EP2171106B1 - Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides - Google Patents

Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
hydrophobic
solid
process according
dispersion
mixture
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.)
Not-in-force
Application number
EP08785971A
Other languages
German (de)
English (en)
Other versions
EP2171106A1 (fr
Inventor
Imme Domke
Alexej Michailovski
Hartmut Hibst
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.)
BASF SE
Original Assignee
BASF SE
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39797971&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2171106(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Priority to PL08785971T priority Critical patent/PL2171106T3/pl
Priority to EP08785971A priority patent/EP2171106B1/fr
Publication of EP2171106A1 publication Critical patent/EP2171106A1/fr
Application granted granted Critical
Publication of EP2171106B1 publication Critical patent/EP2171106B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03CMAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00Magnetic separation
    • B03C1/005Pretreatment specially adapted for magnetic separation
    • B03C1/01Pretreatment specially adapted for magnetic separation by addition of magnetic adjuvants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03CMAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00Magnetic separation
    • B03C1/02Magnetic separation acting directly on the substance being separated
    • B03C1/30Combinations with other devices, not otherwise provided for
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/08Subsequent treatment of concentrated product
    • B03D1/10Removing adhering liquid from separated materials
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0002Preliminary treatment
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0002Preliminary treatment
    • C22B15/0004Preliminary treatment without modification of the copper constituent
    • C22B15/0008Preliminary treatment without modification of the copper constituent by wet processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION 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
    • B03CMAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C2201/00Details of magnetic or electrostatic separation
    • B03C2201/20Magnetic separation whereby the particles to be separated are in solid form

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%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
  • Treatment Of Sludge (AREA)

Abstract

La présente invention concerne un procédé pour séparer au moins une substance hydrophobe d'un mélange contenant au moins cette ou ces substances hydrophobes et au moins une substance hydrophile, ce procédé comprenant les étapes suivantes : (A) la production d'une suspension ou d'une dispersion du mélange à traiter dans au moins un agent de dispersion adapté, (B) la mise en contact de la suspension ou de la dispersion issue de l'étape (A) avec au moins une surface hydrophobe solide pour que la ou les substances hydrophobes à séparer se lient à celle-ci, (C) le retrait de la ou des surfaces hydrophobes solides, auxquelles la ou les substances hydrophobes sont liées à l'issue de l'étape (B), de la suspension ou de la dispersion contenant la ou les substances hydrophiles et (D) la séparation de la ou des substances hydrophobes de la surface hydrophobe solide. Selon l'invention, ce procédé sert à séparer des minéraux sulfurés (hydrophobes), en particulier des sulfures de cuivre, de mélanges contenant des oxydes métalliques hydrophiles (minéraux de gangue). La surface solide peut être p. ex. un tapis roulant pourvu d'une surface texturée hydrophobe.

Claims (11)

  1. Procédé pour séparer au moins une substance hydrophobe d'un mélange comprenant ladite au moins une substance hydrophobe et au moins une substance hydrophile, comprenant les étapes :
    (A) préparation d'une suspension ou d'une dispersion du mélange à traiter dans au moins un dispersant approprié,
    (B) mise en contact de la suspension ou de la dispersion de l'étape (A) avec au moins une surface solide hydrophobe pour la liaison de ladite au moins une substance hydrophobe à séparer sur celle-ci, où la surface solide hydrophobe est la paroi intérieure d'un tube, la surface d'une plaque, la surface d'une bande transporteuse ou la paroi intérieure d'un réacteur,
    (C) élimination de ladite au moins une surface solide hydrophobe, sur laquelle ladite au moins une substance hydrophobe est liée de l'étape (B) de la suspension ou de la dispersion, dans laquelle est contenue ladite au moins une substance hydrophile et
    (D) séparation de ladite au moins une substance hydrophobe de la surface solide hydrophobe.
  2. Procédé selon la revendication 1, caractérisé en ce que ladite au moins une substance hydrophobe est au moins un composé métallique ou un charbon hydrophobe et ladite au moins une substance hydrophile est au moins un composé métallique hydrophile.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que ladite au moins une substance hydrophobe se trouvant dans le mélange est hydrofugée avant l'étape (B) avec au moins une substance.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que ledit au moins un composé métallique hydrophobe est choisi dans le groupe constitué par les minerais sulfurés.
  5. Procédé selon l'une quelconque des revendications 2 à 4, caractérisé en ce que ledit au moins un composé métallique hydrophile est choisi dans le groupe constitué par les composés métalliques de type oxyde.
  6. Procédé selon la revendication 4, caractérisé en ce que les minerais sulfurés sont choisis dans le groupe des minerais de cuivre, constitué par la chalcopyrite CuFeS2, la bornite Cu5FeS4, la chalcocite Cu2S et leurs mélanges.
  7. Procédé selon la revendication 5, caractérisé en ce que les composés métalliques de type oxyde sont choisis dans le groupe constitué par le dioxyde de silicium SiO2, le feldspath, le mica et leurs mélanges.
  8. Procédé salon l'une quelconque des revendications 1 à 7, caractérisé en ce que le dispersait dans l'étape (A) est l'eau.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la séparation dans l'étape (D) a lieu par traitement de la surface solide hydrophobe avec une substance choisie dans le groupe constitué par les solvants organiques, les composés basiques, les composés acides, les oxydants, les composés tensioactifs et leurs mélanges.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'après l'étape (D), la surface solide hydrophobe est à nouveau alimentée dans l'étape (B).
  11. Utilisation d'une surface solide hydrophobe pour séparer au moins une substance hydrophobe d'un mélange comprenait ladite au moins une substance hydrophobe et au moins une substance hydrophile, où la surface solide hydrophobe est la paroi intérieure d'un tube, la surface d'une plaque, la surface d'une bande transporteuse, la paroi intérieure d'un réacteur.
EP08785971A 2007-07-17 2008-07-08 Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides Not-in-force EP2171106B1 (fr)

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 (fr) 2007-07-17 2008-07-08 Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07112607 2007-07-17
PCT/EP2008/058854 WO2009010422A1 (fr) 2007-07-17 2008-07-08 Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides
EP08785971A EP2171106B1 (fr) 2007-07-17 2008-07-08 Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides

Publications (2)

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

Family

ID=39797971

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08785971A Not-in-force EP2171106B1 (fr) 2007-07-17 2008-07-08 Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides

Country Status (17)

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

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010007075A1 (fr) * 2008-07-18 2010-01-21 Basf Se Séparation sélective de substances au moyen de particules magnétiques modifiées
EP2376230B1 (fr) 2008-12-11 2014-07-30 Basf Se Enrichissement de minerais de valeur à partir de résidu minier (tailings)
AU2010217681B2 (en) * 2009-02-24 2016-07-07 Basf Se Cu-Mo separation
JP5683498B2 (ja) 2009-03-04 2015-03-11 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se 磁性の疎水性凝集塊
ES2437415T3 (es) * 2009-03-04 2014-01-10 Basf Se Separación magnética de minerales de metal no ferroso mediante acondicionamiento de varias etapas
DE102009038666A1 (de) 2009-08-24 2011-03-10 Siemens Aktiengesellschaft Verfahren zur kontinuierlichen magnetischen Erztrennung und/oder -aufbereitung sowie zugehörige Anlage
PE20130762A1 (es) 2009-11-11 2013-06-27 Basf Se Procedimiento para concentrar componentes separados por via magnetica de suspensiones de minerales y para expulsar dichos componentes de un separador magnetico con pocas perdidas
US11331676B2 (en) 2010-02-01 2022-05-17 Virginia Tech Intellectual Properties, Inc. Cleaning and dewatering fine coal
US9518241B2 (en) 2010-02-01 2016-12-13 Virginia Tech Intellectual Properties, Inc. Method of separating and de-watering fine particles
US9789492B2 (en) 2010-02-01 2017-10-17 Virginia Tech Intellectual Properties, Inc. Cleaning and dewatering fine coal
WO2011114303A1 (fr) * 2010-03-18 2011-09-22 Basf Se Amélioration de la qualité du concentré dans l'enrichissement d'un minerai de platine ug-2
US20110229384A1 (en) * 2010-03-18 2011-09-22 Basf Se Concentrate quality in the enrichment of ug-2 platinum ore
AU2012213470A1 (en) 2011-02-01 2013-08-15 Basf Corporation Apparatus for continuous separation of magnetic constituents and cleaning magnetic fraction
US9731221B2 (en) 2011-05-25 2017-08-15 Cidra Corporate Services, Inc. Apparatus having polymer surfaces having a siloxane functional group
AU2012258595B2 (en) * 2011-05-25 2017-06-01 Cidra Corporate Services Inc. Method and system for releasing mineral from synthetic bubbles and beads
GB201115823D0 (en) 2011-09-13 2011-10-26 Novel Polymer Solutions Ltd Mineral processing
PE20141342A1 (es) 2011-12-13 2014-10-15 Cidra Corporate Services Inc Separacion mineral usando membranas y filtros funcionalizados de polimero o revestido de polimero
US9216420B2 (en) 2012-05-09 2015-12-22 Basf Se Apparatus for resource-friendly separation of magnetic particles from non-magnetic particles
PE20142378A1 (es) 2012-05-09 2015-01-29 Basf Se Aparato para la separacion con poco uso de recursos de particulas magneticas a partir de particulas no magneticas
US10751693B2 (en) 2012-05-22 2020-08-25 CiDRA Corporate Service Inc. Mineral recovery using hydrophobic polymer surfaces
EP2861352B1 (fr) * 2012-06-11 2019-04-10 Virginia Tech Intellectual Properties, Inc. Procédés de séparation et de déshydratation de particules fines
WO2014029715A1 (fr) 2012-08-21 2014-02-27 Basf Se Agencement magnétique pour le transport de matériau magnétisé
WO2014068142A1 (fr) 2012-11-05 2014-05-08 Basf Se Appareil permettant la séparation continue de constituants magnétiques
CA2911663C (fr) * 2013-05-13 2020-03-24 Cidra Corporate Services Inc. Surfaces polymeres ayant un groupe fonctionnel siloxane
US9889452B2 (en) * 2013-12-20 2018-02-13 Chemtreat, Inc. Methods for facilitating mineral extraction
AU2015266609B2 (en) * 2014-05-30 2019-12-12 Cidra Corporate Services Inc. Mineral recovery using hydrophobic polymer surfaces
CA2966807C (fr) 2014-11-27 2023-05-02 Basf Se Entree d'energie pendant l'agglomeration de separation magnetique
MX2017006699A (es) 2014-11-27 2017-08-21 Basf Se Mejora de la calidad del concentrado.
CN105214853B (zh) * 2015-11-09 2017-08-25 中国矿业大学 一种褐煤浮选方法
WO2017087498A1 (fr) 2015-11-16 2017-05-26 Cidra Corporate Services Inc. Utilisation de milieu modifié pour la récupération de minéraux dans un flux de résidus à la fin d'un processus de séparation par flottation
EP3181230A1 (fr) 2015-12-17 2017-06-21 Basf Se Ultraflottation avec des particules support magnétiquement réactives
CA3039206C (fr) * 2016-10-04 2021-04-27 Cidra Corporate Services Llc Recuperation par flottation hybride de minerais contenant des mineraux
US11066725B2 (en) * 2017-03-01 2021-07-20 Cidra Corporate Services Llc Cyclone underflow scavengering process using enhanced mineral separation circuits (EMSC)
CA3055189C (fr) 2017-03-01 2023-02-14 Cidra Corporate Services Llc Installation de traitement de mineraux
PE20200396A1 (es) * 2017-08-03 2020-02-26 Basf Se Separacion de una mezcla utilizando particulas portadoras magneticas
CN109530078B (zh) * 2018-10-23 2020-07-28 宁波工程学院 一种利用水面振动分离亲疏水微粒的装置
EP4301520A1 (fr) 2021-03-05 2024-01-10 Basf Se Séparation magnétique de particules supportées par des tensioactifs spécifiques
CN113813922B (zh) * 2021-10-09 2023-10-03 郑州大学 一种载体型矿化富集分离药剂及其制备方法和应用

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US893A (en) * 1838-08-25 Machine for threshing and cleaning clover-seed
US465766A (en) * 1891-12-22 roberts
US92893A (en) * 1869-07-20 Improved ore-concentrator and endless sluice-blanket
US2189698A (en) * 1937-01-21 1940-02-06 Metallgesellschaft Ag Method of mechanically separating mineral mixtures
GB1259738A (en) * 1970-02-12 1972-01-12 Ucb Sa Flotation process
SU544464A1 (ru) * 1971-12-01 1977-01-30 Всесоюзный научно-исследовательский институт минерального сырья Способ мокрого магнитного обогащени слабомагнитных руд
US3796308A (en) * 1972-07-24 1974-03-12 Canadian Patents Dev Bacterial oxidation in upgrading sulfidic ores and coals
CA1085760A (fr) * 1976-02-10 1980-09-16 Research Council Of Alberta (The) Procede d'extraction du bitume de sables bitumineux
US4224138A (en) * 1979-05-10 1980-09-23 Jan Kruyer Process for recovering bitumen from oil sand
US4269699A (en) * 1979-10-23 1981-05-26 Canadian Patents & Dev. Ltd. Bioadsorption alteration of iron sulfide surfaces
EP0091923B1 (fr) * 1981-10-26 1987-03-04 W.S.R. Pty. Ltd. Flottation magnetique
US4834898A (en) 1988-03-14 1989-05-30 Board Of Control Of Michigan Technological University Reagents for magnetizing nonmagnetic materials
US5161694A (en) * 1990-04-24 1992-11-10 Virginia Tech Intellectual Properties, Inc. Method for separating fine particles by selective hydrophobic coagulation
EP0869218A1 (fr) * 1995-05-22 1998-10-07 Westvaco Corporation Elimination de colles des vieux papiers avec une force magnetique
JPH07256251A (ja) * 1994-03-18 1995-10-09 Chlorine Eng Corp Ltd 回転ベルト式油回収装置
JPH07275856A (ja) * 1994-04-04 1995-10-24 Chlorine Eng Corp Ltd 回転ベルト式油成分回収装置
JPH07276792A (ja) * 1994-04-05 1995-10-24 Casio Comput Co Ltd 相転移する着色微粒子含有インク材を用いた色材転写熱記録方法および色材転写熱記録装置
JPH07281427A (ja) * 1994-04-05 1995-10-27 Casio Comput Co Ltd 色材転写光記録方法および装置
DE19514515C2 (de) 1995-04-12 1997-03-20 Dirk Dipl Chem Guenther Magnetisierbare Dispersionen
US7759123B2 (en) * 1998-11-13 2010-07-20 Mesosystems Technology, Inc. Removing surface deposits of concentrated collected particles
DE19960132A1 (de) * 1999-12-14 2001-06-21 Alexander Beckmann Verfahren zur Gewinnung von Kupfer und anderen Metallen
SE9904802D0 (sv) * 1999-12-23 1999-12-23 Amersham Pharm Biotech Ab Microfluidic surfaces
CN1511966B (zh) * 2002-12-30 2011-06-08 北京有色金属研究总院 一种高含铁稀土原矿的选矿工艺
JP4165392B2 (ja) * 2003-12-16 2008-10-15 株式会社日立プラントテクノロジー 油汚濁水処理装置
WO2010007075A1 (fr) 2008-07-18 2010-01-21 Basf Se Séparation sélective de substances au moyen de particules magnétiques modifiées
AU2010217681B2 (en) 2009-02-24 2016-07-07 Basf Se Cu-Mo separation

Also Published As

Publication number Publication date
US8408395B2 (en) 2013-04-02
JP2010534554A (ja) 2010-11-11
ES2373621T3 (es) 2012-02-07
ATE524567T1 (de) 2011-09-15
ZA201001077B (en) 2011-04-28
CN101778957B (zh) 2012-07-04
CN101778957A (zh) 2010-07-14
CA2693902A1 (fr) 2009-01-22
JP5496091B2 (ja) 2014-05-21
BRPI0814075A2 (pt) 2015-02-03
PL2171106T3 (pl) 2012-02-29
CA2693902C (fr) 2016-06-28
EP2171106A1 (fr) 2010-04-07
WO2009010422A1 (fr) 2009-01-22
UA99623C2 (ru) 2012-09-10
CL2008002113A1 (es) 2009-10-23
AU2008277789B2 (en) 2012-05-03
AU2008277789A1 (en) 2009-01-22
US20100200510A1 (en) 2010-08-12
RU2010105290A (ru) 2011-08-27
PT2171106E (pt) 2011-10-06
AR067567A1 (es) 2009-10-14
PE20090667A1 (es) 2009-07-04

Similar Documents

Publication Publication Date Title
EP2171106B1 (fr) Procédé d'enrichissement de minerais au moyen de surfaces hydrophobes solides
EP2190584B1 (fr) Traitement de minerais de valeur au moyen de particules magnétiques
EP2403648B1 (fr) Séparation magnétique de minerais métalliques non ferreux par conditionnement en plusieurs étapes
EP2376230B1 (fr) Enrichissement de minerais de valeur à partir de résidu minier (tailings)
EP2498913B1 (fr) Procédé permettant d'augmenter le rendement lors d'un processus de séparation de minerais au moyen de particules magnétiques hydrophobes par l'apport ciblé d'énergie mécanique
EP2401084B1 (fr) Séparation cu-mo
CN106413876B (zh) 含硅聚合物涂布的颗粒
EP2313200B1 (fr) Particules inorganiques comportant un revêtement organique pouvant être commuté hydrophile/hydrophobe sous l'effet de la température
EP2313201B1 (fr) Séparation sélective de substances au moyen de particules magnétiques modifiées
CN107206392B (zh) 浓缩物质量的改善
EP2886611B1 (fr) Particules fonctionnalisées hydrophobes
CN108367300B (zh) 磁响应性载体颗粒的超滤
EP2611859B1 (fr) Particules hydrophobes fonctionnalisées
EP2579987B1 (fr) Utilisation des composants magnétiques natifs de minerais
RU2486261C2 (ru) Способ обогащения руд с помощью твердых гидрофобных поверхностей

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100217

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20100623

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20110928

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502008004900

Country of ref document: DE

Effective date: 20111110

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111214

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2373621

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120207

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111215

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

26N No opposition filed

Effective date: 20120615

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502008004900

Country of ref document: DE

Effective date: 20120615

BERE Be: lapsed

Owner name: BASF SE

Effective date: 20120731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120708

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20130329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120708

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111214

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110914

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080708

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 524567

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130708

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20150624

Year of fee payment: 8

Ref country code: PT

Payment date: 20150624

Year of fee payment: 8

Ref country code: TR

Payment date: 20150619

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20150623

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20150721

Year of fee payment: 8

Ref country code: ES

Payment date: 20150827

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20150731

Year of fee payment: 8

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160708

Ref country code: RO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160708

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170109

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160709

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160708

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220527

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502008004900

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240201