EP2021285A2 - Procédé de production de magnétite - Google Patents

Procédé de production de magnétite

Info

Publication number
EP2021285A2
EP2021285A2 EP07728511A EP07728511A EP2021285A2 EP 2021285 A2 EP2021285 A2 EP 2021285A2 EP 07728511 A EP07728511 A EP 07728511A EP 07728511 A EP07728511 A EP 07728511A EP 2021285 A2 EP2021285 A2 EP 2021285A2
Authority
EP
European Patent Office
Prior art keywords
red mud
magnetite
reaction
reducing agent
iron
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.)
Withdrawn
Application number
EP07728511A
Other languages
German (de)
English (en)
Inventor
Eberhard Krause
Valentin Röhm
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.)
KRSYS GMBH
Original Assignee
Krause-Rohm-Systeme AG
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 Krause-Rohm-Systeme AG filed Critical Krause-Rohm-Systeme AG
Publication of EP2021285A2 publication Critical patent/EP2021285A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/066—Treatment of the separated residue
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide [Fe3O4]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/0409—Waste from the purification of bauxite, e.g. red mud
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • Red mud is produced during aluminum production according to the Bayer process.
  • red mud is a mixture which is mainly composed of iron (III) oxides or hydroxides, titanium oxides, aluminum oxide residues, quartz sand, calcium oxide and sodium oxide. Due to its high content of residual sodium hydroxide, it also has a strongly basic pH in the range between 1 1 and 13.
  • the name red mud comes from the red color caused by iron (III) oxide.
  • 0.5 to 1.5 tonnes of red mud are an unavoidable companion to every ton of aluminum produced. The amount of red mud produced in this way each year amounts to several million tons and, together with the already existing amounts of red mud, represents a serious economic and ecological problem.
  • red mud is considered essentially as waste and therefore supplied for disposal.
  • the disposal of the red mud is usually done by storage in sealed landfills.
  • This form of storage is expensive and expensive, since large landfill areas and facilities are needed and incur high costs for the transport of red mud.
  • the long-term costs arising from landfilling are difficult to calculate and, in addition to the various ecological problems, represent an additional economic problem.
  • red mud contains, depending on the quality of the bauxite originally used, a proportion of 30% to 60% of iron (III) compounds in the form of hematite (Fe 2 O) and goethite (FeO (OH)), it offers itself for the recovery of Iron or iron ore in particular advantageous manner.
  • iron (III) compounds in the form of hematite (Fe 2 O) and goethite (FeO (OH)
  • the workup of the red mud is complicated, inter alia, by the fact that the particles of the red mud, due to the production process, have a very small average diameter in the range between 0.1 and 1.0 ⁇ m.
  • a separation of the iron (III) compounds from the non-iron-containing residual mineral stock therefore represents a complex technical problem and has not yet been satisfactorily resolved.
  • GB 731 923 discloses a process for the thermal treatment of thermally reactive, finely divided solid particles.
  • red mud from the Bayer process can be introduced into a fluidized-bed reactor and kept in a pseudo-liquid fluidized bed state by means of a gas flow passed through the red mud from below.
  • the aerosol formed must be heated to a predetermined temperature and this temperature must be kept as constant as possible during the reaction so that a conversion of hematite into magnetite can take place.
  • For heating the reaction mixture to the target temperature either a preheating of the gas stream, an injection and burning of fossil fuels in the reaction space or a combination of both is provided.
  • the invention provides that the excess amount of heat is absorbed by arranged in the fluidized bed reactor, inert solids. Alternatively, it is provided that cooling water is injected into the reaction space or additional cooling, inert solids are added.
  • the object of the present invention is therefore to provide a process which can be realized on an industrial scale, which makes possible a comprehensive, economically and ecologically advantageous recovery of the iron-containing constituents of red mud and is suitable both for coping with the quantities of red mud produced annually and for processing the landfill already disposed of Red mud is suitable.
  • the object is achieved by a method for recovering valuable material by means of red mud with the features of claim 1.
  • red mud which is produced by the Bayer process used for aluminum production, used in a process for recovering magnetite, which comprises at least the reduction of hematite and / or goethite to magnetite with at least one reducing agent, wherein the reducing agent is at least one vegetable oil and / or includes a fat and / or coal.
  • magnetite is the thermodynamically most stable iron oxide and has a spinel structure AB 2 O 4 in which iron (II) ions occupy the octahedral sites and iron (III) ions occupy the tetrahedral sites. Magnetite, in contrast to hematite and goethite, is strongly ferromagnetic.
  • the inventive method therefore allows by the conversion of the iron-containing components, a separation of the red mud into magnetizable iron ore and a non-magnetizable, low-iron residual mineral stock, which in turn is a valuable material and is variously usable.
  • Vegetable oils are in great diversity and in large quantities worldwide available.
  • the Federal Environment Agency classifies vegetable oils in water hazard class 1 and thus as only slightly hazardous to water. This opens up the possibility in economically and ecologically advantageous, particularly simple and sustainable ways of making renewable biological compounds usable as an environmentally friendly alternative to fossil mineral oils for iron ore mining.
  • Another advantage is the ability to perform the process both continuously and discontinuously.
  • a palm oil and / or a soybean oil and / or a rapeseed oil is used as vegetable oil.
  • palm oils, soybean oils or rapeseed oils are suitable for use in the context of the process according to the invention since, economically speaking, they represent inexpensive and globally available educts.
  • they are largely unproblematic due to their biodegradability under environmental aspects.
  • the method comprises the following steps: a) mixing the red mud with the reducing agent, b) burning the reaction mixture under controlled air supply for a predetermined time interval in a predetermined temperature range, c) separating the solid components from the reaction mixture, d) Crushing the solid components; and e) separating at least a first component comprising at least magnetite from at least one second solid component.
  • Suitable reactor types include, for example, continuous reactors, rotary kilns or any other suitable reactor devices.
  • the reaction itself is carried out in a simple manner by burning the reaction mixture. It is advantageously provided that the reaction takes place during a predetermined time interval under controlled air supply in a predetermined temperature range in order to be able to control the course of the reaction in dependence on the educts used.
  • at least the vegetable oil or the fat together with various oxides from the red mud itself act as a source of oxygen.
  • the solid components of the resulting reaction mixture are separated after completion of the reaction of the liquid or gaseous components.
  • the end of the reaction can be determined in a particularly simple manner by the color change from red (Fe 2 O 3 ) to black (Fe 3 O 4 ).
  • the separation of the solid from the liquid and / or gaseous components is carried out in a simple manner with the aid of a solids separator and / or gas separator coupled to the reaction vessel.
  • the solid components may be present after separation in partially clumped or Grahamgebackener form.
  • the method therefore provides in step d) for facilitating and improving the further workup, a comminution of the solid components.
  • the mass can be ground in a known manner, which again arise the original, fine particles.
  • the powdered mixture of the solid components thus obtained is in the last Step of the method, at least a first, at least magnetite comprehensive component of at least one second component separated.
  • step b) of the method the air supply is controlled so that the reaction proceeds under stoichiometric conditions.
  • the reaction conditions thus selected result in a reaction process similar to the production of wood gas and yield various useful compounds such as elemental carbon, carbon dioxide, carbon monoxide, methane, ethene, hydrogen and water vapor.
  • the resulting elemental carbon serves advantageously as an additional reducing agent and accelerates the reaction.
  • a control of the reaction temperature can be realized.
  • the additional valuable substances can be separated in a known manner and supplied to other uses.
  • the predetermined temperature range in step b) of the method is at least 650 ° C and / or at most 1000 ° C. Carrying out the reaction in the temperature range mentioned ensures advantageously that the reaction conditions can be selected depending on the nature and requirements of the reducing agent used, whereby a variable, simple and cost-reducing option for optimal process control is ensured.
  • the combustion gases recirculated in step b) of the process comprise at least carbon monoxide and / or hydrogen.
  • Each of the two compounds acts as an additional reducing agent.
  • the combustion gas recirculation thus ensures a complete utilization of the usable reaction products and reaction energy on the one hand as well as for an accelerated conversion of hematite and / or goethite into magnetite on the other hand.
  • a further cost reduction is achieved due to the reduced demand for reducing agent.
  • the recirculation of combustion gas thus advantageously makes possible a faster, cheaper and ecologically optimized process design.
  • the method before step c) comprises an additional step f), in which the air supply is controlled for a time interval to be determined so that the reaction proceeds under stoichiometric and / or superstoichiometric conditions.
  • step f) in which the air supply is controlled for a time interval to be determined so that the reaction proceeds under stoichiometric and / or superstoichiometric conditions.
  • step e) of the method comprises using a magnetic separator.
  • the concentration of pure magnetite in an ore separated in this way is at least 90% about twice as high as in high-quality natural ore.
  • a magnetic separator so a technically particularly simple and cost-effective way can be created to separate the red mud practically quantitatively into high-quality, magnetizable iron ore and non-ferrous components.
  • alternative or additional separation processes which make use of other physical or chemical differences of the compounds to be separated, such as flotation separation processes.
  • the red mud and the reducing agent additionally at least one further component comprising at least calcium carbonate is added.
  • the calcium carbonate can be introduced in an advantageous manner in the form of limestone and serves as a reaction promoter. It thus allows a more complete and faster reaction performance using a low-cost starting material, which further savings for the overall process can be achieved.
  • the second component separated in step e) of the method comprises at least one cement aggregate.
  • the low-iron residual mineral stock is suitable as cement aggregate. Without separating the ferrous component, red mud could not be used for this purpose because the high iron content would lead to complex reactions called rust formation.
  • step a) of the process in combination with an additional admixing of calcium carbonate in step a) of the process thus the mineral formation is promoted and gives a hydraulic cement, which is due to its high strength and durability as one of the most important binders in the construction industry use.
  • step a) of the process thus the mineral formation is promoted and gives a hydraulic cement, which is due to its high strength and durability as one of the most important binders in the construction industry use.
  • the cement aggregate comprises silicon dioxide and / or silicates and / or aluminosilicates.
  • Portland cement consists, for example, of about 58 to 66% calcium oxide (CaO), 18 to 26% silicon dioxide (SiO 2 ), 4 to 10% aluminum oxide (Al 2 O 3 ) and 2 to 5% iron oxide (Fe 2 O 3 ).
  • these main constituents mainly form di- or tricalcium silicate (2/3 CaOxSiO 2 ), tetracalcium aluminate ferrite (4 CaOxAl 2 O 3 X Fe 2 O 3 ) and tricalcium aluminate (3 CaOxAl 2 O 3 ).
  • di- or tricalcium silicate (2/3 CaOxSiO 2
  • tetracalcium aluminate ferrite 4 CaOxAl 2 O 3 X Fe 2 O 3
  • tricalcium aluminate 3 CaOxAl 2 O 3
  • Red mud with a water content of about 30% is mixed in a quartz glass vessel with rapeseed oil in a weight ratio of 2: 1 to 10: 1.
  • the reduction of the iron (III) compounds is started by igniting the rapeseed oil.
  • the end of the reaction can be determined by the color change from red (Fe 2 O 3 ) to black (Fe 3 O 4 ).
  • complete conversion of the iron (III) compounds can be achieved by further addition of rapeseed oil.
  • the solid, black-yellowish phase is first separated by filtration of any liquid residual components present.
  • the thus obtained Lovegebackenen particles are in one Mill crushed and separated after grinding with the aid of a magnetic separator in magnetite and non-magnetic cement raw materials (silicates and sand).
  • Red mud from bauxite pulping contains iron oxides / hydroxides in the form of the minerals hematite Fe 2 O 3 and goethite FeO (OH) in 42-50% (w / w), clay minerals of the aluminosilicate group with more than 30% (w / w), SiO 2 in Quantities between 5-10% (w / w) and lime from the recovery of caustic soda in 3-5% (w / w).
  • the water content of red mud is usually between 25-40% (v / w).
  • This mineral mixture is homogeneously mixed with waste or waste vegetable oils such as frying oils in a mixer without heat.
  • the added amount of vegetable oil or vegetable fat should be at least 20% (w / w) to ensure self-supporting combustion.
  • the pasty red mud mass is fed via a screw conveyor into a pellet press, in which pellets are produced for combustion, whereby a reduction of the aqueous constituents occurs by the pressing.
  • the pellets are transported after further drying with residual heat to a pellet stove and burned there under controlled oxygen supply. It is first worked for a period of 10-20 minutes with air or excess oxygen, with firing temperatures of about 900-1000 ° C can be achieved. Under these conditions, various substances contained in the red mud are oxidized, in some cases a reduction of hematite to magnetite is observed, because the oxygen access to the interior of the pellets is hindered. Subsequently, the air supply is reduced, so that the reactions proceed under underöchiomethschen conditions.
  • the reaction temperature can thereby drop to about 650 ° C, which occurs in parallel pyrolysis of the remaining organic components and CO 2 , H 2 and CO arise. Additional CO is formed in further reaction by the Boudouard reaction from CO 2 and resulting free carbon. From this step, the combustion gases are returned to the furnace to ensure the reducing action of, in particular, H 2 and CO gases for the transfer of hematite to magnetite.
  • An alternating procedure with under- or superstoichiometric air supply has been found to be advantageous in order to avoid the formation of too much carbon and thus the formation of iron carbides.
  • the result of the process depends on the operating parameters, the composition of the red mud, the proportion by weight and the type of vegetable oil, the reaction temperature and the control of the air supply. Even in the simplest version of the process with continuous excess air, up to 75% of magnetite and 8% of ilmenite are found in the separated magnetic mineral according to laboratory results.
  • the reduced fine powder is transported after the reduction in a cooling drum with heat exchanger and fed in the next stage after sufficient cooling to a magnetic separator. This separates the components magnetite and ilmenite (iron titanium ore) due to their strong magnetic properties.
  • non-magnetic clay minerals quartz and lime and small amounts of non-magnetic iron ore.
  • the clay minerals can be used as a cement additive, as their chemical composition largely corresponds to the substances occurring in cement and so-called iron cement can be produced. By adding further quicklime, the hydraulic character of the cement surcharge can be adapted to the respective requirements.
  • the non-magnetic mineral residue can be used as a water retainer, soil improver or mineral fertilizer.
  • the red mud is used as a reducing agent solid pressing residue from the vegetable oil extraction or wood chips in the order of up to 20% (w / w) added.
  • This organic additive is burned and results in complete oxidation only at high excess air.
  • iron ore is reduced to magnetite to a level of at least 75%.
  • coking products are produced. Too high a carbon content leads - as already mentioned - to the formation of non-magnetic carbides of the iron, as shown by a reduction in the magnetically separable amount of red mud mineral mixture.
  • the process control is advantageously made allothermic, since at the same time both strongly exothermic reactions such as the oxidation of the carbon (C + O 2 ->
  • Iron (III) compounds to magnetite under these conditions is at least 75%, but can be easily increased by up to 90% or more by conventional measures.
  • the reduced fine powder is then transported in a cooling drum with heat exchanger and fed in the next stage after sufficient cooling to a magnetic separator.
  • the clay minerals can be used as a cement supplement, since their chemical composition largely corresponds to the substances occurring in cement and thus so-called iron cement can be produced. By adding further quicklime, the hydraulic character of the cement surcharge can be adapted to the respective requirements.
  • the non-magnetic mineral residue may be used as a soil conditioner or mineral fertilizer because of the clay minerals as a water retainer or due to the lime and iron content.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Civil Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Treatment Of Sludge (AREA)
  • Compounds Of Iron (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treating Waste Gases (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

Procédé de production de magnétite à l'aide de boue rouge résultant du procédé Bayer utilisé en vue de la production de l'aluminium. Ledit procédé consiste à réduire de l'hématite et / ou de la goethite en magnétite à l'aide d'un agent de réduction qui contient au moins une huile végétale et / ou une graisse et / ou du carbone.
EP07728511A 2006-05-04 2007-04-25 Procédé de production de magnétite Withdrawn EP2021285A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610020840 DE102006020840B4 (de) 2006-05-04 2006-05-04 Verfahren zur Gewinnung von Magnetit
PCT/EP2007/054056 WO2007128695A2 (fr) 2006-05-04 2007-04-25 Procédé de production de magnétite

Publications (1)

Publication Number Publication Date
EP2021285A2 true EP2021285A2 (fr) 2009-02-11

Family

ID=38579803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07728511A Withdrawn EP2021285A2 (fr) 2006-05-04 2007-04-25 Procédé de production de magnétite

Country Status (10)

Country Link
US (1) US9199856B2 (fr)
EP (1) EP2021285A2 (fr)
CN (1) CN101437759A (fr)
AU (1) AU2007247252B2 (fr)
BR (1) BRPI0711307A2 (fr)
CA (1) CA2651956C (fr)
DE (1) DE102006020840B4 (fr)
ME (1) MEP50208A (fr)
RU (1) RU2433956C2 (fr)
WO (1) WO2007128695A2 (fr)

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CN101811090B (zh) * 2010-05-11 2011-11-09 贵州铝城铝业原材料研究发展有限公司 电解铝废料磁选方法
WO2012100004A1 (fr) * 2011-01-18 2012-07-26 Mohsen Amiran Procédés de récupération d'un résidu de magnétite et de bauxite
CN102432074A (zh) * 2011-08-30 2012-05-02 刘明诗 一种拜耳法、拜耳烧结法氧化铝赤泥零污染、零残留处理方法
CN102626670B (zh) * 2012-04-28 2014-08-13 北京科技大学 一种回转窑还原磁化处理赤泥制备铁精粉的方法
CN103290207B (zh) * 2013-06-14 2015-08-12 中南大学 一种赤泥综合回收利用铁和铝的方法
RU2525394C1 (ru) * 2013-06-26 2014-08-10 Федеральное государственное бюджетное учреждение науки Институт металлургии Уральского отделения Российской академии наук (ИМЕТ УрО РАН) Способ переработки оксидных железосодержащих материалов
CN104327886A (zh) * 2014-10-10 2015-02-04 昆明理工大学 一种应用于冶金火法冶炼过程中的燃料还原剂
EP3224204A4 (fr) * 2014-11-24 2018-07-18 Gmr, Llc Séparation des particules dans un procédé de récupération de magnétite à partir d'un résidu de bauxite
WO2017163094A1 (fr) 2016-03-25 2017-09-28 Fakon Vállalkozási Kft. Procédé de traitement de boue rouge et de production de sels de métal de terres rares
CN106115794B (zh) * 2016-06-15 2018-03-02 天津市国润永泰环保科技有限公司 一种采用工业废酸和红泥资源化生产四氧化三铁磁粉的方法
CA3085182A1 (fr) 2017-12-08 2019-06-13 Worcester Polytechnic Institute Production de magnetite a partir de residus de bauxite
RU2683149C1 (ru) * 2018-05-22 2019-03-26 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Способ получения магнетита
CN108866318A (zh) * 2018-07-02 2018-11-23 深圳市中金环保科技有限公司 一种从赤泥中低成本高效分离含铁物质的方法
RU2697539C1 (ru) * 2019-04-09 2019-08-15 Борис Николаевич Улько Способ комплексной переработки мелкодисперсных металлосодержащих отходов
CN110484734A (zh) * 2019-09-19 2019-11-22 辽宁东大矿冶工程技术有限公司 一种高铁赤泥强磁预选-深度还原熔炼的方法
CN110512081A (zh) * 2019-09-19 2019-11-29 辽宁东大矿冶工程技术有限公司 高铁赤泥强磁预选-悬浮态直接还原-高温熔分的方法
RU2750429C1 (ru) * 2021-01-12 2021-06-28 Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук Способ получения магнетита
CN114686680B (zh) * 2022-04-01 2024-05-14 青岛盈坤源矿业科技有限公司 一种赤泥提铁工艺
CN119287156A (zh) * 2024-12-13 2025-01-10 中国恩菲工程技术有限公司 赤泥的处理方法

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EUROPÄISCHE KOMMISSION: "Staatliche Beihilfe N 685/2002 - Deutschland; Mineralölsteuerbefreiung für Biokraftstoffe", 6 April 2004 (2004-04-06), pages 1 - 8, XP055006540, Retrieved from the Internet <URL:http://ec.europa.eu/eu_law/state_aids/comp-2002/n685-02.pdf> [retrieved on 20110908] *

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BRPI0711307A2 (pt) 2011-12-06
US20090175782A1 (en) 2009-07-09
WO2007128695A2 (fr) 2007-11-15
CA2651956A1 (fr) 2007-11-15
RU2433956C2 (ru) 2011-11-20
AU2007247252A1 (en) 2007-11-15
DE102006020840A1 (de) 2007-11-15
DE102006020840B4 (de) 2010-08-12
CN101437759A (zh) 2009-05-20
MEP50208A (bs) 2011-02-10
US9199856B2 (en) 2015-12-01
AU2007247252B2 (en) 2012-07-05
CA2651956C (fr) 2014-02-11
WO2007128695A3 (fr) 2008-01-31
RU2008143358A (ru) 2010-05-10

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