EP2171106B1 - Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen - Google Patents

Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen Download PDF

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Publication number
EP2171106B1
EP2171106B1 EP08785971A EP08785971A EP2171106B1 EP 2171106 B1 EP2171106 B1 EP 2171106B1 EP 08785971 A EP08785971 A EP 08785971A EP 08785971 A EP08785971 A EP 08785971A EP 2171106 B1 EP2171106 B1 EP 2171106B1
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EP
European Patent Office
Prior art keywords
hydrophobic
solid
process according
dispersion
mixture
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Not-in-force
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EP08785971A
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German (de)
English (en)
French (fr)
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EP2171106A1 (de
Inventor
Imme Domke
Alexej Michailovski
Hartmut Hibst
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BASF SE
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BASF SE
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Priority to PL08785971T priority Critical patent/PL2171106T3/pl
Priority to EP08785971A priority patent/EP2171106B1/de
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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
    • C22B1/00—Preliminary treatment of ores or scrap
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/005—Pretreatment specially adapted for magnetic separation
    • B03C1/01—Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/08—Subsequent treatment of concentrated product
    • B03D1/10—Removing adhering liquid from separated materials
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/0004—Preliminary treatment without modification of the copper constituent
    • C22B15/0008—Preliminary treatment without modification of the copper constituent by wet processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C2201/00—Details of magnetic or electrostatic separation
    • B03C2201/20—Magnetic separation of bulk or dry particles in mixtures

Definitions

  • the present invention relates to a process for separating at least one hydrophobic substance from a mixture comprising said at least one hydrophobic substance and at least one hydrophilic substance, and the use of a solid, hydrophobic surface for separating at least one hydrophobic substance from the above-mentioned mixture.
  • the invention comprises the separation of hydrophobic metal compounds, for example metal sulfides from a mixture of these hydrophobic metal compounds and hydrophilic metal oxides for ore enrichment by means of a hydrophobic surface.
  • Flotation is a separation process in which water-dispersed or suspended substances are transported by adhering gas bubbles to the water surface where they are removed with a clearing device.
  • air is introduced into the flotation bath and finely distributed.
  • the hydrophobic particles, such as sulfidic ores, are difficult to wet with water and therefore adhere to the air bubbles. So these particles are carried by the air bubbles to the surface of the pool and can be skimmed off with the foam.
  • a disadvantage of this process is that the air bubbles often lose their ballast on the way up. So that a sufficient yield can be obtained at all, chemical additives, for example xanthates, are added, which are intended to subsequently hydrophobicize the ore particles more strongly.
  • the constant import in air is also associated with a high risk potential.
  • the above-mentioned disadvantage could be circumvented in the so-called magnetic flotation.
  • the sulfidic ore constituents are specifically coupled or coupled to magnetic particles in this method.
  • a magnetic field is applied and the magnetic constituents containing the desired ore constituents are thus separated from the non-magnetic constituents.
  • US 4,657,666 a method for the enrichment of ores, in which the hydrophobic magnetic particle adheres specifically to the hydrophobic, sulfidic ore.
  • the magnetic particle is selected from magnetite or other magnetic iron oxides previously hydrophobized by attachment to silanes.
  • the sulphidic ore is rendered hydrophobic with a mixture of flotation agents / collector agents in the presence of the oxidic gangue.
  • the magnetic particle is separated from the ore by treatment with 50 vol .-% H 2 O 2 -Lösu.
  • US 4,906,382 discloses a process for the enrichment of sulfidic ores in which they are stirred with magnetic pigments modified with bifunctional molecules.
  • One of the two functional groups adheres to the magnetic core.
  • the magnetic particles can be reversibly agglomerated by varying the pH.
  • the magnetic particles can be used to concentrate sulfide ores.
  • DE 195 14 515 discloses a method to concentrate recyclables with magnetite or hematite particles.
  • the magnetite or hematite particles are modified with carboxylic acids or functionalized alkanols.
  • SU-A-544464 discloses a method for separating magnetic and non-magnetic portions by passing this mixture past a rotating induction roller from which the magnetic portions are attracted.
  • a disadvantage of the methods for ore enrichment described in the prior art is that high magnetic fields are required to efficiently separate the magnetized particles from the original mixture. For this complex, expensive devices are necessary. Furthermore, it must be ensured that the magnetic particle coupled to the ore remains stably connected during the flotation process and can be effectively separated again after the separation.
  • the method according to the invention serves to separate at least one hydrophobic substance from a mixture comprising this at least one hydrophobic substance and at least one hydrophilic substance.
  • hydrophobic means that the corresponding surface can be hydrophobic on its own or can subsequently be rendered hydrophobic. It is also possible that a per se hydrophobic surface is additionally hydrophobicized.
  • the at least one hydrophobic substance is at least one hydrophobic metal compound or carbon
  • the at least one hydrophilic substance is preferably at least one hydrophilic metal compound.
  • the process is used in particular for separating sulfidic ores from a mixture comprising these sulfidic ores and at least one hydrophilic metal compound selected from the group consisting of oxidic metal compounds.
  • the at least one hydrophobic metal compound is preferably selected from the group consisting of sulfidic ores.
  • the at least one hydrophilic metal compound is preferably selected from the group consisting of oxidic metal compounds.
  • sulfidic ores which can be used according to the invention are selected, for example, from the group of copper ores consisting of chalcopyrite (copper pyrites) CuFeS 2 , bornite Co 5 FeS 4 , chalcocite (copper gloss) Cu 2 S and mixtures thereof.
  • Suitable oxidic metal compounds which can be used according to the invention are preferably selected from the group consisting of silicon dioxide SiO 2 , preferably hexagonal modifications, feldspars, for example albite Ma (Si 3 Al) O 8 , mica, for example muscovite KAl 2 [(OH, F) 2 AlSi 3 O 10 ], and mixtures thereof.
  • untreated ore mixtures which are obtained from mine deposits are preferably used in the process according to the invention.
  • an ore mixture to be used according to the invention to be separated before the process according to the invention is ground to a particle size ⁇ 100 ⁇ m, more preferably ⁇ 60 ⁇ m.
  • Preferably usable ore mixtures have a content of sulfidic minerals of at least 0.4 wt .-%, particularly preferably at least 10 wt .-%, on.
  • sulphidic minerals which are present in the ore mixtures which can be used according to the invention are those mentioned above.
  • sulfides of metals other than copper may also be present in the ore mixtures, for example sulfides of lead, zinc, molybdenum, PbS, ZnS and / or MoS 2 .
  • oxidic compounds of metals and semimetals for example silicates or borates or other salts of metals and semimetals, for example phosphates, sulfates or carbonates, may be present in the ore mixtures to be treated according to the invention.
  • a typically used ore mixture which can be separated by the method according to the invention, has the following composition: about 30 wt .-% SiO 2 , about 10 wt .-% Na (Si 3 Al) O 8 , about 3 wt. -% Cu 2 S, about 1 wt .-% MoS 2 , balance chromium, iron, titanium and magnesium oxides.
  • Step (A) of the process of the invention comprises preparing a slurry or dispersion of the mixture to be treated in at least one suitable solvent.
  • Suitable dispersants are all dispersants suitable in which the mixtures to be treated are not completely soluble.
  • Suitable dispersants for the preparation of the slurry or dispersion according to step (A) of the process according to the invention are selected from the group consisting of water, water-soluble organic compounds and mixtures thereof.
  • the dispersant in step (A) is water.
  • the amount of dispersant can be chosen according to the invention so that a slurry or dispersion is obtained which is readily stirrable and / or conveyable.
  • the amount of mixture to be treated based on the total slurry or dispersion, is up to 100% by weight, more preferably 0.5 to 10% by weight, most preferably 1 to 5% by weight.
  • the slurry or dispersion can be prepared according to the invention by all methods known to those skilled in the art.
  • the mixture to be treated and the corresponding amount of dispersant or dispersant mixture are combined in a suitable reactor, for example a glass reactor, and devices known to those skilled in the art stirred, for example in a glass pan with a mechanically stirred paddle stirrer.
  • At least one adhesion-improving substance may be added in addition to the mixture to be treated and the dispersing agent or dispersing agent mixture.
  • adhesion-enhancing substances are long and short-chain amines, ammonia, long-chain alkanes and long-chain, unbranched alcohols.
  • the slurry or dispersion dodecylamine is added, the amount, based on the dry ore and magnetic particle amount, preferably 0.1 to 0.5 wt .-%, particularly preferably 0.3 wt .-% is.
  • the optionally added adhesion-improving substance is generally added in an amount which is sufficient to ensure the adhesion-improving effect of this substance.
  • the at least one adhesion-improving substance is added to 0.01 to 10 wt .-%, particularly preferably 0.05 to 0.5 wt .-%, each based on the total slurry or dispersion.
  • the at least one hydrophobic substance present in the mixture is hydrophobicized with at least one substance before step (B) of the process according to the invention.
  • the hydrophobing of the at least one hydrophobic substance can be carried out before step (A), i. before preparing the slurry or dispersion of the mixture to be treated.
  • step (A) i. before preparing the slurry or dispersion of the mixture to be treated.
  • the hydrophobic substance it is also possible for the hydrophobic substance to be separated to be hydrophobized after preparing the slurry or dispersion according to step (A).
  • the mixture to be treated is rendered hydrophobic before step (A) with a suitable substance.
  • hydrophobizing substance all substances which are capable of further hydrophobicizing the hydrophobic metal compound to be separated off at the surface thereof.
  • the hydrophobizing reagent is generally composed of a radical and an anchor group, wherein the anchor group preferably has at least 1, more preferably 3 reactive groups, which interacts with the hydrophobic substance to be separated, preferably the hydrophobic metal compound to be separated.
  • Suitable anchor groups are phosphonic acid groups or thiol groups.
  • hydrophobicizing compounds are added individually or in admixture with each other in an amount of 0.01 to 50 wt .-%, particularly preferably 0.1 to 50 wt .-%, based on the mixture to be treated.
  • These hydrophobicizing substances can be applied to the hydrophobic substance to be separated off, preferably the at least one metal compound to be separated off, by all methods known to the person skilled in the art.
  • the mixture to be treated is ground and / or stirred with the appropriate amount of hydrophobing substance, for example in a planetary ball mill. Suitable devices are known in the art.
  • Step (B) of the process according to the invention comprises contacting the slurry or dispersion from step (A) with at least one solid, hydrophobic surface for attachment of the at least one hydrophobic substance to be separated, preferably the at least one metal compound to be separated to the solid, hydrophobic surface
  • Solid hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor.
  • the binding of the hydrophobic substance to the solid, hydrophobic surface is effected by hydrophobic interactions.
  • the solid hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill, for example solid or mobile, or the inner wall of a reactor. More preferably, the solid, hydrophobic surface is the inner wall of a reactor or the solid or mobile hydrophobic surface of a treadmill having fibrous micro 3D structures on the surface.
  • a solid, hydrophobic surface is used, which is hydrophobic per se by the material which forms the solid, hydrophobic surface.
  • hydrophobic surfaces which are not hydrophobic by themselves are applied by applying at least one hydrophobic layer.
  • a solid surface made of metal, plastic, glass, wood or metal alloys is rendered hydrophobic by applying a hydrophobic compound, which is optionally surface-coated with suitable substances.
  • this surface consisting of hydrophobic compounds is inherently hydrophobic enough to be used in the process according to the invention.
  • the application of the hydrophobic layer can be done, for example, by vapor deposition.
  • all the hydrophobic materials known to those skilled in the art, which are suitable for forming a corresponding hydrophobic layer can be used to form this hydrophobic layer.
  • a hydrophobic layer is a layer that has no polar groups and therefore has a water-repellent character.
  • Examples of suitable compounds are bifunctional compounds which adhere to one functional group on the solid surface by a covalent or coordinative bond and to the other hydrophobic functional group on the ore by a covalent or coordinative bond.
  • groups with which the binding to the inorganic compound takes place are the carboxyl group -COOH, the phosphonic acid group -PO 3 H 2 , the trihalosilyl group -SiHal 3 with Hal equal to one another independently of one another F, Cl, Br, I, trialkoxysilyl group -Si ( OR 5 ) 3 with R 5 are each, independently of one another, C 1 -C 12 -alkyl and / or C 2 -C 12 -alkenyl.
  • the solid, hydrophobic surface is the surface of a continuous treadmill which is agitated by the slurry or dispersion containing the mixture to be treated.
  • the surface of the treadmill can be increased in a preferred embodiment by methods known in the art, for example by applying a three-dimensional structure on the treadmill.
  • An example of such a three-dimensional structure are fibers attached to the surface of the treadmill.
  • the treadmill can be made of any materials known and suitable to those skilled in the art, for example polymers such as polyethylene terephthalate, metallic materials such as aluminum, multi-component materials such as aluminum alloys.
  • the fibers may also be of any suitable and suitable materials known to those skilled in the art.
  • Step (C) of the method according to the invention comprises removing the at least one solid, hydrophobic surface to which the at least one hydrophobic substance, preferably the at least one hydrophobic metal compound is attached from step (B), from the slurry or dispersion in which the at least one a hydrophilic substance is included.
  • the hydrophobic metal to be separated preferably the hydrophobic metal compound to be separated, is at least partially attached to the hydrophobic solid surface.
  • the hydrophilic substance present in the mixture to be treated remains in the slurry or dispersion because it does not bind to the hydrophobic surface.
  • Removal of the loaded, hydrophobic, solid surface may be accomplished by any method known to those skilled in the art. For example, a plate having the hydrophobic solid surface may be lifted out of a bath containing the slurry or dispersion. Furthermore, it is possible according to the invention that the hydrophobic, solid surface is mounted on a treadmill which moves through the slurry or dispersion. When the hydrophobic solid surface is attached to the inside of a pipe or reactor, in a preferred embodiment, the slurry or dispersion is passed through the reactor or through the pipe. Removal of the solid, hydrophobic surface thus occurs by passing the slurry or dispersion past this surface. It is also possible according to the invention that, when the hydrophobic solid surface is the inner wall of a reactor, the removal of this hydrophobic solid surface occurs by draining the slurry or dispersion to be treated from the reactor.
  • Step (D) comprises separating the at least one hydrophobic material, preferably the at least one hydrophobic metal compound, from the solid, hydrophobic surface.
  • step (C) the hydrophobic, solid surface with the hydrophobic substance to be separated from the reaction mixture to be treated, at least partially laden.
  • This separation can be carried out by any of the methods known to those skilled in the art, which are suitable for separating the hydrophobic substance from said surface without impairing either the hydrophobic substance and / or the surface.
  • the separation in step (D) of the process according to the invention is carried out by treating the solid, hydrophobic surface with a substance selected from the group consisting of organic solvents, basic compounds, acidic compounds, oxidizing agents, surface-active compounds and mixtures thereof.
  • organic solvents examples include methanol, ethanol, propanol, for example n-propanol or iso-propanol, aromatic solvents, for example benzene, toluene, xylenes, ethers, for example diethyl ether, methyl t-butyl ether and mixtures thereof.
  • Examples of basic compounds which can be used according to the invention are aqueous solutions of basic compounds, for example aqueous solutions of alkali metal and / or alkaline earth metal hydroxides, for example KOH, NaOH, aqueous ammonia solutions, aqueous solutions of organic amines of the general formula R 7 3 N, where R 7 is selected from Group consisting of C 1 -C 8 -alkyl, optionally substituted with further functional groups.
  • the acidic compounds may be mineral acids, for example HCl, H 2 SO 4 , HNO 3 or mixtures thereof, organic acids, for example carboxylic acids.
  • H 2 O 2 can be used as the oxidizing agent, for example as a 30% strength by weight aqueous solution (perhydrol).
  • Examples of surface-active compounds which can be used according to the invention are nonionic, anionic, cationic and / or zwitterionic surfactants.
  • the hydrophobic solid surface, to which the hydrophobic material to be separated is attached is washed with an organic solvent, more preferably with acetone, to form the hydrophobic substance separated from the hydrophobic, solid surface.
  • an organic solvent more preferably with acetone
  • This process can also be supported mechanically.
  • the organic solvent or other separation reagent mentioned above is applied with pressure on the hydrophobic surface loaded with the hydrophobic ore.
  • ultrasound may be used to assist the separation process, if appropriate in addition.
  • the organic solvent is used in an amount sufficient to dissolve as much as possible of the entire adhering to the hydrophobic surface amount of the hydrophobic metal compounds thereof.
  • 20 to 100 ml of the organic solvent is used per gram of hydrophobic and hydrophilic fabric to be purified. It is preferred according to the invention that the hydrophobic solid surface is treated with several smaller portions, for example two portions of the organic solvent, which together give said total amount.
  • the hydrophobic substance to be separated is present as a slurry or dispersion in said organic solvent.
  • the hydrophobic material can be separated from the organic solvent by any method known to those skilled in the art, for example, decanting, filtering, distilling off the organic solvent, or settling the solids at the bottom of the container, after which the ore can be skimmed off at the bottom.
  • the hydrophobic substance to be separated off preferably the hydrophobic metal compound to be separated, is separated from the organic solvent by filtration.
  • the hydrophobic substance obtainable in this way can be purified by further methods known to the person skilled in the art.
  • the solvent can, if appropriate after purification, be recycled back to the process according to the invention.
  • the hydrophobic solid surface from which the hydrophobic substance has been separated in step (D) is dried.
  • This drying may be carried out by any method known to those skilled in the art, for example by treatment in an oven at a temperature of for example 30 to 100 ° C.
  • the hydrophobic, solid surface which has optionally been dried, is returned to the process according to the invention, ie used again in step (B) of the process according to the invention.
  • the method according to the invention can be carried out so that the treadmill is continuously passed through the slurry or dispersion to be treated, treated with a solvent to separate the hydrophobic particles, dried, and returned to the bath to be treated.
  • the hydrophobic solid surface It is according to the invention required that this is completely freed from the separation reagent used.
  • the present invention also relates to the use of a solid hydrophobic surface for separating at least one hydrophobic substance, preferably a hydrophobic metal compound or carbon, from a mixture comprising said at least one hydrophobic substance and at least one hydrophilic substance, preferably at least one hydrophilic metal compound hydrophobic surface is the inner wall of a tube, the surface of a plate, the surface of a treadmill or the inner wall of a reactor.
  • the recovered amount of Cu 2 S corresponds to a relative amount of 76%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Sludge (AREA)
EP08785971A 2007-07-17 2008-07-08 Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen Not-in-force EP2171106B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL08785971T PL2171106T3 (pl) 2007-07-17 2008-07-08 Sposób wzbogacania rudy za pomocą stałych powierzchni hydrofobowych
EP08785971A EP2171106B1 (de) 2007-07-17 2008-07-08 Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07112607 2007-07-17
PCT/EP2008/058854 WO2009010422A1 (de) 2007-07-17 2008-07-08 Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen
EP08785971A EP2171106B1 (de) 2007-07-17 2008-07-08 Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen

Publications (2)

Publication Number Publication Date
EP2171106A1 EP2171106A1 (de) 2010-04-07
EP2171106B1 true EP2171106B1 (de) 2011-09-14

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EP08785971A Not-in-force EP2171106B1 (de) 2007-07-17 2008-07-08 Verfahren zur erzanreicherung mittels hydrophober, fester oberflächen

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US (1) US8408395B2 (es)
EP (1) EP2171106B1 (es)
JP (1) JP5496091B2 (es)
CN (1) CN101778957B (es)
AR (1) AR067567A1 (es)
AT (1) ATE524567T1 (es)
AU (1) AU2008277789B2 (es)
BR (1) BRPI0814075A2 (es)
CA (1) CA2693902C (es)
CL (1) CL2008002113A1 (es)
ES (1) ES2373621T3 (es)
PE (1) PE20090667A1 (es)
PL (1) PL2171106T3 (es)
PT (1) PT2171106E (es)
UA (1) UA99623C2 (es)
WO (1) WO2009010422A1 (es)
ZA (1) ZA201001077B (es)

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JP2010534554A (ja) 2010-11-11
AU2008277789B2 (en) 2012-05-03
AU2008277789A1 (en) 2009-01-22
US8408395B2 (en) 2013-04-02
US20100200510A1 (en) 2010-08-12
CL2008002113A1 (es) 2009-10-23
PE20090667A1 (es) 2009-07-04
CA2693902A1 (en) 2009-01-22
ATE524567T1 (de) 2011-09-15
AR067567A1 (es) 2009-10-14
ES2373621T3 (es) 2012-02-07
CN101778957B (zh) 2012-07-04
RU2010105290A (ru) 2011-08-27
PT2171106E (pt) 2011-10-06
UA99623C2 (ru) 2012-09-10
BRPI0814075A2 (pt) 2015-02-03
WO2009010422A1 (de) 2009-01-22
EP2171106A1 (de) 2010-04-07
CN101778957A (zh) 2010-07-14
CA2693902C (en) 2016-06-28
ZA201001077B (en) 2011-04-28
JP5496091B2 (ja) 2014-05-21

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