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US20060042413A1 - Method using single furnace carbothermic reduction with temperature control within the furnace - Google Patents

Method using single furnace carbothermic reduction with temperature control within the furnace Download PDF

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Publication number
US20060042413A1
US20060042413A1 US10/932,846 US93284604A US2006042413A1 US 20060042413 A1 US20060042413 A1 US 20060042413A1 US 93284604 A US93284604 A US 93284604A US 2006042413 A1 US2006042413 A1 US 2006042413A1
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US
United States
Prior art keywords
slag
furnace
phase
temperature
reactor
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.)
Abandoned
Application number
US10/932,846
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English (en)
Inventor
Richard Fruehan
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.)
Elkem ASA
Alcoa Corp
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US10/932,846 priority Critical patent/US20060042413A1/en
Assigned to ALCOA INC., ELKEM ASA reassignment ALCOA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FRUEHAN, RICHARD J.
Priority to RU2007111945/02A priority patent/RU2007111945A/ru
Priority to EP05794450A priority patent/EP1794333A2/fr
Priority to BRPI0514819-7A priority patent/BRPI0514819A/pt
Priority to AU2005279732A priority patent/AU2005279732A1/en
Priority to CNA2005800314525A priority patent/CN101023190A/zh
Priority to CA002577565A priority patent/CA2577565A1/fr
Priority to JP2007530444A priority patent/JP2008511760A/ja
Priority to PCT/US2005/031521 priority patent/WO2006026771A2/fr
Assigned to ENERGY, UNITED STATES DEPARTMENT OF reassignment ENERGY, UNITED STATES DEPARTMENT OF CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: ALCOA, INC.
Publication of US20060042413A1 publication Critical patent/US20060042413A1/en
Priority to NO20070674A priority patent/NO20070674L/no
Priority to ZA200702572A priority patent/ZA200702572B/xx
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/02—Light metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/02—Obtaining aluminium with reducing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents

Definitions

  • the present invention relates to a method of producing low carbon aluminum in a single reactor compartment carbothermic furnace with control to lower or raise the temperature of reactants within the interior of the reactor compartment.
  • Reaction (2) takes place at temperatures below 2000° C. and generally between 1900° C. and 2000° C.
  • reaction (3) which is the aluminum producing reaction, takes place at higher temperatures of about 2050° C., and requires substantial heat input.
  • volatile species including gaseous Al, reaction (6), and gaseous aluminum suboxide that is Al 2 O, are formed in reaction (4) or (5).
  • the Al 2 O and Al gases are recovered by reacting them with carbon in a separate reactor usually called the vapor recovery unit or vapor recovery reactor.
  • Kibby '757 patent uses arc heating and a plasma jet in a process that starts at 1850° C.-1950° C., then arc heats to 2100° C., producing Al with ⁇ 10 wt. % C.
  • the latter Kibby '107 utilizes a secondary furnace or separate decarbonization zone requiring transfer of very hot metal and slag to and from the furnace.
  • a method of using a single carbothermic reactor to produce aluminum with low carbon content comprising: (a) providing a single furnace having a single hollow, interior reactor compartment with a plurality of bottom resistance heating electrodes and one or more optional vertical top electrodes; and then; (b) adding Al 2 O 3 and C for start-up of the process to the inside of the furnace and melting their mixture, to provide a (Al 2 O 3 —Al 4 C 3 ) slag and excess Al 4 C 3 having a temperature between about 1875° C.
  • This slag is then used to begin the next cycle.
  • the next cycle is begun by adding some C and Al 2 O 3 to the bottom slag and repeating steps (c) to (e).
  • the tapped aluminum phase is Al ⁇ 3 wt % C and the Al 4 C 3 added in step (c) is from a vapor recovery unit associated with the reactor.
  • step (b) arc heating using retractable, at least one vertical top electrodes are preferably used to provide slag.
  • step (d) addition of Al 2 O 3 at this stage, very importantly, lowers the temperature within the furnace and changes the slag composition transferring a substantial amount of C from aluminum to the slag. This provides a very simple method to produce lower carbon containing aluminum, where only one furnace or reactor is used in the process.
  • FIG. 1 is a flow sheet showing one example of a previously conceptualized system of a carbothermic reduction process for the production of aluminum, including an off-gas vapor recovery reactor to recover the Al 2 O and Al vapors as Al 4 C 3 and/or Al 2 O 3 solids (and Al 4 C 3 —Al 2 O 3 slag); and
  • FIG. 2 is flow sheet showing the steps involved in this invention to produce low carbon aluminum utilizing a single reactor.
  • FIG. 1 is a simplified illustration of one embodiment of a carbotherimc reaction process to produce Al and, recover A 1 , Al 2 O and CO in the off-gases as Al 4 C 3 , Al 2 O 3 and slag and passes this material to the smelting furnace.
  • gas flows are shown as dashed lines and flows of solids and molten substances are shown as solid lines.
  • the off-gas from a carbothermic smelting furnace here, for simplicity, comprising a first stage 1 and possibly a second stage 2 is forwarded via conduits 3 and 4 to an enclosed off-gas reactor 5 operating at a temperature of about 1600° C. to 2050° C. depending on the type reactor.
  • the reactor 5 could be a counter-current moving bed reactor or a fluid bed or a series of fluid beds.
  • the Al-components of the off-gas entering the reactor 5 react with the carbon to form Al 4 C 3 , Al 2 O 3 and Al 4 C 3 —Al 2 O 3 slag material.
  • Conduit 6 can be used to pass this material to stage 2 .
  • the gas from reactor 5 contains primarily CO, and possibly some H 2 from the volatile part of the charcoal reactor charge and little or no Al or Al 2 O.
  • the off gas from reactor 5 has a high energy value as hot CO and could be used to produce electrical energy in a gas turbine or conventional boiler.
  • the aluminum vapor species will have reacted to carbide, condensed to Al 2 O 3 and C or formed an Al 2 O 3 —Al 4 C 3 slag.
  • the Al 4 C 3 —Al 2 O 3 slag and unreacted carbon is fed into the second stage of the carbothermic smelter via conduit 6 .
  • An Al—C liquid alloy exits smelter stage 2 as shown in FIG. 1 , where (s) means solid, (v) means vapor and (liq) means liquid in FIG. 1 .
  • FIG. 2 illustrates the basic steps, reactions and reactants in the method of this invention.
  • This new process uses a single furnace, so no slag recycle is required, and slag resistance heating to avoid excess vaporization.
  • Al 2 O 3 and carbon are added and Al 2 O 3 —Al 4 C 3 slag is produced which can contain excess Al 4 C 3 above saturation.
  • the furnace operates at about 1875° C. to 2000° C. to produce slag.
  • the second step produces an Al-6-8 wt % C alloy at about 2050° C. to 2100° C. and requires additional energy and additional Al 4 C 3 , part of which is the excess from the first step and the remainder is from the vapor recovery unit.
  • slag is produced.
  • metal 21 is produced with about 5 to 7 wt % C on top of a slag phase 22 and gases are released (not shown for the sake of simplicity).
  • an extraction or decarbonization reaction is provided, at lowered temperatures to reduce vapor loss, where added Al 2 O 3 , is at ambient temperature (about 20° C. to about 35° C.), and importantly, helps lower both temperature substantially and provides an alumina rich slag in step 40 .
  • C is transferred from the Al phase to provide an aluminum phase containing less than ( ⁇ ) 5 wt % C phase, preferably a ⁇ 3 wt % C phase 23 , which is then tapped. Steps 30 and 40 merge somewhat.
  • Aluminum carbide is added from the vapor recovery reactor 5 . About 17% of the Al will vaporize as Al 2 O and Al. It is not possible to react all of the slag since the energy is supplied by slag resistance heating through the slag and some slag must remain in the furnace. About 20% of the slag does not react and remains for resistance heating. Some decarburization can occur by raising the temperature after all the carbide is added and reducing the carbide content of the slag and carbon in the metal but this will result in large amounts of Al 2 O and Al vaporization.
  • Al 2 O 3 is added to the furnace to remove carbon from the metal. Some electric power is necessary to heat and melt the Al 2 O 3 while some of the energy comes from the sensible heat of the slag since its temperature is higher than required for decarburization
  • the slag-metal system is allowed to cool to about 1850° C.
  • the slag becomes rich in Al 2 O 3 and carbon is transferred from the metal to the slag (Al 2 C 3 ).
  • the metal is tapped and the resulting Al 2 O 3 rich liquid slag is the starting point for return to slag making.
  • the temperature is increased to about 1900° C.-2000° C. and Al 2 O 3 and carbon are added once more, to produce the desired liquid slag compositions and excess Al 4 C 3 for metal making.
  • substantial amounts of CO are produced which carry Al as Al and Al 2 O gaseous species. These are converted to Al 4 C 3 in the vapor recovery reactor 5 and returned to the furnace during metal making, all as shown in FIG. 2 .
  • a single furnace 11 having side walls and a bottom, and a single, hollow reactor compartment 13 , as shown in FIG. 2 , is used solely in this invention; without interior underflow partition walls/baffles or the like.
  • the furnace can have a substantially rectangular, square, circular or oval shape.
  • bottom resistance heating electrodes 16 preferably located in the side(s) of the reactor as shown.
  • at least one top vertical retractable exterior electrode 12 is used. It can provide an arc to melt the solid Al 2 O 3 and C at start-up or at steady state, added to producing molten slag phase Al 2 O 3 —Al 4 C 3 slag plus additional Al 4 C 3 .
  • the electrodes 12 and 16 can be made from carbon, graphite, or non-consumable inert ceramic materials, where each is individually supplied with electricity by electric current means 19 .
  • the bottom resistance heating electrodes are preferably horizontal and used in metal making to reduce super heating the metal and causing excessive vaporization.
  • the bottom electrodes 16 are also preferably disposed at/adjacent to the bottom phase molten slag phase/level 22 , as shown in steps 20 , 30 and 40 .
  • Al 2 O, vapor, CO and Al exit as streams 3 and 3 ′.
  • the Al 2 O 3 , C, Al 4 C 3 supply means in steps 10 to 30 are preferably gas tight.
  • the purified aluminum stream 26 may then be passed to any number of apparatus, for example, degassing apparatus to remove, for example, H 2 fluxing apparatus to scavage oxides from the melt and eventually to casting apparatus to provide unalloyed primary shapes such as ingots or the like of about 50 lb. (22.7 Kg) to 750 lb. (341 Kg). These ingots may then be remelted for final alloying in a holding or blending furnace or the melt from fluxing apparatus may be directly passed to a furnace for final alloying and casting as alloyed aluminum shapes.
  • degassing apparatus to remove, for example, H 2 fluxing apparatus to scavage oxides from the melt and eventually to casting apparatus to provide unalloyed primary shapes such as ingots or the like of about 50 lb. (22.7 Kg) to 750 lb. (341 Kg).
  • the Al vaporized will produce about 15 moles of carbide. During slag making enough Al is vaporized to produce 10 moles of carbide. A total of 62 moles of carbide are required in the metal making step. With 28 moles of carbide reacting from the slag and about 25 moles from the vapor recovery reactor (“VRR”) there is a deficit of about 9 moles of Al 4 C 3 . This additional carbide can be produced in slag making so the actual starting point is:
  • the slag +Al 4 C 3 is heated to a higher temperature (2050° C.-2100° C.) producing 310 k moles aluminum metal containing about 7.5 wt. % C. About 20 k moles of slag remain for resistance heating.
  • the temperature is increased to about 2000° C. and Al 2 O 3 and carbon are added to produce the desired liquid slag composition and excess Al 4 C 3 for metal making. This will require about 225 k moles of C and 37 k moles of Al 2 O 3 .
  • the metal making step is repeated.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Furnace Details (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Glass Melting And Manufacturing (AREA)
US10/932,846 2004-09-01 2004-09-01 Method using single furnace carbothermic reduction with temperature control within the furnace Abandoned US20060042413A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US10/932,846 US20060042413A1 (en) 2004-09-01 2004-09-01 Method using single furnace carbothermic reduction with temperature control within the furnace
PCT/US2005/031521 WO2006026771A2 (fr) 2004-09-01 2005-09-01 Procede utilisant une reduction carbothermique en four unique avec regulation de la temperature a l'interieur du four
CA002577565A CA2577565A1 (fr) 2004-09-01 2005-09-01 Procede utilisant une reduction carbothermique en four unique avec regulation de la temperature a l'interieur du four
EP05794450A EP1794333A2 (fr) 2004-09-01 2005-09-01 Procede utilisant une reduction carbothermique en four unique avec regulation de la temperature a l'interieur du four
BRPI0514819-7A BRPI0514819A (pt) 2004-09-01 2005-09-01 método usando um único forno de redução carbotérmica com controle de temperatura dentro do forno
AU2005279732A AU2005279732A1 (en) 2004-09-01 2005-09-01 Method using single furnace carbothermic reduction with temperature control within the furnace
CNA2005800314525A CN101023190A (zh) 2004-09-01 2005-09-01 使用具有炉内温度控制的单一炉碳热还原的方法
RU2007111945/02A RU2007111945A (ru) 2004-09-01 2005-09-01 Способ использования карботермического восстановления в единственной печи с регулированием температуры внутри печи
JP2007530444A JP2008511760A (ja) 2004-09-01 2005-09-01 単一炉を使用し、炉内温度制御による炭素熱還元方法
NO20070674A NO20070674L (no) 2004-09-01 2007-02-06 Fremgangsmate for bruk av en enkelt karbotermisk reduksjonsovn med temperaturkontroll i ovnen.
ZA200702572A ZA200702572B (en) 2004-09-01 2007-03-28 Method using single furnace carbothermic reduction with temperature control with the furnace

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/932,846 US20060042413A1 (en) 2004-09-01 2004-09-01 Method using single furnace carbothermic reduction with temperature control within the furnace

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US20060042413A1 true US20060042413A1 (en) 2006-03-02

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US10/932,846 Abandoned US20060042413A1 (en) 2004-09-01 2004-09-01 Method using single furnace carbothermic reduction with temperature control within the furnace

Country Status (11)

Country Link
US (1) US20060042413A1 (fr)
EP (1) EP1794333A2 (fr)
JP (1) JP2008511760A (fr)
CN (1) CN101023190A (fr)
AU (1) AU2005279732A1 (fr)
BR (1) BRPI0514819A (fr)
CA (1) CA2577565A1 (fr)
NO (1) NO20070674L (fr)
RU (1) RU2007111945A (fr)
WO (1) WO2006026771A2 (fr)
ZA (1) ZA200702572B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008011206A1 (fr) * 2006-07-20 2008-01-24 Alcoa Inc. Systèmes et procédés pour la production carbothermique de l'aluminium
US20090013823A1 (en) * 2007-07-09 2009-01-15 Alcoa Inc. Use of alumina-carbon agglomerates in the carbothermic production of aluminum
US20090139371A1 (en) * 2007-12-04 2009-06-04 Alcoa Inc. Carbothermic aluminum production apparatus, systems and methods
US7556667B2 (en) 2007-02-16 2009-07-07 Alcoa Inc. Low carbon aluminum production method using single furnace carbothermic reduction operated in batch mode
US20100147113A1 (en) * 2008-12-15 2010-06-17 Alcoa Inc. Decarbonization process for carbothermically produced aluminum
US7824468B2 (en) 2005-07-27 2010-11-02 Thermical Ip Pty Ltd. Carbothermic processes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2288737A1 (fr) * 2008-05-09 2011-03-02 Thermical IP Pty Ltd. Procédés carbothermiques
KR101105437B1 (ko) * 2010-05-11 2012-01-17 (주)포스코켐텍 폐 마그카본 내화물의 재생방법
NO337267B1 (no) * 2014-02-10 2016-02-29 Elkem As Fremgangsmåte for fremstilling av aluminiumoksidpartikler

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Publication number Priority date Publication date Assignee Title
US2974032A (en) * 1960-02-24 1961-03-07 Pechiney Reduction of alumina
US4033757A (en) * 1975-09-05 1977-07-05 Reynolds Metals Company Carbothermic reduction process
US4099959A (en) * 1976-05-28 1978-07-11 Alcan Research And Development Limited Process for the production of aluminium
US4177060A (en) * 1976-08-23 1979-12-04 Tetronics Research & Development Company Limited Reduction of stable oxides
US4216010A (en) * 1979-01-31 1980-08-05 Reynolds Metals Company Aluminum purification system
US4334917A (en) * 1980-04-16 1982-06-15 Reynolds Metals Company Carbothermic reduction furnace
US4388107A (en) * 1979-01-31 1983-06-14 Reynolds Metals Company Minimum-energy process for carbothermic reduction of alumina
US4409021A (en) * 1982-05-06 1983-10-11 Reynolds Metals Company Slag decarbonization with a phase inversion
US4533386A (en) * 1984-03-27 1985-08-06 Process Development Associates, Inc. Process for producing aluminum
US6440193B1 (en) * 2001-05-21 2002-08-27 Alcoa Inc. Method and reactor for production of aluminum by carbothermic reduction of alumina
US6475260B2 (en) * 1999-01-08 2002-11-05 Alcoa Inc. Carbothermic aluminum production using scrap aluminum as a coolant
US6530970B2 (en) * 2001-05-21 2003-03-11 Alcoa Inc. Method for recovering aluminum vapor and aluminum suboxide from off-gases during production of aluminum by carbothermic reduction of alumina
US6805723B2 (en) * 2003-03-06 2004-10-19 Alcoa Inc. Method and reactor for production of aluminum by carbothermic reduction of alumina

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DE2948640C2 (de) * 1979-12-04 1984-12-20 Vereinigte Aluminium-Werke AG, 1000 Berlin und 5300 Bonn Verfahren und Vorrichtung zur thermischen Gewinnung von Aluminium

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2974032A (en) * 1960-02-24 1961-03-07 Pechiney Reduction of alumina
US4033757A (en) * 1975-09-05 1977-07-05 Reynolds Metals Company Carbothermic reduction process
US4099959A (en) * 1976-05-28 1978-07-11 Alcan Research And Development Limited Process for the production of aluminium
US4177060A (en) * 1976-08-23 1979-12-04 Tetronics Research & Development Company Limited Reduction of stable oxides
US4388107A (en) * 1979-01-31 1983-06-14 Reynolds Metals Company Minimum-energy process for carbothermic reduction of alumina
US4216010A (en) * 1979-01-31 1980-08-05 Reynolds Metals Company Aluminum purification system
US4334917A (en) * 1980-04-16 1982-06-15 Reynolds Metals Company Carbothermic reduction furnace
US4409021A (en) * 1982-05-06 1983-10-11 Reynolds Metals Company Slag decarbonization with a phase inversion
US4533386A (en) * 1984-03-27 1985-08-06 Process Development Associates, Inc. Process for producing aluminum
US6475260B2 (en) * 1999-01-08 2002-11-05 Alcoa Inc. Carbothermic aluminum production using scrap aluminum as a coolant
US6440193B1 (en) * 2001-05-21 2002-08-27 Alcoa Inc. Method and reactor for production of aluminum by carbothermic reduction of alumina
US6530970B2 (en) * 2001-05-21 2003-03-11 Alcoa Inc. Method for recovering aluminum vapor and aluminum suboxide from off-gases during production of aluminum by carbothermic reduction of alumina
US6805723B2 (en) * 2003-03-06 2004-10-19 Alcoa Inc. Method and reactor for production of aluminum by carbothermic reduction of alumina

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7824468B2 (en) 2005-07-27 2010-11-02 Thermical Ip Pty Ltd. Carbothermic processes
US20080016984A1 (en) * 2006-07-20 2008-01-24 Alcoa Inc. Systems and methods for carbothermically producing aluminum
WO2008011206A1 (fr) * 2006-07-20 2008-01-24 Alcoa Inc. Systèmes et procédés pour la production carbothermique de l'aluminium
US7556667B2 (en) 2007-02-16 2009-07-07 Alcoa Inc. Low carbon aluminum production method using single furnace carbothermic reduction operated in batch mode
US7753988B2 (en) 2007-07-09 2010-07-13 Alcoa Inc. Use of alumina-carbon agglomerates in the carbothermic production of aluminum
US20100107815A1 (en) * 2007-07-09 2010-05-06 Alcoa Inc. Use of alumina-carbon agglomerates in the carbothermic production of aluminum
US7819937B2 (en) 2007-07-09 2010-10-26 Alcoa Inc. Use of alumina-carbon agglomerates in the carbothermic production of aluminum
US20090013823A1 (en) * 2007-07-09 2009-01-15 Alcoa Inc. Use of alumina-carbon agglomerates in the carbothermic production of aluminum
US7704443B2 (en) 2007-12-04 2010-04-27 Alcoa, Inc. Carbothermic aluminum production apparatus, systems and methods
US20100162850A1 (en) * 2007-12-04 2010-07-01 Alcoa Inc. Carbothermic aluminum production apparatus, systems and methods
US20090139371A1 (en) * 2007-12-04 2009-06-04 Alcoa Inc. Carbothermic aluminum production apparatus, systems and methods
US7854783B2 (en) 2007-12-04 2010-12-21 Alcoa Inc. Carbothermic aluminum production apparatus, systems and methods
US20100147113A1 (en) * 2008-12-15 2010-06-17 Alcoa Inc. Decarbonization process for carbothermically produced aluminum
US9068246B2 (en) 2008-12-15 2015-06-30 Alcon Inc. Decarbonization process for carbothermically produced aluminum

Also Published As

Publication number Publication date
JP2008511760A (ja) 2008-04-17
CN101023190A (zh) 2007-08-22
CA2577565A1 (fr) 2006-03-09
AU2005279732A1 (en) 2006-03-09
WO2006026771A2 (fr) 2006-03-09
BRPI0514819A (pt) 2008-06-24
WO2006026771A3 (fr) 2006-12-14
ZA200702572B (en) 2008-09-25
EP1794333A2 (fr) 2007-06-13
NO20070674L (no) 2007-02-06
RU2007111945A (ru) 2008-10-10

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Effective date: 20051011

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