EP1383941A1 - Modular electrochemical cell - Google Patents
Modular electrochemical cellInfo
- Publication number
- EP1383941A1 EP1383941A1 EP02713991A EP02713991A EP1383941A1 EP 1383941 A1 EP1383941 A1 EP 1383941A1 EP 02713991 A EP02713991 A EP 02713991A EP 02713991 A EP02713991 A EP 02713991A EP 1383941 A1 EP1383941 A1 EP 1383941A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ring
- grooves
- orifices
- cell according
- pierced
- 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- Withdrawn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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/242—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes comprising framed electrodes or intermediary frame-like gaskets
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2459—Comprising electrode layers with interposed electrolyte compartment with possible electrolyte supply or circulation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/42—Grouping of primary cells into batteries
- H01M6/46—Grouping of primary cells into batteries of flat cells
- H01M6/48—Grouping of primary cells into batteries of flat cells with bipolar electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to electrochemical cells. It relates, more particularly, to a modular electrochemical cell which uses disc-shaped electrodes, advantageously made of diamond, both in monopolar mode and in bipolar mode, with electrode spacings adjustable at will and in the most diverse configurations. allowing, in particular, to work with two or three different liquid flows.
- the cell according to the invention can thus be used, in a very simple manner, both for research and development work as in pilot or industrial installations.
- This type of electrochemical cell finds a particularly interesting application in the depollution of wastewater by oxidation of the contaminants that it contains.
- the modular electrochemical cell according to the invention is characterized in that it comprises:
- intermediate means having, at least, the function of ensuring the circulation and distribution of said fluid between the electrodes
- the electrodes comprise a conductive substrate and a conductive layer of diamond deposited on the substrate.
- each electrode is fixed to a conductive support disc which can be connected to a power source and whose axial position inside the housing is adjustable from the outside to be flush with the external face of the electrode and the edge of the frame.
- the housing advantageously contains a ring surrounding the support disc and whose axial position is adjustable from the outside to compress a seal between the electrode, the housing and the disc.
- the two frames each have an opening which opens inwards by a groove in an arc of a circle and are arranged so that said grooves are diametrically opposite, the opening of a frame used to supply the fluid and the opening of the other frame for its evacuation.
- said intermediate means comprise an insulating washer pierced with orifices situated opposite said grooves, each of these orifices communicating with the internal portion of the washer by a radial channel.
- said intermediate means comprise: - an insulating flat spacing ring pierced with orifices situated opposite said grooves, each of these orifices communicating with the internal portion of the ring by a radial channel, and
- said intermediate means comprise:
- the frames each have two openings which open inwards through two grooves in an arc of diametrically opposite circles, said frames being arranged so that their respective grooves are facing each other, the openings of each frame used respectively for the supply and evacuation of a fluid.
- said intermediate means comprise:
- said intermediate means comprise:
- FIGS. 1 and 2 show, respectively in axial section in exploded perspective, a first embodiment of a monopolar cell
- FIG. 3 represents, in exploded perspective, a second embodiment of a monopolar cell with a large inter-electrode space
- FIG. 4 represents, in exploded perspective, a third embodiment of a bipolar cell
- FIG. 5 represents, in exploded perspective, a fourth embodiment of a membrane cell
- FIG. 6 shows, in exploded perspective, a fifth embodiment of a cell with two membranes. It will be noted that, in the present description, the elements common to the various embodiments of the invention are designated by the same reference numbers.
- FIGs 1 and 2 there are shown in 10 and 12 two identical sets. Each is based on a frame 14, made of polypropylene, which has the shape of a disc having two truncated portions 16 diametrically opposite to form two flat faces serving as a stable base for the device.
- the cage 14 is pierced with a central cylindrical housing inside which takes place a movable ring with L-shaped section 18, of aluminum or plastic, receiving, also in a mobile manner, a disc 20, of copper or nickel.
- the outer face of the disc 20 receives, by tin welding or by bonding by means of a silver-based paste, an electrode 22 formed of a substrate which can be, for example, made of silicon, of carbide of silicon, titanium or zirconium, coated on its external face with a layer of doped diamond to be electrically conductive.
- This electrode can advantageously be produced according to the technique described in the document FR 99 02483.
- the inner face of the disc 20 is fixed to the end of a central screw 24 passing through a tapped hole formed in the bottom of the cage 14 and the other end of which receives a locking nut 26.
- the bottom of the cage 14 is pierced with six tapped holes, regularly distributed around its periphery, receiving a screw 28 actuable from the outside to act on the ring 18 by means of a coil spring 30.
- edge of the ring 18 facing the electrode 22 has a bevelled face on the outside, which acts on an O-ring 32 trapped between the electrode, the housing wall and the disc.
- the cage 14 is pierced on its edge, outside the perimeter occupied by the electrode, of a tapped hole into which a nozzle 34 is screwed intended for the connection of a pipe not shown.
- This nozzle opens, inside, in a groove 36 having the shape of an arc of a circle of approximately 90 °, of the same axis as the assembly.
- the figures show, in reality, two diametrically opposite grooves 36 because, in a configuration described below, the cell according to the invention needs them.
- the cell also comprises, between the two assemblies 10 and 12, a supply washer 38 which is made of an elastomer as, for example, one of the products sold under the designations of Viton and EPDM.
- This washer has an external contour corresponding to that of the cages 14 and a circular internal contour of the same diameter as that of the electrodes 22.
- the washer 38 is pierced with circular orifices 40 of diameter corresponding to the thickness of the groove 36 and forming a belt of the same radius as it.
- the orifices 40 are thus located opposite the groove 36.
- Each of these orifices communicates with the internal portion of the washer 38 by a radial channel 42.
- the two assemblies 10 and 12, with the washer 38 inserted between them and the end pieces 34 arranged in a diametrically opposite manner, are assembled by means of six bolts and nuts distributed at the periphery of the cell.
- FIG. 2 shows the heads 44 of these bolts and the holes 46 made in the cages 14 and the washer 38 to allow their passage.
- the screws 24 are respectively connected to the terminals of an appropriate power source, while liquid supply and evacuation pipes are respectively connected to the end pieces 34.
- the liquid introduced into the cell by the one of the tips is, typically, polluted wastewater.
- the electrolysis process carried out in the cell will allow purified water to appear on the other end accompanied by gas resulting from the reaction.
- the liquid introduced under pressure for example at the bottom of the left-hand assembly 10 opens into the lower groove 36 then into the orifices 40 of the washer 38 which are located opposite it, before being injected into the space separating the two electrodes 22 through the radial channels 42 associated with the orifices 40.
- the liquid is subjected, in this space, to the electrolysis process and is then introduced, at the top of the assembly on the right 12, in the upper groove 36 through the channels 42 and corresponding orifices 40 before being evacuated to the outside.
- the electrodes 22 have a diameter of the order of 10 cm and a thickness of between 0.5 and 3 mm, while disc 20 has a thickness of 10 to 12 mm.
- the thickness of the washer 38 is also between 0.5 and 3 mm.
- the cell which has just been described is suitable for fluids with relatively low conductivity.
- high conductivity electrolytes typically greater than 3 - 5 mS / cm
- the supply washer 38 is replaced, as shown in FIG. 3, by a spacer ring 48, made of polypropylene, and by two identical washers 50, arranged on either side of the ring 48, and produced, like the washer 38, in an elastomer.
- These three components have the same external and internal contours as the washer 38.
- the spacer ring 48 has the same series of circular orifices 40 and the same radial channels 42 as the washer 38.
- the washers 50 only have, in addition to the holes 46 for the passage of the bolts, two slots 52 (of which only one is useful) of the same shape as the slots 36 and positioned so as to come to their gaze during assembly of the cell.
- the cell described above can also take a bipolar structure.
- the supply washer 38 of the first embodiment is replaced, as shown in Figure 4, by a ring 54 of polypropylene, and by two identical washers 56, arranged on either side of the ring 54, and made of an elastomer.
- These three components have the same external and internal contours as the washer 38.
- the interior of the ring receives an electrode 58, of the same thickness and of the same diameter as the electrodes 22. It is formed of a conductive substrate coated on its two sides of a layer of diamond doped to be made electrically conductive.
- the electrode 58, as well as the two electrodes 22, can advantageously be produced according to the teaching of document EP 810147.9.
- the ring 54 comprises, in addition to the holes for the passage of the bolts, two diametrically opposite slots 60, of the same shape as the grooves 36 and positioned so as to come to their gaze during assembly of the cell.
- the two washers 56 are identical to the washer 38. In this embodiment, they are the ones that distribute and collect the liquid.
- the bipolar cell of FIG. 4 can comprise several intermediate electrodes 58 associated with a ring 54, in order to ensure, as for the cell of FIG. 3, a larger interelectrode space.
- additional washers 56 are inserted between the different rings 54.
- the assemblies 10 and 12 of FIG. 1 are replaced by assemblies 62 and 64 which are distinguished only by the fact that they comprise two end pieces 34 and necessarily two circular grooves 36, diametrically opposite, the liquid to be treated then being supplied by one of the end pieces and emerging through the other.
- This cell works with two electrolytes which do not mix and form respectively, according to a known process, an anolyte flow and a catholyte flow.
- the supply washer 38 of FIG. 1 is replaced by a stack, the central element of which is a membrane 66 made of an electrically conductive material and selectively permeable to certain ions, such as an ion exchange membrane. in Nafion.
- the membrane 66 may be replaced by a porous diaphragm.
- the membrane 66 On either side of this element, there are, arranged symmetrically, two washers 68 made of elastomer, then two rings 70 made of polypropylene and, finally, two new washers 72 made of fluorinated elastomer. All these components have the same external contour as the washer 38 and have the six holes 46 for the passage of the assembly bolts.
- the washers 68 and 72 and the ring 70 also have the same circular interior contour as the washer 38.
- FIG. 6 represents a fifth embodiment of the cell according to the invention.
- the supply washer 38 of FIG. 1 is replaced by a stack of elements having the same external contour as the washer 38 and having the six holes 46 for the passage of the assembly bolts.
- the central element is a hollow ring 74, made of polypropylene, provided with two diametrically opposite ends 76, intended to be connected respectively to a supply pipe and to a liquid discharge pipe.
- the cell of FIG. 6 can work, according to a known process, with three separate flows, namely a flow of anolyte and a flow of catholyte, circulating respectively in the assemblies 62 and 64, and a flow of liquid to be treated circulating through the ring 74.
- various elements of the cell such as, for example, the washer 38 in FIG. 1, can be provided in their center with a grid 82 serving as a promoter of turbulence and a spacer between electrodes.
- This grid is advantageously made of an insulating and chemically stable material, such as polypropylene or polyethylene.
- an electrochemical cell is proposed whose modular structure, linked to the use of interchangeable elements, allows it a wide variety of configurations meeting the various needs of users.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02713991A EP1383941A1 (en) | 2001-05-01 | 2002-04-22 | Modular electrochemical cell |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01810430 | 2001-05-01 | ||
EP01810430A EP1254972A1 (en) | 2001-05-01 | 2001-05-01 | Modular electrochemical cell |
EP02713991A EP1383941A1 (en) | 2001-05-01 | 2002-04-22 | Modular electrochemical cell |
PCT/CH2002/000221 WO2002088430A1 (en) | 2001-05-01 | 2002-04-22 | Modular electrochemical cell |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1383941A1 true EP1383941A1 (en) | 2004-01-28 |
Family
ID=8183887
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01810430A Withdrawn EP1254972A1 (en) | 2001-05-01 | 2001-05-01 | Modular electrochemical cell |
EP02713991A Withdrawn EP1383941A1 (en) | 2001-05-01 | 2002-04-22 | Modular electrochemical cell |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01810430A Withdrawn EP1254972A1 (en) | 2001-05-01 | 2001-05-01 | Modular electrochemical cell |
Country Status (4)
Country | Link |
---|---|
US (1) | US7335284B2 (en) |
EP (2) | EP1254972A1 (en) |
JP (1) | JP2004525765A (en) |
WO (1) | WO2002088430A1 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE227844T1 (en) * | 1997-02-06 | 2002-11-15 | Therasense Inc | SMALL VOLUME SENSOR FOR IN-VITRO DETERMINATION |
AU2002337876A1 (en) | 2001-10-15 | 2003-04-28 | United States Filter Corporation | Apparatus for fluid purification and methods of manufacture and use thereof |
DE102004027623A1 (en) * | 2004-06-05 | 2005-12-22 | Degussa Initiators Gmbh & Co. Kg | Process for the preparation of peroxodisulfates in aqueous solution |
KR100712031B1 (en) | 2005-08-31 | 2007-04-30 | 이상진 | Device for treatment the water of fuel and fluid water |
US20070209942A1 (en) * | 2006-03-08 | 2007-09-13 | Shyu Wen S | Device for separating anolyte from catholyte in electrolyzer |
US20080090146A1 (en) * | 2006-10-12 | 2008-04-17 | David Batson | Bipolar Battery Electrode Structure and Sealed Bipolar Battery Assembly |
JP4460590B2 (en) * | 2007-06-22 | 2010-05-12 | ペルメレック電極株式会社 | Conductive diamond electrode structure and method for electrolytic synthesis of fluorine-containing material |
JP5207529B2 (en) | 2008-06-30 | 2013-06-12 | クロリンエンジニアズ株式会社 | Sulfuric acid electrolytic tank and sulfuric acid recycling type cleaning system using sulfuric acid electrolytic tank |
US20110108438A1 (en) * | 2009-10-02 | 2011-05-12 | Tretheway James A | Electrochemical Liquid Treatment System Using Dose Control |
WO2011068883A1 (en) * | 2009-12-01 | 2011-06-09 | A123 Systems, Inc. | Electrical insulator for electrochemical cell |
CN101913686A (en) * | 2010-09-06 | 2010-12-15 | 华中科技大学 | Pulse power water treatment reactor |
TW201228942A (en) | 2010-11-12 | 2012-07-16 | Siemens Pte Ltd | Method of providing a source of potable water |
WO2012075425A2 (en) | 2010-12-03 | 2012-06-07 | Electrolytic Ozone Inc. | Electrolytic cell for ozone production |
EP2697730A4 (en) * | 2011-04-15 | 2015-04-15 | Advanced Diamond Technologies Inc | Electrochemical system and method for on-site generation of oxidants at high current density |
US20140174915A1 (en) * | 2012-12-20 | 2014-06-26 | Bruce J. Trott | Hydrogen/oxygen generator apparatus and system |
US20140262770A1 (en) * | 2013-03-14 | 2014-09-18 | Liquid Light, Inc. | Electrochemical cell system for rapid evaluation of electrochemical processes and materials used therein |
CN105209159B (en) | 2013-03-15 | 2018-06-12 | 懿华水处理技术有限责任公司 | For the flow distributor of Electrochemical separation |
JP6118359B2 (en) * | 2015-03-31 | 2017-04-19 | 株式会社日本トリム | Electrolyzed water generator |
GB201522500D0 (en) * | 2015-12-21 | 2016-02-03 | Element Six Technologies Ltd | Electrochemical cell comprising electrically conductive diamond electrodes |
JP7245738B2 (en) * | 2019-07-19 | 2023-03-24 | 住友化学株式会社 | Electrochemical sensor unit, electrochemical sensor electrode, and electrochemical sensor electrode manufacturing method |
US11978590B1 (en) * | 2023-03-28 | 2024-05-07 | University Of Sharjah | Integrated thermal management system with a symmetrical supercapacitor cell |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3108255C2 (en) * | 1981-03-05 | 1986-05-07 | Kernforschungsanlage Jülich GmbH, 5170 Jülich | Assembly unit for electrolysis cells for alkaline water electrolysis and process for producing the same |
FR2649792B1 (en) * | 1989-07-17 | 1991-09-20 | Commissariat Energie Atomique | DEVICE FOR THE CONTINUOUS PRODUCTION OF A STANDARD IONIC SOLUTION |
JP2911381B2 (en) * | 1995-03-01 | 1999-06-23 | 神鋼パンテツク株式会社 | Hydrogen / oxygen generator |
US5795450A (en) * | 1997-03-04 | 1998-08-18 | Shinko Pantec Co., Ltd. | Apparatus for producing hydrogen and oxygen |
US5928489A (en) * | 1997-06-16 | 1999-07-27 | Georgia Tech Research Corp. | Low temperature removal and recovery of hydrogen halides using an electrochemical membrane |
JP3859358B2 (en) * | 1998-05-26 | 2006-12-20 | クロリンエンジニアズ株式会社 | Electrolyzed water production equipment |
FR2784386B1 (en) | 1998-10-13 | 2000-11-10 | Rhodia Chimie Sa | USE OF HYDROXYCARBONATE, HYDROXYOXYCARBONATE OR ALUMINUM OXYCARBONATE AS FILLER IN A RUBBER COMPOSITION |
NZ512645A (en) * | 1998-12-07 | 2002-10-25 | Zappi Water Purification Syste | Electrolytic apparatus, methods for purification of aqueous solutions and synthesis of chemicals |
FR2790268B1 (en) * | 1999-02-25 | 2001-05-11 | Suisse Electronique Microtech | ELECTROLYSIS CELL WITH BIPOLAR ELECTRODE COMPRISING DIAMOND |
DE19911746A1 (en) * | 1999-03-16 | 2000-09-21 | Basf Ag | Diamond electrodes |
EP1262577B1 (en) * | 2001-05-24 | 2004-02-25 | Casale Chemicals S.A. | Electrochemical reactor |
-
2001
- 2001-05-01 EP EP01810430A patent/EP1254972A1/en not_active Withdrawn
-
2002
- 2002-04-22 EP EP02713991A patent/EP1383941A1/en not_active Withdrawn
- 2002-04-22 US US10/476,740 patent/US7335284B2/en not_active Expired - Fee Related
- 2002-04-22 JP JP2002585703A patent/JP2004525765A/en not_active Abandoned
- 2002-04-22 WO PCT/CH2002/000221 patent/WO2002088430A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO02088430A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20040146779A1 (en) | 2004-07-29 |
US7335284B2 (en) | 2008-02-26 |
EP1254972A1 (en) | 2002-11-06 |
WO2002088430A1 (en) | 2002-11-07 |
JP2004525765A (en) | 2004-08-26 |
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