EP1527213B1 - Procede et systeme de refroidissement d une cuve d electrolyse pour la production d aluminium - Google Patents

Procede et systeme de refroidissement d une cuve d electrolyse pour la production d aluminium Download PDF

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Publication number
EP1527213B1
EP1527213B1 EP03763932A EP03763932A EP1527213B1 EP 1527213 B1 EP1527213 B1 EP 1527213B1 EP 03763932 A EP03763932 A EP 03763932A EP 03763932 A EP03763932 A EP 03763932A EP 1527213 B1 EP1527213 B1 EP 1527213B1
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EP
European Patent Office
Prior art keywords
droplets
cooling
shell
transfer fluid
heat transfer
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.)
Revoked
Application number
EP03763932A
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German (de)
English (en)
French (fr)
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EP1527213A2 (fr
Inventor
Laurent Fiot
Claude Vanvoren
Airy-Pierre Lamaze
Bernard Eyglunent
Jean-Luc Basquin
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.)
Rio Tinto France SAS
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Aluminium Pechiney SA
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Application filed by Aluminium Pechiney SA filed Critical Aluminium Pechiney SA
Priority to SI200331233T priority Critical patent/SI1527213T1/sl
Publication of EP1527213A2 publication Critical patent/EP1527213A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium

Definitions

  • the invention relates to the production of aluminum by igneous electrolysis, in particular by the Hall-Héroult electrolysis process, and the installations intended for the industrial implementation of this production.
  • the invention relates more specifically to the control of thermal flows of the electrolysis cells and the cooling means which make it possible to obtain this control.
  • Aluminum metal is produced industrially by igneous electrolysis, namely by electrolysis of alumina in solution in a bath based on molten cryolite, called an electrolyte bath, in particular according to the well-known Hall-Héroult process.
  • the electrolyte bath is contained in tanks, called “electrolysis cells”, comprising a steel box, which is coated internally with refractory and / or insulating materials, and a cathode assembly located at the bottom of the tank. Anodes are partially immersed in the electrolyte bath.
  • electrolysis cell normally designates the assembly comprising an electrolytic cell and one or more anodes.
  • the electrolysis current which circulates in the electrolyte bath and the liquid aluminum sheet through the anodes and cathode elements and which can reach intensities greater than 500 kA, operates the reduction reactions of the alumina and also makes it possible to maintain the electrolyte bath at a temperature of the order of 950 ° C. by Joule effect.
  • the electrolysis cell is regularly supplied with alumina so as to compensate for the consumption of alumina resulting from the electrolysis reactions.
  • the electrolysis cell is generally controlled in such a way that it is in thermal equilibrium, that is to say that the heat dissipated by the electrolysis cell is globally compensated by the heat produced in the cell, which comes from essentially electrolysis current.
  • the thermal equilibrium point is generally selected so as to achieve the most favorable operating conditions from a not only technical but also economic point of view.
  • the possibility of maintaining an optimum setpoint temperature is a significant saving in the cost of producing aluminum due to the maintenance of the current efficiency (or Faraday efficiency) at a very high value, which reaches values greater than 95% in the most efficient factories:
  • the thermal equilibrium conditions depend on the physical parameters of the cell (such as the dimensions and nature of the constituent materials or the electrical resistance of the cell) and the operating conditions of the cell (such as the temperature of the bath or the intensity of the electrolysis current).
  • the cell is often constituted and conducted so as to cause the formation of a solidified bath slope on the side walls of the tank, which in particular makes it possible to inhibit the attack of the coatings of said walls by the liquid cryolite.
  • the plaintiff has set itself the objective of finding means, effective and adaptable, to evacuate and dissipate the heat produced by the electrolysis cell, which can easily be put in place and which do not require any major modifications of the cell, and in particular of the box, nor an important infrastructure, nor the additional operating cost prohibitive.
  • the Applicant has particularly sought ways to change the power of cells, which easily adapt to different cell types or different modes of operation of the same type of cell, and which are suitable for industrial installations with a large number of cells in series.
  • the subject of the invention is a method for cooling an igneous electrolysis cell for the production of aluminum in which a heat-transfer fluid absorbs heat from said cell by a phase change of all or part of said fluid in contact with the cell of the cell.
  • a "coolant divided” is produced, such as droplets of a coolant, and all or part of said droplets in contact with the vessel chamber, so as to cause the vaporization of all or part of them.
  • the coolant vapor formed by the vaporization of all or part of said droplets in contact with the box can be removed by natural ventilation (such as convection), by blowing or by suction.
  • the vaporization takes heat from the cell and this heat can then be removed with the coolant vapor.
  • the divided form of the heat transfer fluid makes it possible to preserve the latent heat of evaporation of the fluid until it comes into contact with the chamber of the vessel.
  • the droplets heat up and vaporize, at least partially, in contact with the box and the steam thus produced carries a quantity of thermal energy, a large part of which corresponds to the latent heat of evaporation of the fluid.
  • the Applicant therefore had the idea of benefiting from the high heat absorption capacity associated with the vaporization of the droplets to considerably increase the cooling power of the coolant.
  • the formation of a heat transfer fluid in divided form in a gas makes it possible to obtain a thermal conductivity, a specific heat and a higher latent heat than the gas alone.
  • the Applicant has also had the idea that the splitting or splitting of the fluid into distinct droplets makes it possible, in addition, to produce a substantially homogeneous but discontinuous heat transfer fluid, which breaks, in particular, the electrical continuity of the heat transfer fluid, while preserving a high thermal capacity to the coolant.
  • the electrolysis cell is provided with at least one confinement means forming a confined space in proximity to a determined surface of at least one of the walls of the chamber of the vessel and droplets of a heat transfer fluid are produced in said space.
  • the means of containment may possibly be in contact with the box. It can possibly be attached or attached to the box or secured to it.
  • the invention also relates to a cooling system of an igneous electrolysis cell for the production of aluminum which is characterized in that it comprises at least one means for producing droplets of a heat transfer fluid, preferably near the chamber of the tank, and a means for bringing said droplets in contact with the box, so as to cause the vaporization of all or part thereof.
  • the cooling system according to the invention may also comprise means for evacuating the vaporized coolant.
  • the cooling system further comprises at least one containment housing, at least one coolant supply means and at least one means for producing droplets of said fluid in said housing.
  • the containment boxes which are typically placed at a determined distance from the surface of the vessel box, promote the contact of the droplets with a specific surface of the box. They are preferably placed near the side walls of the box. They may optionally be contiguous or attached to the walls of the box or be integral with it.
  • Said cooling system is able to implement the cooling method according to the invention.
  • the subject of the invention is also a method of regulating an electrolysis cell intended for the production of aluminum by igneous electrolysis, including a method of cooling the cell according to the invention.
  • the invention also relates to an electrolysis cell for the production of aluminum by igneous electrolysis comprising a cooling system according to the invention.
  • the invention also relates to the use of the cooling method according to the invention for cooling a cell production of aluminum by igneous electrolysis.
  • the invention also relates to the use of the cooling system according to the invention for cooling an aluminum production cell by igneous electrolysis.
  • the invention applies in particular to the production of aluminum by the Hall-Héroult process.
  • the invention makes it possible to reduce the thickness of the internal refractory linings (or “crucibles") of the cells of electrolysis cells, in particular the side walls, and to increase by as much the internal volume of the crucible able to contain the bath of 'electrolysis.
  • the figure 1 represents, in cross-section, an electrolysis cell for the production of typical aluminum using prebaked anodes made of carbonaceous material.
  • the figure 2 illustrates, schematically and in cross section, an electrolysis cell comprising a cooling system according to a preferred embodiment of the invention.
  • the figure 3 illustrates, schematically and in cross section, a portion of the cooling system according to a preferred embodiment of the invention.
  • the figure 4 illustrates, schematically and in side view, an electrolytic cell tank provided with a cooling system according to a preferred embodiment of the invention.
  • the figure 5 illustrates, schematically and according to section AA of the figure 3 , an electrolysis cell provided with a cooling system according to a preferred embodiment of the invention.
  • an electrolysis cell (1) for producing aluminum by igneous electrolysis typically comprises a vessel (20), anodes (7) and alumina feed means (11).
  • the anodes are connected to an anode frame (10) by means of support and fixing means (8, 9).
  • the tank (20) comprises a metal box (2), typically made of steel, internal lining elements (3, 4) and cathode elements (5).
  • the lining elements (3, 4) are generally blocks of refractory materials, which may be, in whole or in part, thermal insulators.
  • the cathode elements (5) include connecting bars (or cathode bars) (6), typically made of steel, to which are fixed the electrical conductors for the routing of the electrolysis current.
  • the coating elements (3, 4) and the cathode elements (5) form, inside the tank, a crucible for containing the electrolyte bath (13) and a liquid metal sheet (12) when the cell is in operation, during which the anodes (7) are partially immersed in the electrolyte bath (13).
  • the electrolyte bath contains dissolved alumina and, in general, an alumina-based cover (or crust) (14) covers the electrolyte bath.
  • the inner side walls (3) may be covered with a solidified bath layer (15).
  • the coating elements (3, 4) often consist of edge slabs made of carbonaceous material or based on carbon compounds, such as an SiC-based refractory, and broth pasta.
  • the electrolysis current passes through the anode frame (10) into the electrolyte bath (13), support and fixing means (8, 9), anodes (7), cathode elements (5) and ) and cathode bars (6).
  • the aluminum metal that is produced during the electrolysis normally accumulates at the bottom of the tank and there is established a fairly sharp interface (19) between the liquid metal (12) and the molten cryolite bath ( 13).
  • the position of this bath-metal interface can vary over time: it rises as the liquid metal accumulates at the bottom of the tank and lowers when liquid metal is removed from the tank .
  • electrolysis cells are generally arranged in line, in buildings called electrolysis halls, and electrically connected in series using connecting conductors. More specifically, the cathode bars (6) of an "upstream” tank are electrically connected to the anodes (7) of a so-called “downstream” tank, typically via connecting conductors (16, 17, 18). and means for supporting and connecting (8, 9, 10) anodes (7).
  • the cells are typically arranged to form two or more parallel lines. The electrolysis current thus cascades from one cell to the next.
  • the anodes (7) are typically made of carbonaceous material, although they can also consist, in whole or in part, of a non-consumable material, called "inert” material, such as a metallic material or ceramic / metal composite (or “Cermet").
  • Spraying all or part of the coolant droplets causes a heat transfer from the box to the coolant, which allows to take heat from the box and cool.
  • said droplets are brought into contact with a determined surface (107) of the box (2), which makes it possible to select the most thermally advantageous surfaces and thus to increase the cooling efficiency of the tank in certain conditions.
  • the contact with the box (2) is a thermal contact, in that it makes it possible to take thermal energy from the box by the vaporization of all or part of the droplets of coolant.
  • the droplets may be brought into contact with the box, and more precisely the outer surface of the box, in various ways, such as by confinement in the vicinity of the box, by channeling, by projection, or a combination of these means.
  • the method of cooling an electrolysis cell (1) intended for the production of aluminum by igneous electrolysis is characterized in that, in addition, the cell is equipped with electrolysis (1) of at least one means (101), referred to as "confinement means", to form a confined space (102) in proximity to (or possibly in contact with) a determined surface (107) of at least one walls (21, 22, 23) of the box (2), preferably at least one of the side walls (21, 22) of the box (2), and in that it comprises the production of droplets of a heat transfer fluid in said space (102), so as to put all or part of said droplets in contact with said surface (107).
  • the cell is equipped with electrolysis (1) of at least one means (101), referred to as "confinement means", to form a confined space (102) in proximity to (or possibly in contact with) a determined surface (107) of at least one walls (21, 22, 23) of the box (2), preferably at least one of the side walls (21, 22) of the box (2), and in that it comprises the production of drop
  • near means at a distance typically less than 20 cm, or even less than 10 cm.
  • the droplets are typically produced at a determined distance D from one of the walls (21, 22, 23) of the box (2), that is to say that the zone (s) of production of the coolant divided is located at a determined distance D from said wall.
  • the heat transfer fluid is then conveyed, typically in the liquid state, to said determined distance D.
  • the droplets are preferably formed near the chamber of the vessel in order to prevent coalescence (or agglomeration) thereof before their vaporization in contact with said wall, ie the determined distance is preferably low (preferably less than about 20 cm, and more preferably less than 10 cm).
  • the production areas are typically located in one or more containment housings (101).
  • the droplets can be produced continuously or discontinuously.
  • the production rate of said droplets may be variable.
  • the cooling method advantageously comprises controlling the production rate of said droplets.
  • the volume proportion of coolant droplets can then be varied in a controlled manner. This variant of the invention makes it possible to finely control the extraction of heat from the cell.
  • Said droplets typically have a size of between 0.1 and 5 mm, and preferably between 1 and 5 mm. Droplets of size less than about 0.1 mm have the disadvantage of being easily driven by the movements of the ambient air, or by the possible flow of evacuation of vaporized droplets, before coming into contact with the caisson.
  • the droplets form a mist, preferably a dense mist, in order to promote the vaporization of the droplets and to increase the cooling efficiency.
  • said droplets are produced by spraying said heat transfer fluid, typically from the liquid phase.
  • This spraying can be carried out using at least one nozzle.
  • the heat transfer fluid is advantageously water because this substance has a very high latent heat of vaporization.
  • Said water is preferably purified, in order to reduce its electrical conductivity and to limit the deposits on the wall of the box which could, in the long term, reduce the cooling efficiency.
  • This purification is advantageously carried out, upstream, with the aid of a treatment column (113). It typically comprises a deionization operation of the water.
  • the purified water contains in total a quantity of ions (anions and cations) of less than 10 ⁇ g per liter of water, and more preferably less than 1 ⁇ g per liter of water.
  • the confinement means (101) comprises at least one housing, that is to say that the heat transfer fluid is confined by means of at least one housing ( 101).
  • This housing is placed at a determined distance from the wall of the box.
  • This embodiment makes it possible to increase the probability of physical contact between said droplets and the surface of the box (and preferably a determined surface (107) of the box), and to prevent their dispersion in the space surrounding the bowl.
  • the containment housing (101) typically has a determined internal space or volume (102), but is preferably open, typically on the cabinet side. It may be possible to individually control the rate of droplet formation in each containment housing (101).
  • the containment means (101) can be attached to or attached to the box (2) or integral with it.
  • said housing (101) it is advantageous to place said housing (101) so that it overlaps the average level of the interface (19) between the electrolyte bath (13) and the liquid metal ply (12); ie so as to be located on both sides of the average level of said interface.
  • the cooling method according to the invention may furthermore comprise an evacuation of all or part of the coolant vapor formed by the vaporization of all or part of said droplets in contact with the box (2) (and in particular in contact with said determined surface (107).
  • This evacuation can be carried out by natural ventilation, by suction or by blowing, or a combination of these means.
  • the coolant vapor is typically discharged continuously.
  • the vaporized heat transfer fluid is channeled (typically by suction or blowing) to a place remote from the tanks, which can be located in the same hall or outside thereof, or the heat transfer fluid can optionally be cooled, so as to condense the coolant vapor, and reintroduced into the cooling circuit.
  • the droplets are mixed with a carrier gas in order to facilitate the evacuation of the vaporized heat-transfer fluid and to promote the evaporation of any coolant condensates.
  • the carrier gas may be added to said droplets.
  • the carrier gas may advantageously be used to produce the coolant droplets by spraying.
  • the carrier gas can be conveyed in compressed form.
  • the carrier gas is typically air, but it is possible, within the scope of the invention, to use other gases or gas mixtures.
  • the heat transfer fluid evacuated typically comprises steam and a few fine non-vaporized droplets. It may optionally contain a liquid condensate of said heat transfer fluid recovered at a distance from the box.
  • the cooling system (100) of an electrolysis cell (1) intended for the production of aluminum by igneous electrolysis said cell (1) comprising a tank (20) comprising a metal box (2). ) having side walls (21, 22) and at least one bottom wall (23), said tank (20) being adapted to contain an electrolyte bath (13) and a liquid metal sheet (12), is characterized in that it comprises at least one means (103) for producing droplets of a coolant, typically in the vicinity of the box (2) of the cell (1), and means (101) for putting all or part of said droplets in contact with the box (2), so as to cause the vaporization of all or part thereof.
  • the confinement boxes (101) are typically close to the walls (21, 22, 23) of the box (2) or possibly in contact with the box (2). They are advantageously placed close to or in contact with at least one of the side walls (21, 22) of said box (2).
  • the expression "near” means at a determined distance typically less than 20 cm, or even less than 10 cm.
  • the containment boxes (101) can be contiguous or attached to the box (2) or integral with it.
  • Each containment housing (101) forms a confined space (102) typically corresponding to a determined internal volume.
  • the containment housing (101) is advantageously open, typically on the side of the box (2), so as to promote heat exchange between the box and the droplets.
  • the containment housing (101) may optionally be open, in particular in its upper part (101a) and / or in its lower part (101b).
  • Said system advantageously comprises a plurality of containment boxes (101) distributed around the box (2) and, preferably, on the side walls (21, 22) of the box (2).
  • Each containment box (141) is advantageously placed so as to overlap the average level of the interface (19) between the electrolyte bath (13) and the liquid metal sheet (12).
  • each housing is typically placed substantially symmetrically with respect to the average level of the interface (the height H1 above the average level (19) and the height H2 below the average level (19) are then substantially equal).
  • the average depth P of the confinement boxes (101) is typically less than 20 cm.
  • the height H of the housings, on the side of the surface (107), is typically between 20 cm and 100 cm, or even between 20 cm and 80 cm.
  • the width L containment boxes (101) may be smaller than or equal to the spacing E between the stiffeners (25); they can also integrate with, or integrate, said stiffeners.
  • the determined surface (107) covered by the housings is typically between 0.2 and 1 m 2 , and more typically between 0.3 and 0.5 m 2 .
  • the means (103) for producing droplets is advantageously a spraying means.
  • This means typically comprises at least one nozzle, such as a fog nozzle.
  • the containment boxes may include one or more means (103) for producing droplets.
  • the offset ⁇ H between the atomization means (103) and the average level (19) of the metal bath interface may be positive, zero or negative, ie the nozzle may be above or below the level of the interface or at the same level as said interface.
  • the supply means (105, 111, 112, 113, 114) in a heat transfer fluid typically comprise conveying means (105, 111, 112, 114), such as ducts, and a treatment column (113).
  • the conveying means typically comprise a distribution duct (111), an electrical insulating duct (112) and a heat-transfer fluid supply duct (114).
  • the system according to the invention further comprises at least one means (104, 110), such as a conduit, for supplying each containment box (101) with carrier gas, possibly under pressure.
  • at least one means (104, 110) such as a conduit, for supplying each containment box (101) with carrier gas, possibly under pressure.
  • it further comprises means (108), such as a mixer, for producing said droplets with said carrier gas.
  • the cooling system according to the invention advantageously comprises at least one means (109) for controlling the rate of production of the coolant droplets.
  • the cooling system advantageously comprises means (106, 120, 121, 122, 123, 124) for discharging all or part of the vaporized heat transfer fluid in contact with the box (2).
  • the evacuation means make it possible to evacuate the vapor of heat transfer fluid formed by the vaporization of all or part of said droplets in contact with said surface (107).
  • the evacuation means (106, 120, 121, 122, 123, 124), which typically comprise channeling means, are able to evacuate all or part of the coolant vapor after evaporation or vaporization of all or part of said droplets in contact with the box (2).
  • said evacuation means typically comprise exhaust ducts (106, 120, 121, 124) and suction or blowing means (123).
  • the exhaust ducts typically include a manifold (120), an electrical insulating duct (121) and an outlet duct (124).
  • the suction or blowing means (123) is typically a fan.
  • These means may also include a condenser (122) for condensing the droplets of heat transfer fluid in suspension.
  • the condenser may advantageously comprise means for cooling the condensed heat transfer fluid in order to be able to reintroduce it into the cooling circuit at a predetermined temperature, which is generally significantly lower than the vaporization temperature. It is advantageous to provide means for promoting the flow and evacuation of any heat transfer fluid condensates, such as a slope in certain exhaust ducts (in particular in the collector duct (120)).
  • the exhaust ducts may include a manifold (106), which may be located at the top (101a) or bottom (101b) of the housings.
  • the Applicant estimated the number of containment boxes required for a tank of 350 kA is typically between 30 and 60 approximately.
  • the amount of liquid heat transfer fluid to be supplied to each housing is typically between 25 and 125 l / h. It also considers that the fraction of coolant droplets actually evaporated in contact with the box is between 20 and 60%.
  • the thermal power dissipated is typically between 5 and 25 kW / m 2 .
  • the Applicant also considers that, if a carrier gas is used, the carrier gas flow per package advantageously is typically between 25 Nm 3 / h and 150 Nm 3 / h.

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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 Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Cooling Or The Like Of Electrical Apparatus (AREA)
EP03763932A 2002-07-09 2003-07-07 Procede et systeme de refroidissement d une cuve d electrolyse pour la production d aluminium Revoked EP1527213B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200331233T SI1527213T1 (sl) 2002-07-09 2003-07-07 Postopki in sistem za hlajenje elektrolizne celice za izdelovanje aluminija

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0208629A FR2842215B1 (fr) 2002-07-09 2002-07-09 Procede et systeme de refroidissement d'une cuve d'electrolyse pour la production d'aluminium
FR0208629 2002-07-09
PCT/FR2003/002098 WO2004007806A2 (fr) 2002-07-09 2003-07-07 Procede et systeme de refroidissement d'une cuve d'electrolyse pour la production d'aluminium

Publications (2)

Publication Number Publication Date
EP1527213A2 EP1527213A2 (fr) 2005-05-04
EP1527213B1 true EP1527213B1 (fr) 2008-03-05

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EP03763932A Revoked EP1527213B1 (fr) 2002-07-09 2003-07-07 Procede et systeme de refroidissement d une cuve d electrolyse pour la production d aluminium

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US (1) US7527715B2 (is)
EP (1) EP1527213B1 (is)
CN (1) CN100406617C (is)
AR (1) AR040391A1 (is)
AT (1) ATE388254T1 (is)
AU (1) AU2003263266B2 (is)
BR (1) BR0312376A (is)
CA (1) CA2489146C (is)
DE (1) DE60319539T2 (is)
EG (1) EG24759A (is)
ES (1) ES2301827T3 (is)
FR (1) FR2842215B1 (is)
IS (1) IS7683A (is)
NO (1) NO20050624L (is)
NZ (1) NZ537406A (is)
OA (1) OA12872A (is)
RU (1) RU2324008C2 (is)
SI (1) SI1527213T1 (is)
WO (1) WO2004007806A2 (is)
ZA (1) ZA200500161B (is)

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CN113432439B (zh) * 2021-07-29 2022-09-06 东北大学 一种铝电解槽停止运作后的冷却方法
RU2770602C1 (ru) * 2021-09-16 2022-04-18 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Катодное устройство алюминиевого электролизера
CN115468377B (zh) * 2022-09-15 2023-08-29 洛阳大生新能源开发有限公司 一种电解液制备用冷却装置

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ATE388254T1 (de) 2008-03-15
DE60319539D1 (de) 2008-04-17
WO2004007806A2 (fr) 2004-01-22
CA2489146A1 (fr) 2004-01-22
ES2301827T3 (es) 2008-07-01
US20060118410A1 (en) 2006-06-08
FR2842215B1 (fr) 2004-08-13
AU2003263266A1 (en) 2004-02-02
EG24759A (en) 2010-08-01
ZA200500161B (en) 2006-07-26
FR2842215A1 (fr) 2004-01-16
AR040391A1 (es) 2005-03-30
IS7683A (is) 2005-02-03
CN100406617C (zh) 2008-07-30
WO2004007806A3 (fr) 2004-04-08
NZ537406A (en) 2007-05-31
OA12872A (fr) 2006-09-15
CN1665963A (zh) 2005-09-07
US7527715B2 (en) 2009-05-05
BR0312376A (pt) 2005-04-12
AU2003263266B2 (en) 2008-10-30
CA2489146C (fr) 2011-10-18
RU2005103232A (ru) 2005-08-10
EP1527213A2 (fr) 2005-05-04
DE60319539T2 (de) 2009-03-26
RU2324008C2 (ru) 2008-05-10
NO20050624L (no) 2005-02-04
SI1527213T1 (sl) 2008-08-31

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