EP1073780A1 - Electrolysis apparatus for producing halogen gases - Google Patents
Electrolysis apparatus for producing halogen gasesInfo
- Publication number
- EP1073780A1 EP1073780A1 EP99916899A EP99916899A EP1073780A1 EP 1073780 A1 EP1073780 A1 EP 1073780A1 EP 99916899 A EP99916899 A EP 99916899A EP 99916899 A EP99916899 A EP 99916899A EP 1073780 A1 EP1073780 A1 EP 1073780A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolysis
- anode
- cathode
- housing
- openings
- 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
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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
- C25B9/75—Assemblies comprising two or more cells of the filter-press type having bipolar 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- 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
- C25B9/70—Assemblies comprising two or more cells
Definitions
- the invention relates to an electrolysis apparatus for the production of halogen gases from aqueous alkali halide solution with a plurality of plate-shaped electrolytic cells arranged side by side in a stack and in electrical contact, each of which has a housing made of two half-shells made of electrically conductive material with external contact strips on at least one rear wall of the housing, wherein the housing has devices for supplying the electrolysis current and the electrolysis input materials and devices for discharging the electrolysis current and the electrolysis products and each have two essentially planar electrodes (anode and cathode), the anode and the cathode having blind-like openings for a flow through the electrolysis input materials and the electrolysis products provided and separated from each other by a partition and arranged parallel to each other and by means of metallic stiffeners with the respectively assigned Back wall of the housing are electrically connected.
- the individual electrolytic cells are manufactured in such a way that the respective housing consists of two half-shells with the interposition of the necessary devices and - 2 -
- the cathode and anode as well as the partition and by fixing them together by means of metallic stiffeners and anode and housing or cathode and housing are attached to one another in an electrically conductive manner, then the plate-shaped electrolytic cells produced in this way are arranged next to one another in an electrically conductive stack and against one another in the stack for the purpose of sustainable contact be tense.
- the electrolysis current is fed to the cell stack on one outer cell of the stack, it passes through the cell stack in a direction substantially perpendicular to the central planes of the plate-shaped electrolysis cells and it is discharged at the other outer cell of the stack. Relative to the middle level, the electrolysis current reaches mean current density values of at least 4 kA / m 2 .
- Such an electrolysis apparatus is known from DE 196 41 125 AI by the applicant.
- the anode or the cathode are connected to the respective rear wall of the housing halves via vertical, web-like metallic stiffeners.
- the vertical, web-like metallic stiffeners are designed as webs aligned with the contact strips, the side edges of which rest against the rear wall and the anode or cathode over the entire height of the rear wall and the anode or cathode.
- the vertical webs divide the electrode back space into individual electrolyte-carrying segments within the respective housing half. So that there is no completely uneven concentration distribution in the electrolyte along the depth of the respective housing half, an inlet distributor is provided in the bottom of each housing half, through which the electrolysis input substances are fed into the individual - 4 -
- segments formed by the webs can be fed into the half-shells.
- Gas-generating electrolysis processes such as, for example, chlor-alkali electrolysis, hydrochloric acid electrolysis or alkaline water electrolysis are carried out by means of an electrolyser designed in this way.
- chlor-alkali electrolysis aqueous alkali halide solutions, for example sodium and potassium chloride, are decomposed in the electrolysis cell under the influence of the electric current into an aqueous alkali solution, for example sodium or potassium hydroxide solution, and in a halogen gas, for example chlorine and hydrogen.
- water electrolysis water is decomposed and hydrogen and oxygen are formed on the electrodes.
- the spatial separation of the electrode spaces takes place by means of the partition mentioned at the outset, generally a diaphragm or a so-called ion exchange membrane.
- the diaphragm is made of a porous material that is chemically, thermally and mechanically stable with regard to the media, temperatures and pressures that occur in the cell.
- the ion exchange membrane is generally perfluorinated hydrocarbons. These membranes are gas and almost liquid-tight, but allow ions to be transported in an electrical field. - 5 -
- a particular peculiarity of these electrolysis processes lies in the fact that the diaphragm or the ion exchange membrane is pressed against at least one of the two electrodes. This is necessary because it fixes the partition and is therefore largely mechanically unloaded. Often, the partition may only rest on one of the two electrodes, since this is the only way to ensure that all components (electrodes and partition) have the longest possible service life. If the partition wall comes into direct contact with both electrodes, a chemical reaction between the partition wall and the electrodes or the gases developed at the electrodes can take place in some cases.
- a distance between the membrane and the cathode is thus established in the chlor-alkali electrolysis, since otherwise the electrocatalyst or, in the case of inactive nickel cathodes, nickel is released from the electrode.
- nickel oxide diaphragms which are used in alkaline water electrolysis. If the distance to the hydrogen-developing electrode is too small, the nickel oxide is reduced to nickel and thus conductive, which ultimately leads to a short circuit.
- the support of the membrane or the diaphragm on at least one electrode leads to a gas build-up in the electrolyte boundary layer between the electrode and the membrane or the diaphragm in gas-developing processes - 6 -
- Such electrodes are preferably provided with openings (perforated sheet metal, expanded metal, wattle or thin sheets with blind-like openings), so that despite their planar arrangement in the electrolysis cell, the gases formed in the boundary layer during electrolysis can more easily enter the back space of the electrolysis cell.
- the gas bubbles rising in the electrolyte agglomerate particularly in the edges or edges of the openings oriented downward in the cell, and remain firmly in place in the interstices between the adjacent partition (membrane) and the opening edges.
- These bubbles interfere with electricity transport, i.e. the mass transport through the partition, because they block the membrane exchange surface and thus make it inaccessible, i.e. inactive.
- the foam formation leads to pressure fluctuations within the electrochemical cell, since the foam at least temporarily closes the cell outlet for the gas formed.
- the outlet is blown free again by a slight increase in pressure within the cell, which leads to the known effect of the surge flow and to the pressure fluctuations mentioned - 8th -
- the life span of membranes in particular is influenced by the concentration distribution.
- concentration distribution For example, the more homogeneous the salt concentration in the anode compartment of a chlor-alkali electrolyzer, the longer the life of the membrane.
- additional circulation is either generated via externally arranged pumps, or an internal circulation is created by installing a baffle in the cell due to a difference in density.
- the object of the invention is to provide an electrolysis apparatus which can also be operated at current densities above 4 kA / m 2 and, accordingly, increased gas generation in the boundary layer while maintaining long-term service life of the membrane and with low pulsation.
- this design according to the invention enables gas to be removed from the membrane - 9 -
- a suction effect which is caused by the movement of the glass bubbles along the edge of the electrode, ensures that the fresh electrolyte is sucked into the electroactive zone between the membrane or diaphragm and the electrode, which is a necessary prerequisite for a long membrane life in chloralkali electrolysis, for example.
- there is a directional flow since all gas bubbles are forced in one direction.
- the density of the electrolyte / gas mixture drops on one side due to the increasing gas content, which leads to an internal circulation which is 10 to 100 times greater than when entering the electrolyte stream. Excellent homogenization of the electrolyte is thereby achieved.
- the angle of inclination of the blind-like openings with respect to the horizontal lies between 7 ° and 10 °.
- the underside of the respective housing is arranged parallel to the horizontal and the blind-like openings of the anode and cathode are arranged inclined to the underside of the respective housing.
- the electrolysis apparatus per se can then only be modified slightly compared to known electrolysis apparatus, only the anode and the cathode have to be installed at an incline and have to be designed correspondingly at the edge so that they can be installed accordingly.
- the underside of the respective housing is arranged inclined to the horizontal.
- the individual housings then practically do not have to be changed compared to previously known housings, they only have to be installed at an incline with respect to the horizontal, as a result of which the blind-like openings of the cathode and anode are automatically arranged inclined with respect to the horizontal.
- FIG. 1 shows a section through two electrolysis cells of an electrolysis apparatus arranged side by side
- Fig. 2 shows a detail of Fig. 1 in perspective and in
- FIG. 3 also shows an enlarged detail from FIG. 1 in a perspective representation.
- An electrolysis apparatus for producing halogen gases from aqueous alkali halide solution has a plurality of plate-shaped electrolysis cells 2 which are arranged next to one another in a stack and are in electrical contact, of which two such electrolysis cells 2 are shown arranged next to one another in FIG. 1 by way of example.
- Each of these electrolysis cells 2 has a housing made of two half-shells 3, 4, which are provided with flange-like edges, between which a partition (membrane) 6 is clamped in each case by means of seals 5.
- the membrane 6 can optionally also be clamped in another way.
- a plurality of contact strips 7 arranged by welding or the like. are attached or applied to the outside of the relevant rear wall 4A. These contact strips 7 establish electrical contact with the adjacent electrolytic cell 2, namely with the relevant rear wall 3A, on which no separate contact strip is provided.
- a planar anode 8 and a planar cathode 9 are provided within the respective housing 3, 4, adjacent to the membrane 6, the anode 8 and the cathode 9 each being connected to stiffeners arranged in alignment with the contact strips 7, which as webs 10 are trained.
- the webs 10 are preferably attached to the anode or cathode 8, 9 in a metallically conductive manner along their entire side edge 10A.
- the webs 10 taper from their side edges 10A across their width to the adjacent side edge 10B and have a height there that corresponds to the height of the contact strips 7. They are accordingly fastened with their two edges 10B over the entire height of the contact strips 7 to the rear side of the housing rear wall 12A or 4A opposite the contact strips 7. - 13 -
- a suitable device for the respective electrolysis cell 2 is provided for supplying the electrolysis products; such a device is indicated by 11.
- a device for removing the electrolysis products is also provided in each electrolysis cell, but this is not shown.
- the electrodes are designed in such a way that they flow or allow the electrolysis input product or the output products 3 to flow through, for which purpose the anode 8 and the cathode 9 are designed like blinds, i.e. each consist of individual blind-like electrode rods, and are present between the blind-like openings.
- the individual electrode rods are designated 8A and 9A, while the blind-like openings are designated 8B and 9B. It is essential for the invention that these blind-like openings 8B, 9B are arranged inclined to the horizontal, preferably at an angle between 7 ° and 10 °. This angle is designated ⁇ in FIG. 2.
- a suction effect which is caused by the movement of the glass bubbles along the edge of the electrode, ensures that fresh electrolyte is provided in the electroactive zone between membrane 6 or diaphragm and electrode 8, 9, which is a necessary prerequisite, for example, in chlor-alkali electrolysis is a long membrane life.
- there is a directional flow since all glass bubbles are forced in one direction. This flow is indicated by the arrows in Fig. 2.
- the density of the electrolyte gas mixture drops on one side due to the increasing gas content, which leads to an internal circulation which is 10 to 100 times greater than the incoming electrolyte flow. Excellent homogenization of the electrolyte is thereby achieved.
- the structure of the electrolysis apparatus does not otherwise differ from known electrolysis apparatus.
- the stringing together of several plate-shaped electrolysis cells 2 takes place in a framework, the so-called cell framework.
- the plate-shaped electrolysis cells 2 are suspended between the two upper longitudinal beams of the cell frame so that their plate plane is perpendicular to the longitudinal beam axis. So that the plate-shaped electrolysis cells 2 can transmit their weight to the upper flange of the side member, they have a cantilever-like holder on each side of the upper plate edge.
- the holder extends horizontally in the direction of the plate plane and extends beyond the edges of the flanges.
- the lower edge of the cantilever-like holder lies on the upper flange.
- the plate-shaped electrolysis cells 2 hang comparatively like files in a hanging file in the cell frame.
- the plate surfaces of the electrolytic cells are in mechanical and electrical contact, as if they were stacked.
- Electrolysers of this type are called suspended stack type electrolysers.
- the electrolytic cells 2 are connected in an electrically conductive manner to adjacent electrolytic cells in a stack via the contact strips 7. From the contact strips 7, the current then flows through the half-shells via the webs 10 into the anode 8. After passing through the membrane 6, the current is absorbed by the cathode 9 in order to flow via the webs 10 into the other half-shell or its rear wall 3A flow and pass here into the contact strip 7 of the next cell. In this way, the electrolysis current passes through the entire electrolytic cell stack, being introduced on one outer cell and being discharged on the other outer cell.
- the design of the electrolysis cells 2 in the lower region with the electrolyte inlet is not shown in detail in the figures.
- the electrolyte can enter either selectively or with a so-called inlet distributor.
- the inlet distributor is designed so that a tube is arranged in the element that has openings. Since a half-shell is segmented by the webs 10, which represent the connection between the rear walls 3A and 4A and the electrodes 8, 9, an optimal concentration distribution is achieved if both half-shells 3, 4 are equipped with an inlet distributor, the length of the inlet distributor arranged in the half-shell corresponds to the width of the half-shell and each segment - 17 -
- ment is supplied with the respective electrolyte through at least one opening in the inlet distributor.
- the sum of the cross-sectional area of the openings in the inlet distributor should be less than or equal to the inner cross-section of the distributor pipe.
- the two half-shells 3, 4 are provided in the flange area with flanges which are screwed.
- the cells thus constructed are either suspended or placed in a cell frame (not shown).
- the attachment or setting in the cell structure is carried out via holding devices, not shown, located on the flanges.
- the electrolysis apparatus 1 can consist of a single cell or preferably by stringing together a plurality of electrolysis cells 2 in a hanging stack type. If several individual cells are pressed together according to the hanging stack principle, the individual cells must be aligned plane-parallel before the clamping device is closed, since otherwise the current transfer from one individual cell to the next cannot take place via all contact strips 7.
- brackets (not shown) or on the cell frame and cell frame are - 18 -
- the brackets on the element flange frame are covered with a plastic, e.g. PE, PP, PVC, PFA, FEP, E / TFE, PVIF or PTFE, relined, while the contact surfaces on the cell frame are also coated with one of these plastics.
- the plastic can only be placed on or guided over a groove, glued, welded or screwed on. It is only essential that the plastic pads are fixed. Characterized in that two plastic surfaces touch, the individual elements located in the frame are so easy to move that they can be aligned in parallel by hand without additional lifting or sliding device. When the tensioning device is closed, the elements lay flat over the entire rear wall due to their easy displacement in the cell frame, which is the prerequisite for an even current distribution.
- the cell is electrically isolated from the cell framework in this way.
- the invention is not limited to the embodiments shown in the drawings. Further configurations are possible without leaving the basic idea.
- the respective electrodes 8, 9 can be inclined accordingly - 19 -
- the respective electrolytic cell 2 are installed.
- the entire electrolytic cell is arranged obliquely, such that the underside of the respective housing half-shell is arranged inclined with respect to the horizontal, so that the blind-like openings 8A, 9B are inevitably arranged inclined and with respect to the Figures 2 and 3 sets the effect described.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19816334 | 1998-04-11 | ||
DE19816334A DE19816334A1 (en) | 1998-04-11 | 1998-04-11 | Electrolysis apparatus for the production of halogen gases |
PCT/EP1999/002200 WO1999053122A1 (en) | 1998-04-11 | 1999-03-31 | Electrolysis apparatus for producing halogen gases |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1073780A1 true EP1073780A1 (en) | 2001-02-07 |
EP1073780B1 EP1073780B1 (en) | 2002-02-13 |
Family
ID=7864380
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99916899A Expired - Lifetime EP1073780B1 (en) | 1998-04-11 | 1999-03-31 | Electrolysis apparatus for producing halogen gases |
Country Status (20)
Country | Link |
---|---|
US (1) | US6503377B1 (en) |
EP (1) | EP1073780B1 (en) |
JP (1) | JP4460770B2 (en) |
KR (1) | KR100549653B1 (en) |
CN (1) | CN1142326C (en) |
AR (1) | AR019037A1 (en) |
AT (1) | ATE213286T1 (en) |
AU (1) | AU742537B2 (en) |
BR (1) | BR9909589A (en) |
CA (1) | CA2328150C (en) |
DE (2) | DE19816334A1 (en) |
JO (1) | JO2116B1 (en) |
MA (1) | MA24828A1 (en) |
NO (1) | NO20005082L (en) |
PL (1) | PL343179A1 (en) |
RU (1) | RU2215064C2 (en) |
TN (1) | TNSN99037A1 (en) |
TW (1) | TW494144B (en) |
WO (1) | WO1999053122A1 (en) |
ZA (1) | ZA992619B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10249508A1 (en) * | 2002-10-23 | 2004-05-06 | Uhde Gmbh | Electrolysis cell with an inner channel |
DE102005003527A1 (en) * | 2005-01-25 | 2006-07-27 | Uhdenora S.P.A. | An electrolytic cell for the production of chlorine has an anode and a cathode separated from each other by electrically conductive spacers on either side of the ion exchange membrane |
DE102005006555A1 (en) * | 2005-02-11 | 2006-08-17 | Uhdenora S.P.A. | Electrode for electrolysis cells |
DE102006020374A1 (en) * | 2006-04-28 | 2007-10-31 | Uhdenora S.P.A. | Insulating frame for an electrolysis cell for producing chlorine, hydrogen and/or caustic soda comprises an edge region directly connected to an inner front surface and structured so that an electrolyte can pass through it |
DE102006046808A1 (en) * | 2006-09-29 | 2008-04-03 | Uhdenora S.P.A. | Electrolysis cell used for chlor-alkali electrolysis comprises one electrode curved between two bars in the direction of the opposite-lying electrode |
DE102006046807A1 (en) * | 2006-09-29 | 2008-04-03 | Uhdenora S.P.A. | Electrolysis cell used for chlor-alkali electrolysis comprises one electrode curved between two bars in the direction of the opposite-lying electrode |
DE102006055709B3 (en) * | 2006-11-23 | 2008-02-07 | Uhdenora S.P.A. | Measuring cell for electrodes and electrode coating has two chambers with chambers of opposite polarity either side of a membrane |
KR100992716B1 (en) * | 2009-10-13 | 2010-11-05 | 석상엽 | Electrolyzer for withdrawing valuable metal which having more contact specific surface area |
DE102010021833A1 (en) | 2010-05-28 | 2011-12-01 | Uhde Gmbh | Electrode for electrolysis cell |
CN102912399B (en) * | 2012-11-13 | 2016-03-23 | 四川石棉华瑞电子有限公司 | One changes into production line Cathode plate structure |
BR112015018444A2 (en) | 2013-02-05 | 2018-05-08 | Agricultural Technology Research Institute | composition to prevent mycoplasma spp. infection, and expression vector |
EP3464683B1 (en) | 2016-05-26 | 2021-07-07 | Calera Corporation | Anode assembly, contact strips, electrochemical cell, and methods to use and manufacture thereof |
EP4053307A1 (en) | 2021-03-01 | 2022-09-07 | thyssenkrupp nucera AG & Co. KGaA | Electrolysis cell, electrolysis device for chlor-alkali electrolysis and use of an electrolysis cell for chlor-alkali electrolysis |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR850671A (en) * | 1939-02-22 | 1939-12-22 | ||
DE2420011C2 (en) * | 1974-04-25 | 1983-05-11 | Sigri Elektrographit Gmbh, 8901 Meitingen | Sintered electrode for electrochemical processes |
GB1595193A (en) * | 1977-03-04 | 1981-08-12 | Ici Ltd | Diaphragm cell |
DE2914869A1 (en) * | 1979-04-12 | 1980-10-30 | Hoechst Ag | ELECTROLYSIS |
DE3219704A1 (en) * | 1982-05-26 | 1983-12-01 | Uhde Gmbh, 4600 Dortmund | MEMBRANE ELECTROLYSIS CELL |
DE3228884A1 (en) * | 1982-08-03 | 1984-02-09 | Metallgesellschaft Ag, 6000 Frankfurt | VERTICALLY ARRANGED PLATE ELECTRODE FOR GAS GENERATING ELECTROLYSIS |
US4511440A (en) * | 1983-12-22 | 1985-04-16 | Allied Corporation | Process for the electrolytic production of fluorine and novel cell therefor |
DE3501261A1 (en) * | 1985-01-16 | 1986-07-17 | Uhde Gmbh, 4600 Dortmund | ELECTROLYSIS |
US4753718A (en) * | 1986-11-20 | 1988-06-28 | Fmc Corporation | Hydrogen peroxide electrolytic cell |
SE465966B (en) * | 1989-07-14 | 1991-11-25 | Permascand Ab | ELECTRIC FOR ELECTRIC LIGHTING, PROCEDURE FOR ITS MANUFACTURING AND APPLICATION OF THE ELECTRODE |
JPH05195275A (en) * | 1991-07-16 | 1993-08-03 | Hoechst Ag | Electrolytic apparatus |
DE4306889C1 (en) * | 1993-03-05 | 1994-08-18 | Heraeus Elektrochemie | Electrode arrangement for gas-forming electrolytic processes in membrane cells and their use |
DE4415146C2 (en) * | 1994-04-29 | 1997-03-27 | Uhde Gmbh | Electrode for electrolytic cells with an ion exchange membrane |
DE19641125A1 (en) * | 1996-10-05 | 1998-04-16 | Krupp Uhde Gmbh | Electrolysis apparatus for the production of halogen gases |
-
1998
- 1998-04-11 DE DE19816334A patent/DE19816334A1/en not_active Withdrawn
-
1999
- 1999-03-06 JO JO19992116A patent/JO2116B1/en active
- 1999-03-11 TW TW088103745A patent/TW494144B/en not_active IP Right Cessation
- 1999-03-15 TN TNTNSN99037A patent/TNSN99037A1/en unknown
- 1999-03-31 RU RU2000128031/12A patent/RU2215064C2/en not_active IP Right Cessation
- 1999-03-31 EP EP99916899A patent/EP1073780B1/en not_active Expired - Lifetime
- 1999-03-31 AT AT99916899T patent/ATE213286T1/en not_active IP Right Cessation
- 1999-03-31 CN CNB998049786A patent/CN1142326C/en not_active Expired - Fee Related
- 1999-03-31 KR KR1020007011268A patent/KR100549653B1/en not_active IP Right Cessation
- 1999-03-31 BR BR9909589-0A patent/BR9909589A/en active Search and Examination
- 1999-03-31 AU AU35220/99A patent/AU742537B2/en not_active Ceased
- 1999-03-31 DE DE59900867T patent/DE59900867D1/en not_active Expired - Lifetime
- 1999-03-31 JP JP2000543664A patent/JP4460770B2/en not_active Expired - Fee Related
- 1999-03-31 WO PCT/EP1999/002200 patent/WO1999053122A1/en active IP Right Grant
- 1999-03-31 PL PL99343179A patent/PL343179A1/en unknown
- 1999-03-31 CA CA002328150A patent/CA2328150C/en not_active Expired - Fee Related
- 1999-04-05 MA MA25523A patent/MA24828A1/en unknown
- 1999-04-09 AR ARP990101620A patent/AR019037A1/en active IP Right Grant
- 1999-04-09 ZA ZA9902619A patent/ZA992619B/en unknown
-
2000
- 2000-10-09 NO NO20005082A patent/NO20005082L/en not_active Application Discontinuation
- 2000-10-12 US US09/689,457 patent/US6503377B1/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO9953122A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE19816334A1 (en) | 1999-10-14 |
NO20005082L (en) | 2000-12-11 |
KR20010042594A (en) | 2001-05-25 |
JP2002511530A (en) | 2002-04-16 |
ZA992619B (en) | 2000-10-12 |
TNSN99037A1 (en) | 2001-12-31 |
RU2215064C2 (en) | 2003-10-27 |
NO20005082D0 (en) | 2000-10-09 |
US6503377B1 (en) | 2003-01-07 |
WO1999053122A1 (en) | 1999-10-21 |
KR100549653B1 (en) | 2006-02-08 |
JO2116B1 (en) | 2000-05-21 |
JP4460770B2 (en) | 2010-05-12 |
AU3522099A (en) | 1999-11-01 |
CN1296530A (en) | 2001-05-23 |
MA24828A1 (en) | 1999-12-31 |
ATE213286T1 (en) | 2002-02-15 |
AU742537B2 (en) | 2002-01-03 |
PL343179A1 (en) | 2001-07-30 |
CA2328150A1 (en) | 1999-10-21 |
AR019037A1 (en) | 2001-12-26 |
EP1073780B1 (en) | 2002-02-13 |
CA2328150C (en) | 2009-12-08 |
CN1142326C (en) | 2004-03-17 |
DE59900867D1 (en) | 2002-03-21 |
TW494144B (en) | 2002-07-11 |
BR9909589A (en) | 2000-12-19 |
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