WO2001086026A1 - Bipolare mehrzweckelektrolysezelle für hohe strombelastungen - Google Patents
Bipolare mehrzweckelektrolysezelle für hohe strombelastungen Download PDFInfo
- Publication number
- WO2001086026A1 WO2001086026A1 PCT/EP2001/005344 EP0105344W WO0186026A1 WO 2001086026 A1 WO2001086026 A1 WO 2001086026A1 EP 0105344 W EP0105344 W EP 0105344W WO 0186026 A1 WO0186026 A1 WO 0186026A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- bipolar
- electrolyte
- electrolytic cell
- sheets
- Prior art date
Links
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
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- 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
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
Definitions
- the invention relates to a bipolar switched multipurpose electrolysis cell in a high design for preferably high current loads between 1 and 10 kA / m 2 per bipolar single cell.
- a bipolar switched multipurpose electrolysis cell in a high design for preferably high current loads between 1 and 10 kA / m 2 per bipolar single cell.
- Bipolar electrolysis cells in filter press design consisting of a clamping frame, the two electrode edge plates with power supply and any number of bipolar electrode plates along with peripheral equipment for the supply and discharge of the electrolyte solutions as well as the cooling or temperature control medium, are known in numerous embodiments and for a wide variety of applications . They can be carried out undivided or divided into two- or multi-chamber cells by means of ion exchange membranes or microporous diaphragms. The required electrode or electrolyte spaces can be designed as separate assemblies or integrated in the electrode edge plates or in the bipolar electrode plates.
- bipolar electrolysis cells Compared to the monopolar electrolysis cells of filter press design, which have an analog structure, the great advantage of bipolar electrolysis cells is that the current supply only needs to be brought from the outside to the two edge plates, while the current transport in the bipolar individual cells only from one side of the electrode plate to the one other side is usually done internally. For the most part, a simple bipolar electrode plate, on which the anode and cathode sides are made of the same electrode material, is not sufficient. In many cases, and particularly in the case of multipurpose electrolysis cells, it is necessary to provide anodes and cathodes made of different materials, preferably consisting of metal sheets. These can then be electrically conductively connected to one another directly or indirectly via contact bodies.
- bipolar multipurpose electrolytic cell with a large height-to-width ratio, which is necessary here in order to achieve the "gas-lift effect" for electrolyte circulation, as part of a versatile and usable gas-lift electrolysis and reaction system is described in DE 44 38 1 24. It is an electrolytic cell construction with a total height of 1.5 to 2.5 m that has been optimized with regard to the use of the buoyancy by the gases developed.
- the bipolar electrode plates consist of electrode base bodies made of impregnated graphite or of plastics with integrated inlets and outlets for the electrolyte solutions and the cooling medium as well as electrodes applied on both sides or, in the case of the graphite base bodies, also integrated electrodes and electrolyte compartments.
- the two electrodes are connected to one another in an electrically conductive manner, in the case of the plastic base body by inserted contact elements.
- Such contact elements are arranged within the sealing surfaces covered by electrolyte frames made of elastic material. The contact is made by the contact pressure during assembly.
- the electrodes used cannot normally be used as metal electrode sheets which are easy to manufacture and thus easily replaceable in the sense of a multi-purpose cell.
- welded constructions are usually unavoidable for the two half cells of a bipolar unit, which often consist of different electrode materials or material composites.
- the outlay on equipment to be operated for this is relatively large. Since the electrical contact between the two half cells of the bipolar units is usually brought about by a large number of screw connections, assembly is considerably more complex than that of the cell constructions, in which this contact can be established automatically when the two are clamped together. Also, the transition to other electrode materials usually requires a modified construction that is adapted to the material properties.
- the monopole design has the fundamental disadvantage that a large number of individual cells have to be connected in series in order to reach a favorable voltage range for the current transformation (e.g. 200 V).
- the electrolyte-side and current-side connection leads to high costs in implementation.
- Another disadvantage of the cells described is the design as a hollow body.
- the removal of the active coating on the anode means that the entire anode body has to be manufactured again. The same applies to the cathode.
- the electrode hollow bodies When the electrode hollow bodies are pressed, they deform and since they have no internal support (this would be extremely difficult to achieve in terms of production technology), this leads to an insufficient plane parallelism of the electrodes. In extreme cases, this can lead to short circuits and thus to the destruction and explosion of the cell.
- the versatile multi-purpose electrolytic cell aimed at for high current loads can therefore hardly be realized on this basis.
- the invention is therefore based on the problem of providing a bipolar multipurpose electrolytic cell constructed according to the filter press principle with plastic base bodies, in which a good and reliable contacting of the metal electrode sheets is ensured even at high current loads while circumventing the disadvantages of the known technical solutions.
- the cathode and anode sheets of a bipolar element are expediently screwed to the respective contact rails on one or both sides by means of countersunk screws.
- this screw connection only serves for better handling and is only responsible to a small extent for the current flow, which is only optimized by the press contact.
- the metal electrode sheets are in the case of the anode sheets made of valve metals, preferably titanium, which in the electrochemically active area in a known manner with active layers of precious metals, noble metal oxides, mixed oxides of noble metals and other metals, and other metal oxides, such as, for. B. lead dioxide are occupied.
- valve metals such as tantalum, niobium or zirconium, can also be used as supports for such active layers. But also leaded, nickel-plated, copper-plated steel or nickel-based alloys are suitable for special applications.
- the anode sheets have a noble metal coating made of solid platinum and can be obtained by hot isostatic pressing of platinum foil and titanium sheet.
- Stainless steel, nickel, titanium, steel and lead are preferably used as the cathode material.
- Openwork metal electrode sheets are to be understood in particular as those made of expanded metals. But perforated sheets or blind electrodes are also possible in another way.
- the contact rails used are preferably copper, which can be tin-plated or silver-plated on the contact surfaces or coated with precious metals.
- the current contact surfaces of the electrodes are preferably provided with well-conductive coatings, e.g. platinum, gold, silver or copper layers applied by electroplating.
- the contact rails and the electrode contacts are preferably gold-plated or platinum-plated, and the current transmission takes place through the press contact which is produced by tensioning the electrode package.
- the following advantages also result in electrodes without gas evolution: first, with the same width of the contact rails, the available contact area increases proportionally to the cell height, which results in lower thermal loads on the contacts.
- the transport of electricity from the contact areas through the metal electrode plates is also favored, since with the same effective electrode area, the same thickness of the electrode plates and the same current load, the cross-section relevant for the current transport increases with the height of the electrode plates and, at the same time, the path length for the current transport decreases with increasing height . Under these boundary conditions, the electrical resistance and thus the voltage drop in the electrode plates decrease with the square of the cell height.
- the thinner and taller electrode plates to be used according to the invention can therefore be made of much thinner or less electrically conductive electrode plates or of significantly higher current loads. This is of great importance particularly in the case of perforated electrode sheets, in which a reduction in the cross section for the current transport has to be accepted. Also, in the case of mounting the cell stack in the case of thin sheet metal electrodes, any ripple in the sheet is compensated for after pressing and thus a plane parallelism of the electrode is achieved.
- the contacts Due to copper pipes soldered to the outside of the contact rails, the contacts can be opened or cooled by means of cooling water even with high current loads be kept below room temperature. In this way, heating of the cell frame, the sealing system and the current contacts and the associated problems such as deformation and overheating are completely avoided.
- the plane parallelism of the electrodes to each other is the prerequisite for high current yields and uniform electrode corrosion.
- the height of the cell plays a role in cooling the highly stressed contact rails.
- the contacts in particular at higher electrolyte temperatures in a bipolar cell constructed according to the invention, assume a significantly lower temperature than in the electrolysis cells with internal contact elements, in which, under comparable conditions, significantly higher temperatures are measured on the contact elements than in the interior of the cell.
- the advantage of the distance between the cell frame and the contact web is that it can be used to drain a possibly small amount of electrolyte. If electrolyte penetrates the contact gap, salt is formed and the contact deteriorates within a very short time.
- the leaking coolant is set at a level below the height of the inlet. This creates a vacuum that can be adjusted by means of the level difference, which sucks the anode sheet onto the plastic base body and at the same time improves the plane parallelism and prevents the anode from bulging in the event of pressure fluctuations in the cell. This measure enables a very small electrode gap of 2 to 4 mm and thus a low electrolyte resistance and a high flow rate to be achieved.
- Fig. 1 a shows a simplified vertical section of a first invention
- Fig. 1 b is a sectional view along the line Ib-Ib in Fig. 1 a; 2a shows a simplified vertical section of a second embodiment according to the invention with two solid electrode sheets, both cooled from the rear.
- Fig. 2b is a sectional view taken along the line IIb-llb in Fig. 2a;
- FIG 3a shows a simplified vertical section of a third embodiment according to the invention with two perforated metal electrode sheets without additional cooling.
- Fig. 3b is a sectional view taken along the line IIIb-IIIb in Fig. 3a;
- FIG. 4 shows a simplified vertical section through a bipolar electrolytic cell with three bipolar electrode plates constructed according to FIG. 1 a and a clamping frame shown in simplified form.
- FIGS. 1 a to 3 c three exemplary embodiments of a divided bipolar multipurpose electrolysis cell are shown by way of example and schematically in sectional views through the electrochemically active areas, the upper figures showing side views and the lower figures showing top views.
- the bipolar multipurpose electrolytic cell as shown in its first embodiment according to FIGS. 1 a and 1 b, and with the reference number 1 0, is part of an electrolysis device, not shown.
- the bipolar multipurpose electrolytic cell 10 consists of an electrode base body 1 2 made of plastic, to which metal electrode sheets or electrode plates are attached on both sides, in this embodiment one electrode plate 14 is solid, and the other electrode plate 16 is broken through in the electrochemically active region.
- the electrode base body 12 has a double-T shape in cross section both in the vertical and in the horizontal direction, as a result of which channels 18, 20 are formed between the electrode base body 12 and the respective electrode sheets 14, 16.
- an electrolyte sealing frame 22 made of elastic material is additionally attached, which forms a further channel 24 on the outside of the solid electrode sheet 14 viewed from the electrode base body 1 2.
- the channel 18 formed between the electrode base body 12 and the solid electrode sheet 14 serves to receive cooling liquid for cooling the solid electrode sheet 14 and optionally the electrode base body 12 and is referred to below as the cooling space.
- Inlets and outlets for the electrolyte solutions are incorporated in the electrode base body 12, the inlets 26 and 28 being arranged in a lower middle region of the electrode base body 12 and the associated outlets 30 and 32 being arranged in an upper middle region thereof.
- the inlet and outlet lines are connected via respective inlet openings 34, 36 and outlet openings 38, 40 to the electrolyte channels 24 and 20, through which the electrolyte solutions for the electrolysis are passed, the inlet and outlet openings 34 and 38 for the most massive one Guide the electrode plate 14 formed channel 24 through the solid electrode plate 14.
- Cooling chamber 1 8 is provided, into or through which a coolant, in this case cooling water, can be conducted or pumped via feed lines 42 and discharge lines 44 and corresponding connection channels 46 and 48 arranged in a lower or upper middle region of the electrode base body 1 2 .
- a coolant in this case cooling water
- feed lines 42 and discharge lines 44 and corresponding connection channels 46 and 48 arranged in a lower or upper middle region of the electrode base body 1 2 .
- a "lift effect” can also be used, but coolants with a reverse effect would also be conceivable.
- the perforated metal electrode plate does not require additional cooling, since it is sufficiently cooled by the electrolyte solution and only rests on the base body in marginal areas, which prevents heat build-up.
- An ion exchange membrane 50 rests on the perforated metal electrode sheet 1 6 and is attached to the perforated electrode sheet 1 6 by suitable means.
- contact rails 52 contact the laterally elongated metal electrode sheets 14 and 16 and that 2 columns 54 are formed between the respective contact rails and the edge of the base body, which are laterally delimited by the metal electrode sheets .
- FIGS. 2a and 2b A further embodiment of the invention is shown in FIGS. 2a and 2b.
- a multipurpose electrolysis cell denoted by 1 1 0 is shown therein, components which correspond to those of the first embodiment according to FIGS. 1 a and 1 b being provided with the same reference numbers, in each case increased by the number 100. Only the differences are dealt with below, so that reference is made to the description of the first exemplary embodiment.
- Cooling spaces 1 1 8 are provided on both sides of the base body 1 1 2 between the base body 1 1 2 and the electrode sheets in order to cool the solid electrode sheets 1 14.
- the cooling rooms 1 1 8 are in turn supplied with cooling liquid via supply lines 142 and discharge lines 144 as well as corresponding connection channels 146 and 148.
- 3a and 3b show a further multipurpose electrolysis cell according to the invention, designated 210, components, which correspond to those of the first embodiment according to FIGS. 1a and 1b, being provided with the same reference numbers, each increased by the number 200. In the following, only the differences will be narrowed down.
- a solid 14 and a perforated electrode plate 16 are used in the first embodiment, two perforated electrode plates 21 6 are used in this embodiment, with a thin sealing frame 256 on which the Ion exchanger membrane 250 is attached by suitable means.
- the ion exchange membrane 250 can, however, also be arranged directly on an electrode plate, in which case a thin sealing frame is attached to the membrane or the free electrode plate. Due to the exclusive use of perforated electrode sheets, cold rooms are not required in this embodiment.
- FIG. 4 illustrates the current transport through a cell made up of three bipolar electrode plates constructed according to the invention and the two edge electrode plates with current supply on both sides and plastic base bodies widened up to the side contact rails.
- FIG. 1 a The construction variant according to FIG. 1 a was based on one perforated and one solid metal electrode sheet per bipolar electrode sheet. The designations of the numbered components are the same as in FIG. 1.
- the invention is not restricted to the constructive embodiments shown in FIGS. 1 to 4.
- undivided cells or multi-chamber cells can also be constructed using the principle of the invention.
- microporous diaphragms can also be used.
- the inlets and outlets for the electrolyte solutions can also be arranged differently than shown here, e.g. they can be led out of the upper and lower end faces of the plastic base body or they are routed to the edge plates via manifolds within the bipolar electrode plates.
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- 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 Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Hybrid Cells (AREA)
- Electrolytic Production Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002407875A CA2407875C (en) | 2000-05-09 | 2001-05-09 | Bipolar multipurpose electrolysis cell for high current loads |
JP2001582609A JP4808898B2 (ja) | 2000-05-09 | 2001-05-09 | 高電流負荷のためのバイポーラ多目的電解セル |
AU2001281770A AU2001281770A1 (en) | 2000-05-09 | 2001-05-09 | Bipolar multi-purpose electrolytic cell for high current loads |
BR0110700-3A BR0110700A (pt) | 2000-05-09 | 2001-05-09 | Célula de eletrolìse multifuncional bipolar para corrente intensa |
US10/258,386 US7018516B2 (en) | 2000-05-09 | 2001-05-09 | Bipolar multi-purpose electrolytic cell for high current loads |
ES01960214T ES2398742T3 (es) | 2000-05-09 | 2001-05-09 | Celda de electrólisis bipolar de usos múltiples, para altas cargas con corriente eléctrica |
EP01960214A EP1285103B1 (de) | 2000-05-09 | 2001-05-09 | Bipolare mehrzweckelektrolysezelle für hohe strombelastungen |
NO20025397A NO20025397D0 (no) | 2000-05-09 | 2002-11-11 | Bipolar elektrolysecelle for höy strömbelastning til flere formÕl |
HK03108064A HK1055767A1 (en) | 2000-05-09 | 2003-11-06 | Bipolar multi-purpose electrolytic cell for high current loads. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10022592.6 | 2000-05-09 | ||
DE10022592A DE10022592B4 (de) | 2000-05-09 | 2000-05-09 | Bipolare Mehrzweckelektrolysezelle für hohe Strombelastungen |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001086026A1 true WO2001086026A1 (de) | 2001-11-15 |
WO2001086026A8 WO2001086026A8 (de) | 2002-02-21 |
Family
ID=7641326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/005344 WO2001086026A1 (de) | 2000-05-09 | 2001-05-09 | Bipolare mehrzweckelektrolysezelle für hohe strombelastungen |
Country Status (15)
Country | Link |
---|---|
US (1) | US7018516B2 (de) |
EP (1) | EP1285103B1 (de) |
JP (1) | JP4808898B2 (de) |
CN (1) | CN1197999C (de) |
AU (1) | AU2001281770A1 (de) |
BR (1) | BR0110700A (de) |
CA (1) | CA2407875C (de) |
DE (1) | DE10022592B4 (de) |
ES (1) | ES2398742T3 (de) |
HK (1) | HK1055767A1 (de) |
NO (1) | NO20025397D0 (de) |
RU (1) | RU2002132878A (de) |
TW (1) | TW526289B (de) |
WO (1) | WO2001086026A1 (de) |
ZA (1) | ZA200208519B (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007511664A (ja) * | 2003-05-16 | 2007-05-10 | ハイドロジェニクス コーポレイション | 対称形分流板 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10108452C2 (de) * | 2001-02-22 | 2003-02-20 | Karl Lohrberg | Elektrolyseeinrichtung |
SE526127C2 (sv) * | 2003-11-14 | 2005-07-12 | Nilar Int Ab | En packning, ett bipolärt batteri och en metod för tillverkning av ett bipolärt batteri med en sådan packning |
US7722745B2 (en) * | 2004-07-27 | 2010-05-25 | Von Detten Volker | Device for plating contacts in hermetic connector assemblies |
US20080198531A1 (en) * | 2007-02-15 | 2008-08-21 | Lih-Ren Shiue | Capacitive deionization system for water treatment |
DE102010024299A1 (de) | 2010-06-18 | 2011-12-22 | Uhde Gmbh | Einzelelementelektrolysezelle zur Herstellung von Peroxodisulfat |
DE102010063254A1 (de) * | 2010-12-16 | 2012-06-21 | FuMA-Tech Gesellschaft für funktionelle Membranen und Anlagentechnologie mbH | Membran-Elektroden-Anordnung mit zwei Deckschichten |
GR20130100562A (el) * | 2013-10-03 | 2015-05-18 | Θεοδωρος Ευσταθιου Καραβασιλης | Κυτταρο ηλεκτρολυσης με κασετες ηλεκτροδιων |
WO2017113009A1 (en) * | 2015-12-30 | 2017-07-06 | Innovative Hydrogen Solutions, Inc. | Electrolytic cell for internal combustion engine |
JP2024102507A (ja) * | 2023-01-19 | 2024-07-31 | トヨタ自動車株式会社 | 水電解スタック及び水電解システム |
Citations (2)
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EP0500505A1 (de) * | 1991-02-11 | 1992-08-26 | SESPI S.r.l. | Einrichtung für die Elektrolyse und die Elektrodialyse |
WO1993020261A1 (de) * | 1992-04-06 | 1993-10-14 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Bipolare filterpressenzelle zur herstellung von peroxodisulfaten |
Family Cites Families (5)
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US2477139A (en) * | 1944-04-04 | 1949-07-26 | Western Electric Co | Conducting bearing |
DE3420483A1 (de) * | 1984-06-01 | 1985-12-05 | Hoechst Ag, 6230 Frankfurt | Bipolarer elektrolyseapparat mit gasdiffusionskathode |
DE3938160A1 (de) * | 1989-11-16 | 1991-05-23 | Peroxid Chemie Gmbh | Elektrolysezelle zur herstellung von peroxo- und perhalogenatverbindungen |
DE4438124A1 (de) * | 1994-10-27 | 1996-05-02 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Gas-Lift-Elektrolyse- und Reaktionssysteme zur Herstellung von Produkten und zur Anwendung in der Umwelttechnik |
JPH0995791A (ja) * | 1995-10-04 | 1997-04-08 | Sasakura Eng Co Ltd | 固体高分子電解質水電解装置及びその電極構造 |
-
2000
- 2000-05-09 DE DE10022592A patent/DE10022592B4/de not_active Expired - Fee Related
-
2001
- 2001-05-03 TW TW090110646A patent/TW526289B/zh not_active IP Right Cessation
- 2001-05-09 JP JP2001582609A patent/JP4808898B2/ja not_active Expired - Lifetime
- 2001-05-09 CA CA002407875A patent/CA2407875C/en not_active Expired - Fee Related
- 2001-05-09 AU AU2001281770A patent/AU2001281770A1/en not_active Abandoned
- 2001-05-09 CN CNB018092020A patent/CN1197999C/zh not_active Expired - Lifetime
- 2001-05-09 RU RU2002132878/15A patent/RU2002132878A/ru not_active Application Discontinuation
- 2001-05-09 BR BR0110700-3A patent/BR0110700A/pt not_active Application Discontinuation
- 2001-05-09 EP EP01960214A patent/EP1285103B1/de not_active Expired - Lifetime
- 2001-05-09 WO PCT/EP2001/005344 patent/WO2001086026A1/de active Application Filing
- 2001-05-09 ES ES01960214T patent/ES2398742T3/es not_active Expired - Lifetime
- 2001-05-09 US US10/258,386 patent/US7018516B2/en not_active Expired - Lifetime
-
2002
- 2002-10-22 ZA ZA200208519A patent/ZA200208519B/en unknown
- 2002-11-11 NO NO20025397A patent/NO20025397D0/no not_active Application Discontinuation
-
2003
- 2003-11-06 HK HK03108064A patent/HK1055767A1/xx not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0500505A1 (de) * | 1991-02-11 | 1992-08-26 | SESPI S.r.l. | Einrichtung für die Elektrolyse und die Elektrodialyse |
WO1993020261A1 (de) * | 1992-04-06 | 1993-10-14 | Eilenburger Elektrolyse- Und Umwelttechnik Gmbh | Bipolare filterpressenzelle zur herstellung von peroxodisulfaten |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007511664A (ja) * | 2003-05-16 | 2007-05-10 | ハイドロジェニクス コーポレイション | 対称形分流板 |
Also Published As
Publication number | Publication date |
---|---|
WO2001086026A8 (de) | 2002-02-21 |
CN1197999C (zh) | 2005-04-20 |
EP1285103A1 (de) | 2003-02-26 |
RU2002132878A (ru) | 2004-04-10 |
CA2407875A1 (en) | 2002-10-29 |
TW526289B (en) | 2003-04-01 |
NO20025397L (no) | 2002-11-11 |
NO20025397D0 (no) | 2002-11-11 |
US7018516B2 (en) | 2006-03-28 |
AU2001281770A1 (en) | 2001-11-20 |
BR0110700A (pt) | 2003-03-18 |
ZA200208519B (en) | 2003-11-07 |
DE10022592B4 (de) | 2010-03-04 |
CN1427900A (zh) | 2003-07-02 |
US20030150717A1 (en) | 2003-08-14 |
HK1055767A1 (en) | 2004-01-21 |
CA2407875C (en) | 2009-12-29 |
DE10022592A1 (de) | 2001-11-15 |
JP2003534452A (ja) | 2003-11-18 |
ES2398742T3 (es) | 2013-03-21 |
JP4808898B2 (ja) | 2011-11-02 |
EP1285103B1 (de) | 2013-01-02 |
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