FIG. 2 a horizontal section A-A 'through a gas pocket 1.
- the gas pocket structure with the rear wall 11 and the lateral border 9 is carried over the support structure 3.
- the vertical structural beam 2a or, according to a variant shown in the same FIG. 2 or 3, the vertical structural bridge 2b are welded into the gas pocket 15.
- both structures are broken through and do not stand on the horizontal boundary 12 of the gas pocket 15 in order to allow any condensates that may occur to flow away from the oxygen consumption cathode.
- the oxygen consumption cathode 4 is attached to and on the lateral border 9 and the horizontal boundary 12 in an electrically conductive and gas-tight manner and lies on the structural beams or bridges.
- the catholyte gap 14 between the membrane 5 and the oxygen-consuming cathode 4 is defined by the spacer elements 1, which in turn are supported by the membrane on the anode 6, which is held in a defined manner in the anode half-shell 8 via the support structure 7 (see FIG. 2).
- Anode half-shell 8 and cathode half-shell 10 are connected to one another in a liquid-tight manner and form a single element (electrolysis cell).
- electrolysis cell electrolysis cell
- the spacer elements la, lb themselves are tapered at the top and provided with a corresponding dovetail structure at the bottom (FIG. 1). They are attached to the horizontal boundary 12 of the gas pocket 15 at the top with a pin or a push-button-like holding device 13.
- the dovetail of the spacer element lb reaches over the tip of the next spacer element la underneath and is thus clearly positioned.
- a defined gap between the spacer elements la, lb enables their free thermal
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Secondary Cells (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19959079A DE19959079A1 (de) | 1999-12-01 | 1999-12-01 | Elektrochemische Zelle für Elektrolyseure mit Einzelelementtechnik |
DE19959079 | 1999-12-01 | ||
PCT/EP2000/011531 WO2001040549A1 (fr) | 1999-12-01 | 2000-11-20 | Cellule electrochimique pour electrolyseurs conçue selon la technique des elements individuels |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1242653A1 true EP1242653A1 (fr) | 2002-09-25 |
EP1242653B1 EP1242653B1 (fr) | 2005-04-06 |
Family
ID=7931798
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00976055A Expired - Lifetime EP1242653B1 (fr) | 1999-12-01 | 2000-11-20 | Cellule electrochimique pour electrolyseurs con ue selon la technique des elements individuels |
Country Status (22)
Country | Link |
---|---|
US (1) | US6984296B1 (fr) |
EP (1) | EP1242653B1 (fr) |
JP (1) | JP2003515677A (fr) |
KR (1) | KR20020059830A (fr) |
CN (1) | CN1258619C (fr) |
AT (1) | ATE292695T1 (fr) |
AU (1) | AU775645B2 (fr) |
BR (1) | BR0015952A (fr) |
CA (1) | CA2394835A1 (fr) |
CZ (1) | CZ20021886A3 (fr) |
DE (2) | DE19959079A1 (fr) |
ES (1) | ES2240198T3 (fr) |
HK (1) | HK1054412A1 (fr) |
HU (1) | HUP0203519A3 (fr) |
MX (1) | MXPA02005480A (fr) |
NO (1) | NO20022575L (fr) |
PL (1) | PL355720A1 (fr) |
PT (1) | PT1242653E (fr) |
RU (1) | RU2002118331A (fr) |
WO (1) | WO2001040549A1 (fr) |
YU (1) | YU39402A (fr) |
ZA (1) | ZA200203202B (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20021524A1 (it) * | 2002-07-11 | 2004-01-12 | De Nora Elettrodi Spa | Cella con elettrodo a letto in eruzione per elettrodeposiwione di metalli |
JP4899294B2 (ja) * | 2004-06-10 | 2012-03-21 | 株式会社日立製作所 | 水素燃料製造システム,水素燃料製造方法および水素燃料製造プログラム |
DE102005003527A1 (de) * | 2005-01-25 | 2006-07-27 | Uhdenora S.P.A. | Elektrolysezelle mit erweiterter aktiver Membranfläche |
IT1391774B1 (it) | 2008-11-17 | 2012-01-27 | Uhdenora Spa | Cella elementare e relativo elettrolizzatore modulare per processi elettrolitici |
DE102020206449A1 (de) | 2020-05-25 | 2021-11-25 | Siemens Aktiengesellschaft | Verfahren zum Befestigen einer Elektrode |
DE102020206448A1 (de) * | 2020-05-25 | 2021-11-25 | Siemens Aktiengesellschaft | Vorrichtung zum Befestigen einer Elektrode |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3655167A (en) * | 1970-08-18 | 1972-04-11 | Peter W Skille | Fence corner |
DE4444114C2 (de) | 1994-12-12 | 1997-01-23 | Bayer Ag | Elektrochemische Halbzelle mit Druckkompensation |
DE19622744C1 (de) | 1996-06-07 | 1997-07-31 | Bayer Ag | Elektrochemische Halbzelle mit Druckkompensation |
DE19641125A1 (de) * | 1996-10-05 | 1998-04-16 | Krupp Uhde Gmbh | Elektrolyseapparat zur Herstellung von Halogengasen |
DE19715429A1 (de) * | 1997-04-14 | 1998-10-15 | Bayer Ag | Elektrochemische Halbzelle |
DE19859882A1 (de) * | 1998-12-23 | 1999-12-09 | W Strewe | Ionenaustauschermembranzelle für hohe Produktleistungen |
US6283162B1 (en) * | 1999-09-09 | 2001-09-04 | Boyd L. Butler | Thin boom tube exhaust pipes, method of sheet metal construction thereof, and exhaust systems which utilize such exhaust pipes for increased ground clearance on race cars |
-
1999
- 1999-12-01 DE DE19959079A patent/DE19959079A1/de not_active Withdrawn
-
2000
- 2000-11-20 JP JP2001542612A patent/JP2003515677A/ja not_active Withdrawn
- 2000-11-20 ES ES00976055T patent/ES2240198T3/es not_active Expired - Lifetime
- 2000-11-20 US US10/148,138 patent/US6984296B1/en not_active Expired - Fee Related
- 2000-11-20 RU RU2002118331/12A patent/RU2002118331A/ru not_active Application Discontinuation
- 2000-11-20 CN CNB008166625A patent/CN1258619C/zh not_active Expired - Fee Related
- 2000-11-20 YU YU39402A patent/YU39402A/sh unknown
- 2000-11-20 HU HU0203519A patent/HUP0203519A3/hu unknown
- 2000-11-20 EP EP00976055A patent/EP1242653B1/fr not_active Expired - Lifetime
- 2000-11-20 DE DE50010013T patent/DE50010013D1/de not_active Expired - Fee Related
- 2000-11-20 KR KR1020027006974A patent/KR20020059830A/ko not_active Application Discontinuation
- 2000-11-20 AU AU13960/01A patent/AU775645B2/en not_active Ceased
- 2000-11-20 AT AT00976055T patent/ATE292695T1/de not_active IP Right Cessation
- 2000-11-20 CA CA002394835A patent/CA2394835A1/fr not_active Abandoned
- 2000-11-20 WO PCT/EP2000/011531 patent/WO2001040549A1/fr active IP Right Grant
- 2000-11-20 MX MXPA02005480A patent/MXPA02005480A/es unknown
- 2000-11-20 BR BR0015952-2A patent/BR0015952A/pt not_active Application Discontinuation
- 2000-11-20 CZ CZ20021886A patent/CZ20021886A3/cs unknown
- 2000-11-20 PT PT00976055T patent/PT1242653E/pt unknown
- 2000-11-20 PL PL00355720A patent/PL355720A1/xx not_active Application Discontinuation
-
2002
- 2002-04-23 ZA ZA200203202A patent/ZA200203202B/en unknown
- 2002-05-30 NO NO20022575A patent/NO20022575L/no unknown
-
2003
- 2003-09-19 HK HK03106737.2A patent/HK1054412A1/zh unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0140549A1 * |
Also Published As
Publication number | Publication date |
---|---|
NO20022575D0 (no) | 2002-05-30 |
BR0015952A (pt) | 2002-08-06 |
PL355720A1 (en) | 2004-05-17 |
NO20022575L (no) | 2002-05-30 |
HK1054412A1 (zh) | 2003-11-28 |
DE19959079A1 (de) | 2001-06-07 |
AU1396001A (en) | 2001-06-12 |
ATE292695T1 (de) | 2005-04-15 |
YU39402A (sh) | 2004-12-31 |
KR20020059830A (ko) | 2002-07-13 |
ES2240198T3 (es) | 2005-10-16 |
HUP0203519A3 (en) | 2003-04-28 |
ZA200203202B (en) | 2003-04-23 |
CA2394835A1 (fr) | 2001-06-07 |
EP1242653B1 (fr) | 2005-04-06 |
MXPA02005480A (es) | 2002-12-13 |
US6984296B1 (en) | 2006-01-10 |
AU775645B2 (en) | 2004-08-12 |
CZ20021886A3 (cs) | 2002-10-16 |
JP2003515677A (ja) | 2003-05-07 |
CN1258619C (zh) | 2006-06-07 |
CN1408032A (zh) | 2003-04-02 |
WO2001040549A1 (fr) | 2001-06-07 |
RU2002118331A (ru) | 2004-03-27 |
DE50010013D1 (de) | 2005-05-12 |
PT1242653E (pt) | 2005-08-31 |
HUP0203519A2 (hu) | 2003-03-28 |
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Legal Events
Date | Code | Title | Description |
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