EP1362133B1 - Cellule d'electrolyse a electrode de diffusion de gaz fonctionnant a une pression regulee - Google Patents

Cellule d'electrolyse a electrode de diffusion de gaz fonctionnant a une pression regulee Download PDF

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Publication number
EP1362133B1
EP1362133B1 EP02701293A EP02701293A EP1362133B1 EP 1362133 B1 EP1362133 B1 EP 1362133B1 EP 02701293 A EP02701293 A EP 02701293A EP 02701293 A EP02701293 A EP 02701293A EP 1362133 B1 EP1362133 B1 EP 1362133B1
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EP
European Patent Office
Prior art keywords
cell
chambers
chamber
oxygen
gas
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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.)
Expired - Lifetime
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EP02701293A
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German (de)
English (en)
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EP1362133A1 (fr
Inventor
Giuseppe Faita
Fulvio Federico
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Uhde Chlorine Engineers Italia SRL
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Uhdenora SpA
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    • 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
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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

Definitions

  • electrochemical cells such as for example chlor-alkali electrolysis for obtaining chlorine gas and caustic soda or potash, water electrolysis mainly for obtaining hydrogen, the electrolysis of salts for obtaining the corresponding bases and acids, for example caustic soda and sulphuric acid from sodium sulphate, metal deposition, mainly copper and zinc.
  • the physiological problem affecting all these processes is the energy consumption, which usually constitutes a substantial portion of the overall production cost. As the cost of electric energy shows in all geograophical areas a constant trend towards increase, the importance of decreasing the energy consumption in the above mentioned electrochemical processes is clear.
  • the energy consumption in an electrochemical process primarily depends on the cell voltage: it is therefore soon evident the reason for the efforts directed to the improvement of the cell design, with the use of more catalytic electrodes and with the decrease of the ohmic drops in the cell structure itself and in the electrolytes, for example by decreasing the interelectrodic gap.
  • a sodium chloride solution less frequently potassium chloride, is fed to a cell containing an anode, wherein chlorine gas is evolved, while at the cathode hydrogen is evolved with the concurrent of sodium hydroxide (caustic soda - potassium hydroxide when the cell is fed with potassium chloride).
  • the caustic soda close to the cathode is maintained separate from the sodium chloride solution present in the anodic area by a membrane made of a perfluorinated polymer containing anionic groups, for example sulphonic or carboxylic groups.
  • Said membranes are commercialized by various Companies, such as for example DuPont/USA, Asahi Glass and Asahi Chemical/Japan.
  • a chlor-alkali electrolysis cell comprising a cathode fed with a gas containing oxygen has an energy consumption which is physiologically remarkably lower that that typical of the conventional technology.
  • the reason for this result is essentially of thermodynamic nature, as the two cells, the conventional one and the one containing the oxygen cathode, are characterized by two different overall reactions:
  • the oxygen cathode is substantially made of a porous support, preferably conductive, having applied thereto a microporous layer made of an assembly of electrocalytic particles mechanically stabilized by a binder resistant to the operating conditions.
  • This layer may comprise a further film also incorporating preferably conductive but not electrocatalytic particles, and a binder.
  • the porous layer may consist of a mesh, a variously perforated sheet, carbon/graphite cloth, carbon/graphite paper or sinterized materials.
  • an electrode as the above described is used as an oxygen consuming cathode for chlor-alkali electrolysis, in a parallel position with respect to the cationic membrane, in direct contact or at a limited distance therefrom, indicatively 2-3 mm, the caustic soda produced by the reaction of oxygen onto the electrocalytic particles must be in some way discharged to avoid a progressive filling of the micro-porosity of the layer. In fact should a complete filling occur, oxygen could not diffuse through the pores to reach the catalytic particles, where the reaction takes place.
  • the discharge of the produced caustic soda may be obtained essentially in two ways, either towards the membrane when the cathode is parallel and at a certain distance from the cationic membrane, or towards the oxygen atmosphere, on the opposite side with respect to the one facing the membrane, in the case the cathode is in contact with the membrane.
  • a liquid film 2-3 mm thick as already said, is normally kept in circulation upwards (cells are equipped with vertically disposed electrodes) both to withdraw the produced caustic from the cell as well to remove the heat produced by the reaction, and finally to control the caustic soda concentration within predetermined limits which permit to prolong the ion exchange membrane lifetime:
  • This situation creates a pressure gradient between caustic soda and oxygen at the two sides of the cathode, which actually acts as a separation wall.
  • This gradient may be positive (pressure of the caustic soda higher than that of oxygen) and in this case it increases from top to bottom due to the hydraulic head.
  • the gradient may be negative (pressure of oxygen higher than that of caustic soda) and in this case it decreases from top to bottom once again due to the hydraulic head of caustic soda.
  • cathodes capable of resisting to pressure differential in the range of 30 cm (intended as water column).
  • the cells suitable for housing the same cannot have a height above 30 cm.
  • the cathode is either completely flooded with the total filling of the porosity by caustic soda with positive differential or completely gas filled with a heavy loss of oxygen in the caustic soda in the case of a negative differential.
  • the ion exchange membranes available on the market are irreversibly damaged when in contact, even for relatively short times, with caustic soda at a concentration above 35%. Therefore, it has been suggested to operate the cell equipped with an oxygen cathode in direct contact with the membrane with diluted solutions of alkali chloride, as it is known that the quantity of transported water increases as the alkali chloride concentration decreases.
  • the operation flexibility permitted by this factor is limited as too low concentrations of alkali chloride negatively affect the membrane efficiency, increase the oxygen content in chlorine and can decrease the operating lifetime of the anodes.
  • the second problem is connected to the fact that gas diffusion cathodes let percolate minimum quantities of caustic soda on the gas side or give rise to condensation of part of the water vapor contained in the oxygen. In any case there is always a small but not negligible formation of a liquid phase which must be removed continuously to avoid flooding of the oxygen chambers corresponding to each strip of gas diffusion cathode.
  • the device illustrated in DE 19954247 A1 does not permit the removal of the condensate phases and therefore its performance are bound to be inevitably spoiled with time.
  • the invention intends to disclose the design of an electrolysis cell containing a liquid electrolyte and at least a gas diffusion electrode with a surface in contact with the liquid electrolyte and the opposite surface connected with at least two gas chambers, wherein said chambers are provided with devices characterized by dynamic pressure drop, such as for example rotameters, and the connection between two subsequent chambers is provided by said devices.
  • the design is characterized by the fact that said devices maintain a constant pressure in said chambers even under strong variations of the gas flow.
  • each gas chamber be supplied with at least a discharge element for the accumulated liquid. Said element, exploiting the pressure differential between two subsequent chambers, permits the flow of the liquid phase from a chamber to the subsequent one until it is discharged in the liquid electrolyte flow leaving the cell.
  • FIG. 1 A preferred embodiment of the device of the invention is illustrated in Fig. 1 , which schematizes a side view cross-section of an industrial cell incorporating at least one gas diffusion electrode.
  • a multiplicity of cells as that of Fig. 1 are assembled to form an assembly known as electrolyzer, normally according to a preferred configuration called filter-press.
  • electrolyzer normally according to a preferred configuration called filter-press.
  • reference will be made to the chlor-alkali electrolysis with air diffusion cathodes, and more particular oxygen.
  • this is not to be considered as a limitation of the invention as several other applications may be easily foreseen, for example for hydrochloric acid electrolysis, sodium sulphate and the electrometallurgy field.
  • Fig. 1 the main components of the electrolysis cell are identified by numbers, as hereinafter indicated:
  • the gas (oxygen in the present case) diffusion cathode is fixed onto a frame, identified by 11 in Fig. 2 , by various methods, for example by a purely mechanical method with screws or metallurgically by welding, preferably laser welding.
  • This connection performs two functions: electric current transmission to the gas diffusion cathode and sealing between caustic soda and oxygen, to avoid either the caustic soda penetration into the back side of the cathode compartment, filled with oxygen, flooding the same, or, conversely, oxygen bubbling in caustic soda altering the flow uniformity and hindering the electric current passage.
  • gaskets not shown in the figure, may be inserted between the oxygen diffusion cathode and the frame 11.
  • the frame 11 is fixed to the cathode shell 6 by means of conductive supports 12. These conductive supports are made of strips of sheets fixed, for example by linear welding, preferably of the laser type, to the cathode shell 6 and to the frame 11 along their whole perimeter. In this way the assembly cathodic shell 6 - supports 12 - frame 11 - diffusion cathode 9 defines chambers 13 insulated one from another, three of them in the specific case of Fig. 1 . Obviously a different number of chambers may be obtained in practice.
  • Each chamber is equipped with at least a dynamic pressure drop device 14 and at least one discharge element 15 for the accumulated liquid, according to the present invention. In each chamber the liquid may accumulate with time as a result of both moderate electrolyte percolation (caustic soda in the present case) through micro-defects of the diffusion cathode and condensation of at least part of the water vapor contained in oxygen.
  • the residual amount of oxygen crosses then the first device 14 which permits to establish a pressure difference between the first chamber just crossed and the subsequent one.
  • the subsequent chamber the above illustrated situation is repeated: longitudinal flow, partial reaction at the diffusion cathode, crossing of the second device. The same situation occurs in the subsequent chambers.
  • the residual oxygen is then discharged through nozzle 17.
  • the value of the pressure differential is defined by the weight of the float, which in turn may be regulated by adding suitable elements or by adjusting the geometrical dimensions and/or the density of the material used for the construction. Indications on both the theory on which the operation of the rotameters is based and on the type of possible designs are given in the manual " Perry's Chemical Engineers' Handbook, 7.th Edition, McGraw - Hill"-at pages 10 -18 ff .
  • the purpose of dividing the space occupied by oxygen into a certain number of chambers is to vary, even if in a discontinuous manner, the oxygen pressure in the vertical direction, that is in the same direction wherein also the pressure exerted by the caustic soda head varies. More particularly, the purpose of the design is to maintain a low value of pressure differential between caustic soda and oxygen in every point across the wall represented by the porous film which constitutes the gas diffusion cathode.
  • the reason for maintaining this difference at a low value derives from the need to minimize the mechanical stress on the diffusion cathode to avoid deformation and tearing and to prevent percolation of caustic soda on the oxygen side and oxygen bubbling in the gap 10 between the ion exchange membrane and the gas diffusion cathode.
  • the gas diffusion cathodes of the prior art do not tolerate pressure differentials above more or less 30 - 40 cm of water column. If, without introducing limitations to the invention, the height of each chamber is 30 cm and if the rotameter positioned out the outlet of each chamber provides for a gas pressurization equal to 30 cm of water column or slightly more, then the pressure difference between caustic soda and gas results approximately nil at the bottom of the chamber and equal to 30 cm or slightly more in the upper part of the chamber, therefore certainly within the tolerance limits for the diffusion cathode. This situation characterizes the first upper chamber on the hypothesis that the discharge pressure of caustic soda and oxygen be the same.
  • each chamber is carried out preferably by means of rotameters
  • other devices may be used as well, provided that they can ensure a pressurization in the range of tens of cm of water column and substantially independent from the gas flow rate
  • devices made of a pipe, whose upper end is closed by a mobile shutter maintained in place by a return spring are probably suitable for achieving the advantages of the invention.
  • each oxygen chamber having the purpose of maintaining the pressure difference between caustic soda and oxygen across the diffusion cathode within moderate limits for all the vertical extension of the cell, is defined, as above mentioned, a pressure compensation system.
  • the cathodic shell 6 is provided with caustic soda feeding nozzles 18 and discharge nozzles 19, each one connected to an internal perforated pipe, 20 and 21 respectively, whose purpose is ensuring a homogeneous distribution.
  • Caustic soda penetrates inside the gap 10 between the membrane and the oxygen diffusion cathode through an opening 22 obtained in the lower portion of frame 11 and leaves the gap through a further opening 23 made in the upper portion of frame 11.
  • the gap 10 may be empty or filled with a spacer (not shown in Fig. 1 ), for example a large size mesh or other structure, preferably elastic, for example a mattress of interwoven wires.
  • a spacer for example a large size mesh or other structure, preferably elastic, for example a mattress of interwoven wires.
  • the construction design of the oxygen chambers illustrated in Fig. 1 obviously is not the only one applicable.
  • the chambers may be prefabricated as independent boxes and provided with a peripheral flat flange to permit fixing by welding, preferably laser welding, to the frame 11.
  • the assembly frame - boxes is then fixed inside the cathodic shell 6 to the supports 12 already described.
  • the bottoms of the boxes may be directly welded to the wall of the cathodic shell, and in this case the supports 12 are no more necessary.
  • the periphery of the frame 11 is extended to form a flat flange.
  • the independent boxes are fixed as previously mentioned.
  • the assembly thus obtained, provided with the necessary above illustrated nozzles, may be directly used as cathodic shell.
  • the construction material of the cathodic shell 6, the supports 12, the frame 11, the rotameters 14 and, in one of the possible construction alternatives, of the boxes for housing the oxygen chambers is nickel.
  • Some of these parts may be silver-plated, to ensure a further reduced release of nickel, for example frame 11, and the mesh which may be applied to frame 11 to maintain the best current distribution to the oxygen diffusion cathode.
  • An aspect of the present invention is that the oxygen chambers are capable of releasing the liquid phases which are collected on the bottom by the accumulation of liquid due to both small leaks of caustic soda through microdefects of the cathode and the at least partial condensation of the water vapor contained in the oxygen.
  • the discharge element of the liquid phase identified by 15 in Figures 1 , 3 and 6 , is made of a pipe 24 fixed to the ceiling. 25 of the chamber with the upper end 26 practically in contact with the ceiling itself and the lower end 27 slightly spaced from the bottom 28 of the chamber itself.
  • the empty pipe 24 represents a path for oxygen in parallel with rotameter 14. To avoid that the operation of the rotameter be substantially spoiled and in particular to avoid that the pressurization value may be affected, it is necessary that the gas flow rate through pipe 24 represent a minor portion of the overall gas flow.
  • the overall gas flow of the oxygen feed is about 3 m 3 /hour and is reduced indicatively to 1 m 3 /hour at the outlet.
  • the gas flow through the pipe 24 be not more than 10 % of the flow-rate in the rotameter 14, a value of 0.1 - 0.3 m 3 /hour is obtained.
  • pipe 24 must have a very small diameter, in any case not above 1 mm, with the possible risk of stoppage due to the micropowders released by the material of construction of the gas diffusion cathode.
  • An alternative and more reliable embodiment is based on the use of a pipe 24 having a substantially larger diameter containing at the inside a hydrophilic porous, chemically resistant material, such as for example a fiber pressed material 30, such as zirconium oxide fibers.
  • a hydrophilic porous, chemically resistant material such as for example a fiber pressed material 30, such as zirconium oxide fibers.
  • This material is preferably saturated with water during assembly and provides for an efficient barrier toward the gas passage.
  • the hydrophilic nature of the filling of pipe 24 facilitates the absorption of the liquid phase separated onto the bottom of each cell, in particular when the hydrophilic material is in contact with the bottom of the chamber.
  • element 15 may consist of a short piece of pipe 24, containing the hydrophilic fibers 30 which are prolonged nearly till the bottom 28 of each chamber, for example reaching a distance of some millimeters from the bottom, or lying on the bottom itself. In this case the liquid rises along the fibers by capillarity up to the piece of pipe 24 where the bundle of fibers is pressed and due to the pressure difference, it is transferred above.
  • Another embodiment is represented by the use of sticks of porous ceramic material, for example sinterized zirconium oxide, fixed through a suitable collar to a hole in the ceiling 25 of each chamber.
  • porous ceramic material for example sinterized zirconium oxide

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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)

Claims (14)

  1. Cellule d'électrolyse contenant un électrolyte liquide et au moins une électrode de diffusion de gaz dont une surface est en contact avec ledit électrolyte et la surface opposée est reliée à au moins deux chambres contenant ledit gaz, lesdites chambres étant du type à compensation de pression,
    caractérisée en ce que
    chacune desdites chambres est pourvue d'un dispositif d'évacuation dudit gaz, du type à chute de pression dynamique, capable d'assurer à l'intérieur de chacune desdites chambres une valeur de pression sensiblement indépendante du débit dudit gaz.
  2. Cellule selon la revendication 1, dans laquelle lesdites chambres sont reliées entre elles au moyen desdits dispositifs d'évacuation.
  3. Cellule selon l'une des revendications 1 ou 2, dans laquelle ledit au moins un dispositif d'évacuation est un rotamètre.
  4. Cellule selon la revendication 3, dans laquelle les surfaces internes dudit rotamètre sont hydrophobes.
  5. Cellule selon la revendication 1, dans laquelle ledit au moins un dispositif d'évacuation comprend un volet mobile relié à un ressort de rappel.
  6. Cellule selon l'une des revendications 1 à 5, dans laquelle la différence entre la charge hydraulique de l'électrolyte et la pression du gaz à l'intérieur desdites chambres est maintenue dans une limite de 30 - 40 cm de colonne d'eau le long de la hauteur de ladite cellule, ladite limite correspondant, de préférence, à environ 30 cm de colonne d'eau.
  7. Cellule selon l'une des revendications 1 à 6, caractérisée, en outre, en ce qu'au moins l'une desdites chambres est pourvue d'au moins un dispositif de soutirage du liquide collecté sur le fond.
  8. Cellule selon la revendication 7, dans laquelle ledit dispositif de soutirage est constitué d'un conduit d'un diamètre n'excédant pas 1 mm, fixée au plafond de ladite au moins une chambre, l'extrémité supérieure étant sensiblement en contact avec ledit plafond et l'extrémité inférieure située à proximité du fond de ladite au moins une chambre mais sans être en contact avec celui-ci, ou dans laquelle ledit dispositif de soutirage est constitué d'un conduit contenant un matériau poreux, hydrophile et chimiquement résistant, ledit conduit étant fixé au plafond de ladite au moins une chambre, l'extrémité supérieure étant sensiblement en contact avec ledit plafond et l'extrémité inférieure située à proximité du fond de ladite cellule mais sans être en contact avec celui-ci.
  9. Cellule selon la revendication 8, dans laquelle ledit matériau poreux consiste en un faisceau de fibres comprimées, lesdites fibres étant, de préférence, de l'oxyde de zirconium.
  10. Cellule selon la revendication 9, dans laquelle ledit faisceau de fibres est en contact avec le fond de ladite chambre.
  11. Cellule selon la revendication 7, dans laquelle ledit dispositif de soutirage est constitué d'un conduit fixé au plafond de ladite au moins une chambre, l'extrémité supérieure étant sensiblement en contact avec ledit plafond et l'extrémité inférieure sensiblement séparée du fond de ladite chambre, ledit conduit contenant un matériau chimiquement résistant, poreux et hydrophile, ledit matériau poreux ayant soit une longueur suffisante pour sortir dudit conduit jusqu'à seulement quelques millimètres dudit fond, soit une longueur suffisante pour être en contact avec ledit fond.
  12. Cellule selon la revendication 11, dans laquelle ledit matériau poreux est un faisceau de fibres, de préférence un faisceau de fibres d'oxyde de zirconium.
  13. Cellule selon la revendication 7, dans laquelle le dispositif de soutirage est constitué d'un collier fixé au plafond de ladite au moins une chambre et supporte une baguette de matériau poreux céramique, ledit matériau céramique étant, de préférence, de l'oxyde de zirconium fritté.
  14. Cellule d'électrolyse selon les revendications précédentes, dans laquelle ladite électrolyse est une électrolyse à l'alcali et au chlore et ladite électrode de diffusion de gaz est une cathode de diffusion d'air ou d'oxygène.
EP02701293A 2001-02-23 2002-02-22 Cellule d'electrolyse a electrode de diffusion de gaz fonctionnant a une pression regulee Expired - Lifetime EP1362133B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT2001MI000362A ITMI20010362A1 (it) 2001-02-23 2001-02-23 Cella di elettrolisi con elettrodo a diffusione di gas operante a pressione controllata
ITMI20010036 2001-02-23
PCT/EP2002/001910 WO2002068720A1 (fr) 2001-02-23 2002-02-22 Cellule d'electrolyse a electrode de diffusion de gaz fonctionnant a une pression regulee

Publications (2)

Publication Number Publication Date
EP1362133A1 EP1362133A1 (fr) 2003-11-19
EP1362133B1 true EP1362133B1 (fr) 2011-07-27

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EP02701293A Expired - Lifetime EP1362133B1 (fr) 2001-02-23 2002-02-22 Cellule d'electrolyse a electrode de diffusion de gaz fonctionnant a une pression regulee

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EP (1) EP1362133B1 (fr)
AT (1) ATE518022T1 (fr)
ES (1) ES2370387T3 (fr)
IT (1) ITMI20010362A1 (fr)
WO (1) WO2002068720A1 (fr)

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US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
US10287223B2 (en) 2013-07-31 2019-05-14 Calera Corporation Systems and methods for separation and purification of products

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US9200375B2 (en) 2011-05-19 2015-12-01 Calera Corporation Systems and methods for preparation and separation of products
SA112330516B1 (ar) * 2011-05-19 2016-02-22 كاليرا كوربوريشن انظمة وطرق هيدروكسيد كهروكيميائية مستخدمة لأكسدة المعدن
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10619254B2 (en) 2016-10-28 2020-04-14 Calera Corporation Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide
WO2019060345A1 (fr) 2017-09-19 2019-03-28 Calera Corporation Systèmes et procédés utilisant un halogénure de lanthanide
DE102017219766A1 (de) * 2017-11-07 2019-05-09 Siemens Aktiengesellschaft Anordnung für die Kohlendioxid-Elektrolyse
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
DE19622744C1 (de) * 1996-06-07 1997-07-31 Bayer Ag Elektrochemische Halbzelle mit Druckkompensation
DE19715429A1 (de) * 1997-04-14 1998-10-15 Bayer Ag Elektrochemische Halbzelle
DE19954247C2 (de) * 1999-11-11 2002-11-14 Wolfgang Strewe Elektrolysezelle mit Gasdiffusionselektrode für großtechnische Anlagen sowie Verwendungen der Elektrolysezelle

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287223B2 (en) 2013-07-31 2019-05-14 Calera Corporation Systems and methods for separation and purification of products
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products

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Publication number Publication date
WO2002068720A1 (fr) 2002-09-06
ITMI20010362A1 (it) 2002-08-23
ES2370387T3 (es) 2011-12-15
ATE518022T1 (de) 2011-08-15
EP1362133A1 (fr) 2003-11-19

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