CN1759206A - Apparatus for carrying out an electrolytic process on a halogenide compound - Google Patents
Apparatus for carrying out an electrolytic process on a halogenide compound Download PDFInfo
- Publication number
- CN1759206A CN1759206A CNA038262363A CN03826236A CN1759206A CN 1759206 A CN1759206 A CN 1759206A CN A038262363 A CNA038262363 A CN A038262363A CN 03826236 A CN03826236 A CN 03826236A CN 1759206 A CN1759206 A CN 1759206A
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- China
- Prior art keywords
- electrolytic solution
- transmission medium
- heat transmission
- present
- electrolyzer
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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.)
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- 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
- C25B15/00—Operating or servicing cells
-
- 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
-
- 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
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46155—Heating or cooling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to an apparatus for carrying out an electrolytic process on a halogenide compound, in which apparatus several electrolytic cells are electrically connected in series, which electrolysis cells each comprise a cell element, provided with underlying supply pipes for supplying electrolyte and with collecting discharge pipes disposed near the upper side thereof for discharging electrolyte and the gases formed during the electrolytic process, a cathode compartment including a cathode and an anode compartment including an anode, and a diaphragm or semi-permeable membrane, in which the electrolytic cells have been pressed together between two end plates with a certain bias, so that each anode compartment and each cathode compartment is constructed as one unit together with the supply pipes and the collecting discharge pipes.
Description
The present invention relates to a kind of equipment that is used for halide compound is carried out electrolytic process, several electrolyzers in this equipment (electrolytic cell) are electrically connected in series, each comprises described electrolyzer: the pond element, provide the bottom supply pipe, be used to supply electrolytic solution, and provide the collection delivery pipe that is provided with near its upside, be used to the gas that discharges electrolytic solution and during described electrolytic process, form; Comprise the cathode compartment of negative electrode and comprise the anodic anolyte compartment; And barrier film or semipermeable partition; Wherein said electrolyzer is pressed together having between two end plates (end plate) of certain biasing, makes each anolyte compartment and each cathode compartment be configured to a unit with described supply pipe and described collection delivery pipe.
From U.S. Patent No. 5,064, known a kind of being used for from the device of hypochlorous acid (hypochlorous acid) preparation chloric acid (chloric acid) in 514, this device comprises only single pond structure.Therefore known described device does not comprise bipolar electrode or intermediate plate from described file.The cooling system that is used for described device is by forming adjacent to two cooling plates of anode and the setting of negative electrode backboard, described plate has hollowing out of opening on adjacent to described negative electrode and anodic side or the groove district is arranged, but it is being closed adjacent to the cold plate surface place on the side of described backboard and is being solid.Described have the groove district will permit the circulation of refrigerant so that control the heat that is produced during the described electrolytic process.Because construct as used herein, described refrigerant and described electrode directly electrically contact.
From U.S. Patent No. 5,082,543 known a kind of electrolyzers that are used to produce pressure filter (filter press) type of peroxide (peroxy) and perhalogeno (perhalogenate) compound.Known described pond is half filter press type from described file, because each pond is to separate to be electrically connected.Therefore, do not use bipolar electrode or intermediate plate.The employed electrode that is made of metal fully is a double-walled, refrigerant between described parallel wall by pumping.In practice, because a large amount of electrical connections, the complete submergence of described pond in refrigerant is impossible.Because the structure of described double-walled electrode, the refrigerant by wherein is under the electrode voltage.
Known a kind of reactor that is used to generate ozone from German prospectus No 199 10 639; Yet described file does not provide any information about employed electrolyzer.
The equipment of mentioning in foreword itself is known from NL 8303210, wherein prepares by means of electrolytic process and wishes to be used for the water such as swimming-pool water, tap water or waste water is carried out the chlorine that chlorine is handled.Described Dutch open file illustrates by two anolyte compartments and two electrolyzers that cathode compartment is formed with alternately relation setting.Being arranged between the first anode chamber and first cathode compartment is the film of being made by the material that is suitable for this purpose, and this film is permeable and be impermeable to negatively charged ion to positively charged ion.Similarly the modularization pool unit is formed by second anode chamber, second cathode compartment and the cation-permeable that is arranged between it.Described modularization pool unit is adjacent one another are and be provided with, and wherein inserts impermeable liner of liquid or isolator.End plates is arranged on the end of described pool unit structure, and tie-rod (tie rod) or other stationary installation that is fit to are passed through wherein, and described tie-rod also extends through described pool unit so that in this mode entire structure is kept together.Each pond element is provided with collection tube, is also referred to as degasser (degasser), and the gas that forms during described electrolytic process separates with described electrolytic solution therein.
The temperature that a shortcoming of the above equipment is the described electrolyzer that is connected in series can be elevated to the fact of the level of not expecting.Because chemistry and mechanical reason it is desirable to have the possibility that influences described temperature in practice.In practice, so-called heat exchanger is used to this purpose, however this heat exchanger be installed in outside the described pond piece (cell block), this means that temperature is externally influenced.Yet such external influence can not prevent described electrolyzer and particularly show unallowed thermal deviation in described pond package center.Therefore it is desirable to provide a kind of equipment,, can mainly realize heat affecting in the position of described thermal deviation maximum by means of it.
Therefore, the purpose of this invention is to provide a kind of equipment that is used for halide compound is carried out electrolytic process, this equipment provides the possibility in the internal heat influence of the position of described thermal deviation origin, guarantees inner thermostability thus.
Another object of the present invention provides a kind of equipment that is used for halide compound is carried out electrolytic process, and this equipment is collected may be owing to leaking corrosive liquid or the gas that forms.
According to the present invention, be present in as the assembly of in foreword, mentioning that the invention is characterized in end plate and electrolyzer and comprise liquid, in the container of heat transmission medium, wherein non-conductive pond is separated (partition) and is present between described negative electrode and the described anode, except supply pipe and collection delivery pipe corresponding to described pond element, described pond is separated and is also comprised one or more passages (through channel) that pass through, be used for making the heat transmission medium that is present in described container to pass through wherein, described passage forms in separate in described pond in such a manner, make the described heat transmission medium that is present in the described passage not be under the voltage, and outside described electrolyzer, being present in the electrolytic solution in the described electrolyzer and being present in does not have the liquid contact to take place between the heat transmission medium in the described container.
According to the present invention, therefore the whole pond encapsulation that comprises two end plates is positioned over heat transmission medium, for example in the water, two functions of the actual execution of wherein said heat transmission medium, it is the function of heat-eliminating medium, not only internally carried out in the passage but also execution externally outside described electrolyzer, in described container being present in described pond pass through in separating, and the function that stops the medium of any leakage.Because the signal portion of the electric energy of supplying for electrolytic process as the result of the cooling that realized in the present invention action is collected in the described heat transmission medium, energy recovers to become feasible, has realized energy saving as its result.
In principle, employed among the present invention can have any shape of expecting by passage, for example circle, rectangle, trapezoidal or the like.The present invention is used in particular for wanting in the environment of gaseous halide, for example with the sterilizing agent that acts on swimming pool or tap water.
In a preferred embodiment, each combination of negative electrode and anodic is separated by current pond, makes refrigerating function always to carry out in the position that heat generates.Preferably use bipolar electrode.
In a certain embodiments, for the heat transmission medium that is present in the described container, it is desirable to pass through passage in the pressure mode, this can for example realize by placing one or more pumps.
For example by changing the temperature and/or the cycling rate of described medium, for example by means of pump circulation, use one or more pumps, be present in heat transmission medium in the described container and also can be used in the temperature of regulating in the described electrolytic cell package and the temperature of described electrolytic process thus.Because whole electrolysis cells is immersed in the described heat transmission medium, the risk that gas or electrolyte leakage are gone out also is prevented from.
One particular embodiment of the present invention are characterised in that inversion element (reversing element) is provided with adjacent to electrolytic cell package, this inversion element is provided with the bottom supply pipe, be used to supply electrolytic solution to the adjacent cell encapsulation, and further be provided with near the collection delivery pipe that is provided with of side thereon, be used for discharging the electrolytic solution of adjacent cell encapsulation and the gas that during described electrolytic process, forms, be used to realize the returning of electrolytic solution from described collection delivery pipe to described supply pipe, this inversion element is provided with one or more passages that pass through, be used to make passing through wherein of described heat transmission medium, described passage is so disposed so that outside described electrolyzer, be present in the described electrolyzer electrolytic solution be present in described container in heat transmission medium between do not have liquid to contact generation.
In a particular embodiment, described non-conductive pond is separated and is provided with device, is used to make each adjacent electrode electrical interconnection and does not take place via any exchange of the electrolytic solution between two electrolyzers of described connection between each electrode metal or electrolytic corrosion.
In addition, might guide by being present in the heat transmission medium in the described container, so that the heat energy that is included in the described electrolytic solution is passed to described heat transmission medium via the discarded electrolytic solution that a pipe will will discharge after described electrolytic process.
Below with reference to many accompanying drawings the present invention is being described, yet described accompanying drawing should not be construed as and constituted limitation of the present invention.
Fig. 1 is the skeleton view of current device.
Fig. 2 is the schematic cross-sectional view of the equipment of Fig. 1.
Fig. 3 is when schematically showing that separate the forebay.
Fig. 4 is schematically showing of separating of the pond of Fig. 3.
According to Fig. 1, two electrolyzers of the filter press type that is electrically connected in series are present in the container 1, and described container 1 comprises heat transmission medium 2, for example water; For the sake of simplicity, be used to supply electrolytic solution, for example the element of HCl does not illustrate in the drawings.Should be appreciated that the present invention never is subject to these.Anode 14 separates with negative electrode 15 by semipermeable partition 6.Negative electrode 15 is separated 9 by means of the pond and is separated with anode 16, and anode 16 separates with negative electrode 17 by semipermeable partition 6.Experience electrolytic process via supply pipe 7 and 22 the electrolytic solution collecting delivery pipe 13,19 and be used to supply electrolytic solution at anode through electrolyzers, during this process, form chlorine, for example, this chlorine ends to collect in the delivery pipe 19 and subsequently via described anolyte compartment and leaves described equipment via gas discharge pipe 12.Because electrolytic process, form hydrogen at negative electrode 15,17, this sources of hydrogen is from described cathode compartment and be collected in and collect in the delivery pipe 13, separating between generation electrolytic solution and the hydrogen in this collections delivery pipe 13.From described collection delivery pipe 13, still Re electrolytic solution can be subsequently via managing 24 from described equipment exhausting, and described pipe 24 is conducted through described medium so that realize transmission ofenergy.At last, the hydrogen that has formed in described electrolyzer is via pipe 11 dischargings.In order to realize the suitable electrolyte flow in the current device, preferably use inversion element 4, it is provided with the bottom supply pipe, be used for electrolytic solution is fed to the adjacent cell encapsulation, and it further is provided with the collection delivery pipe that is provided with near its upside, be used for discharging the electrolytic solution of adjacent electrolysis encapsulation and the gas that during described electrolytic process, forms, be used to realize the returning of electrolytic solution from described collection delivery pipe to described supply pipe.In order to control the temperature that is present in the electrolytic solution in the described inversion element, described inversion element is provided with one or more by the passage (not shown), be used to make heat transmission medium 2 to pass through wherein, described passage is so disposed so that outside described electrolyzer, the electrolytic solution in being present in described electrolyzer be present in described container in heat transmission medium between do not have liquid to contact generation.
Fig. 2 is the schematic side elevation of the electrolyzer of Fig. 1.In Fig. 2, indicate electrolyte flow in the described electrolytic cell package by means of arrow, it is evident that therefrom inversion element 4 is arranged to make the liquid from collecting delivery pipe 13,19 to turn back to the supply pipe 7 and 22 that is used for electrolytic solution is fed in question electrolyzer.
Fig. 3 is the sectional view as the embodiment of forebay separation 9, and is wherein schematically illustrated by passage 20.Particularly by making heat transmission medium pass through passage 20, describedly be arranged to make temperature regulation in the position that heat release mainly takes place by passage 20, promptly on described electrode surface, carry out.Pond shown in Figure 3 separate 9 can by two symmetric half form, (or its each in) polish (mill out) by passage 20 in described two half one, described afterwards two half be assembled to form and comprised a described unit by passage 20.By with an angle described passage being set so slightly, in case the integral body of end plate and electrolyzer is immersed in the heat transmission medium, described passage will easily be filled with heat transmission medium.
Fig. 4 illustrates the pond and separates 9, and wherein anode 15 is arranged on the one side and negative electrode 16 is arranged on opposite side.Anode 15 and negative electrode 16 are connected 21,23 and electrical interconnection via what be made up of two kinds of different metals, described connection 21,23 so design so that there are not two exchange of electrolyte between the electrolyzer to take place via described connection 21,23.To from Fig. 4, it is evident that, particularly by via one or how make described heat transmission medium 2 separate 9 by described pond by passage 20, any cooling that may need will occur in the position that heat release mainly takes place, promptly near the position of anode 15 and negative electrode 16.
Claims (4)
1. equipment that is used for halide compound is carried out electrolytic process, several electrolyzers are electrically connected in series in this equipment, each comprises described electrolyzer: the pond element, provide the bottom supply pipe, be used to supply electrolytic solution, and provide the collection delivery pipe that is provided with near its upside, be used to the gas that discharges electrolytic solution and during described electrolytic process, form; Comprise the cathode compartment of negative electrode and comprise the anodic anolyte compartment; And barrier film or semipermeable partition; Wherein said electrolyzer is pressed together having between two end plates of certain biasing, make each anolyte compartment and each cathode compartment be configured to a unit with described supply pipe and described collection delivery pipe, the assembly that is characterised in that end plate and electrolyzer is present in and comprises liquid, in the container of heat transmission medium, wherein non-conductive pond is separated and is present between described negative electrode and the described anode, except supply pipe and collection delivery pipe corresponding to described pond element, described pond is separated and is also comprised one or more passages that pass through, be used for making the heat transmission medium that is present at described container to pass through wherein, described passage forms in separate in described pond in such a manner, make the heat transmission medium that is present in the described passage not be under the voltage, and outside described electrolyzer, the electrolytic solution in being present in described electrolyzer be present in described container in heat transmission medium between do not have liquid to contact generation.
2. according to the equipment of claim 1, be characterised in that inversion element is provided with adjacent to described electrolytic cell package, described inversion element provides the bottom supply pipe, be used for electrolytic solution is fed to the adjacent cell encapsulation, and be further provided with the collection delivery pipe that is provided with near its upside, be used for discharging formed gas during the electrolytic solution of adjacent cell encapsulation and the described electrolytic process, so that returning of the electrolytic solution of realization from described collection delivery pipe to described supply pipe, described inversion element is provided with one or more passages that pass through, be used to make described heat transmission medium to pass through wherein, described passage designs in such a manner, make outside described electrolyzer, the electrolytic solution in being present in described electrolyzer be present in described container in heat transmission medium between do not have liquid to contact generation.
3. according to any one of aforementioned claim or a plurality of equipment, being characterised in that described non-conductive pond is separated is provided with a device, is used for each adjacent electrode of electrical interconnection and any exchange of the electrolytic solution between two electrolyzers via described connection between each electrode metal or electrolytic corrosion does not take place.
4. according to any one of aforementioned claim or a plurality of equipment, be characterised in that described electrolytic solution via pipe set in the heat transmission medium in the described container from described equipment exhausting so that with the thermal energy transfer that comprised in the described electrolytic solution to described heat transmission medium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/NL2003/000234 WO2004085711A1 (en) | 2003-03-27 | 2003-03-27 | Apparatus for carrying out an electrolytic process on a halogenide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1759206A true CN1759206A (en) | 2006-04-12 |
| CN100497749C CN100497749C (en) | 2009-06-10 |
Family
ID=33095815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038262363A Expired - Fee Related CN100497749C (en) | 2003-03-27 | 2003-03-27 | Apparatus for carrying out an electrolytic process on a halogenide compound |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20080116061A1 (en) |
| JP (1) | JP4209848B2 (en) |
| CN (1) | CN100497749C (en) |
| AU (1) | AU2003225421B2 (en) |
| BR (1) | BR0318231A (en) |
| CA (1) | CA2520486C (en) |
| EG (1) | EG23722A (en) |
| HK (1) | HK1086861A1 (en) |
| HR (1) | HRP20050929A2 (en) |
| MX (1) | MXPA05010209A (en) |
| NZ (1) | NZ543198A (en) |
| WO (1) | WO2004085711A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276088A (en) * | 2011-05-17 | 2011-12-14 | 哈尔滨工业大学 | Electrolytic bath system in series and method for removing bromate in drinking water by using system thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1528126A1 (en) | 2003-10-30 | 2005-05-04 | Vandenborre Hydrogen Systems N.V. | An integrated electrolyser module with an internal gas/liquid separator |
| WO2006060912A1 (en) * | 2004-12-07 | 2006-06-15 | Stuart Energy Systems Corporation | Electrolyser and components therefor |
| US20160263341A1 (en) * | 2015-03-09 | 2016-09-15 | Hsin-Yung Lin | Gas generator |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3421994A (en) * | 1962-03-01 | 1969-01-14 | Pullman Inc | Electrochemical apparatus |
| US3274094A (en) * | 1965-02-24 | 1966-09-20 | Chemagnetics Controls Inc | Apparatus for the chlorination of water |
| US3575719A (en) * | 1968-10-09 | 1971-04-20 | Allis Chalmers Mfg Co | Compact cell construction |
| US3997414A (en) * | 1975-05-05 | 1976-12-14 | Huron Chemicals Limited | Gas concentrated and cooled electrolytic cell |
| DE3938160A1 (en) * | 1989-11-16 | 1991-05-23 | Peroxid Chemie Gmbh | ELECTROLYSIS CELL FOR PRODUCING PEROXO AND PERHALOGENATE COMPOUNDS |
| US5064514A (en) * | 1990-03-30 | 1991-11-12 | Olin Corporation | Apparatus for the production of chloric acid |
| NL1005081C2 (en) * | 1997-01-24 | 1998-07-27 | Zilvold Tieleman Hydro Technie | Apparatus for conducting an electrolysis, a cell element applicable herein, method for conducting an electrolysis in such an apparatus, method for preparing chlorine dioxide, reactor for carrying out such a method and an installation for preparing chlorine dioxide. |
| DE19910639A1 (en) * | 1999-03-10 | 2000-09-14 | Fischer Margot | Ozonization reactor for treating liquids, e.g. water, includes an ozone-generating electrolysis cell and an immersion pump and/or vacuum injector for recycling ozone |
| NL1019070C2 (en) * | 2001-10-01 | 2003-04-02 | Gerrit Albert Zilvold | Device for carrying out an electrolysis of a halide compound. |
-
2003
- 2003-03-27 NZ NZ543198A patent/NZ543198A/en not_active IP Right Cessation
- 2003-03-27 US US10/550,697 patent/US20080116061A1/en not_active Abandoned
- 2003-03-27 AU AU2003225421A patent/AU2003225421B2/en not_active Ceased
- 2003-03-27 MX MXPA05010209A patent/MXPA05010209A/en active IP Right Grant
- 2003-03-27 CA CA002520486A patent/CA2520486C/en not_active Expired - Fee Related
- 2003-03-27 WO PCT/NL2003/000234 patent/WO2004085711A1/en active Application Filing
- 2003-03-27 JP JP2004569955A patent/JP4209848B2/en not_active Expired - Fee Related
- 2003-03-27 BR BRPI0318231-2A patent/BR0318231A/en active Search and Examination
- 2003-03-27 CN CNB038262363A patent/CN100497749C/en not_active Expired - Fee Related
-
2005
- 2005-09-24 EG EGNA2005000571 patent/EG23722A/en active
- 2005-10-26 HR HR20050929A patent/HRP20050929A2/en not_active Application Discontinuation
-
2006
- 2006-06-19 HK HK06106963.4A patent/HK1086861A1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276088A (en) * | 2011-05-17 | 2011-12-14 | 哈尔滨工业大学 | Electrolytic bath system in series and method for removing bromate in drinking water by using system thereof |
| CN102276088B (en) * | 2011-05-17 | 2012-08-15 | 哈尔滨工业大学 | Electrolytic bath system in series and method for removing bromate in drinking water by using system thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| HRP20050929A2 (en) | 2006-02-28 |
| BR0318231A (en) | 2006-04-04 |
| CN100497749C (en) | 2009-06-10 |
| JP4209848B2 (en) | 2009-01-14 |
| CA2520486C (en) | 2009-05-26 |
| MXPA05010209A (en) | 2006-02-22 |
| JP2006514163A (en) | 2006-04-27 |
| AU2003225421B2 (en) | 2008-02-07 |
| AU2003225421A1 (en) | 2004-10-18 |
| HK1086861A1 (en) | 2006-09-29 |
| CA2520486A1 (en) | 2004-10-07 |
| WO2004085711A1 (en) | 2004-10-07 |
| EG23722A (en) | 2007-06-25 |
| US20080116061A1 (en) | 2008-05-22 |
| NZ543198A (en) | 2007-09-28 |
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